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dissertation entitled

DEVELOPMENT OF ACTIVE PACKAGING FOR
COSMETICS AND STUDY OF THE MIGRATION OF
OXYGEN SCAVENGER

presented by

Yangjai Shin

has been accepted towards fulﬁllment
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DEVELOPMENT OF ACTIVE PACKAGING FOR COSMETICS AND
STUDY OF THE MIGRATION OF OXYGEN SCAVENGER

By

Yangjai Shin

A DISSERTATION

Submitted to
Michigan State University
in partial fulﬁllment ofthe requirements
for the degree of

DOCTOR OF PHILOSOPHY

Packaging

200‘)

ABSTRACT

DEVELOPMENT OF ACTIVE PACKAGING FOR COSMETICS AND
STUDY OF THE MIGRATION OF OXYGEN SCAVENGER

By
Yangjai Shin

Active packaging systems have been developed to extend the shelf life of
products because passive packaging systems cannot completely solve the problems of
degradation due to oxygen dissolved in products or contained in the headspace in
packages. One of the most commonly used techniques in active packaging is the sachet
type of oxygen absorbing system composed of iron powder. However, the use of a sachet
has been considered a safety problem in Europe due to migration from oxygen
scavengers. Therefore, the overall objective of this research was to develop a multilayer
ﬁlm that could reduce the migration of the main components from iron based oxygen
scavengers more than do sachets, and active packaging which could extend the shelf life
of oxygen sensitive cosmetics containing retinol.

The active packaging rapidly reduced the oxygen concentration of the headspace
compared with conventional packaging. lt reached 0.0 % within 30 days and stayed lower
than 0.] % for I80 days from an initial value of 20.9 %, while conventional packaging

remained near 10.0 % after 180 days stored at 23 °C and 65 % RH. In evaluating the shelf
life of retinol in cosmetics, the concentration in the conventional packaging was rapidly
reduced from 3,464 IU to 2,511 IU after 24 weeks stored at 23 °C and 65 % RH, while
the concentration in the active packages remained over 3,000 l U after 24 weeks.

From SEM & EDS analysis, the main elements of the oxygen scavenger in the

core layer of multilayer ﬁlms were identiﬁed as iron, sodium and chloride. Quantitative

analysis of the migration of the main elements into various food simulants was conducted
using atomic absorption (AA) spectrometry for both types of oxygen scavengers. For the
sum of the main components (NaCl+CaCl3+Fe203) for OS] in 3 % acetic acid, the
highest value among the food simulants was 2.322 mg/L, and for 052 was 0.928 mg/L.
These values were all much less than the EU limit for total migration of 60 mg/L

(90/ l 28/EEC). Throughout the observation of the migration behavior for the main
elements by SEM & EDS, no migration of any of these main elements was detected in
the inner layer adjacent to the core layer containing oxygen scavenger of multilayer ﬁlms,
but they could be observed from the seamed parting line in a tube. This means that the
main elements of oxygen scavenger in the core layer of the OS ﬁlms did not pass through
the inner layer and did not contact the food simulants and cosmetic. Therefore, it is
assumed that the migration detected was from the exposed scam in the tube or from the

exposed edges of the core layer in the migration disks.

Copyright by
YANGJAI SHIN

2009

This dissertation is dedicated to the father’s spirit of the departed, Sooyong Shin

AKNOWLEDGEMENTS

I would like to express my deepest heartfelt thanks to Dr. Susan E.M. Selke as
my advisor for her educational and professional guidance, timely advice. and keen sense
of humor.

I also would like to express my sincere appreciation to Dr. Bruce R. Harte, Dr. M.
Rubino and Dr. llsoon Lee for their research guidance and support as committee members.

I am grateful to Dr. Kathryn G. Severin, Dr. Stanley L. Fleger, Dr. P. Nzokou and
their research groups for all the great input and collaboration in this project. I would like
to thank him for allowing me to use the lab equipment to ﬁnish the evaluation of
migration test by atomic absorption spectrometer and SEM—EDS.

I would like to thank Mr. Yongwook Park, who is a CEO of E.SAENG Co., Ltd..
for encouraging me to develop this project successfully, and both AMORE PACIFIC and
BSA ENG company’s members to develop the process technology of active packaging.

I would like to thank Dr. Joongmin Shin and Mr. Myoungil Kim for sharing their
expertise and supporting me throughout my research, and Mr. D.W. Lee, Dr. J.K. Shim,
and all colleagues in packaging industries.

Finally but not least, my deepest appreciation goes to my monther, Jongsun Lee.

and my brothers. Hyunjae and Sungjae Shin, for their understanding and support. I thank

vi

to my wife Yunyoung Huh for her loving support and continuous encouragement and two
sons, Hanjung and Hyunjung Shin who understood me through the difﬁcult times and

while accomplishing my course work.

Yangjai Shin

East Lansing, MI

May 2009

vii

TABLE OF CONTENTS

LIST OF TABLES .................................................................................. vi
LIST OF FIGURES ............................................................................... vii

KEY TO ABBREVIATIONS OR SYMBOLS .............................................. xx
1. INTRODUCTION ............................................................................... l
1.1. Advances in cosmeceuticals ............................................................... l
1.2. Introduction to retinol ....................................................................... 4
1.2.1. Deﬁnition and properties ............................................................ 4

1.2.2. Applications ........................................................................... 8

1.2.3. Nutrition and dietary intake ......................................................... 9

1.3. Major factors in package design ........................................................... 10

1.4. References 12

2. LITERATURE REVIEW ..................................................................... 14
2.1. Active packaging systems 14
2.1.1. Deﬁnition of active packaging ..................................................... 14
2.1.2. Active packaging technologies ...................................................... 15
2.1.3. Current use and future trends ...................................................... 18
2.2. Oxygen scavenger systems ................................................................ 20
2.2.1. Deﬁnitions ........................................................................... 20
2.2.2. Oxygen scavenging/absorbing technologies ..................................... 22
2.2.3. Recent technologies in oxygen scavengers ....................................... 37
2.3. Regulatory issues ............................................................................. 40
2.4. Migration from active packaging .......................................................... 43
2.5. Advances for active packaging ............................................................ 47
2.5.1. Major issue identiﬁed by Actipak ................................................. 47
2.5.2. Selection of an appropriate oxygen scavenger ................................... 48
2.5.3. Package design and process control ............................................... 48
2.6. References ..................................................................................... 50

3. DEVELOPMENT OF MULTILAYER FILM INCORPORATING
OXYGEN SCAVENGER .................................................................... 56
3.1. Introduction .................................................................................. 56

viii

3.2. Materials and methods ...................................................................................... 58

3.2.1. Experimental work ................................................................... 58
3.2.2. Evaluation of appearance and optical properties ................................ 66
3.2.3. Evaluation of thermal properties ................................................... 67
3.2.4. Mechanical properties ............................................................... 67
3.2.5. Oxygen absorbing capacity ......................................................... 68
3.2.6. Statistical analysis ..................................................................... 69

3.3. Results and discussions .. ...................................................................................... 70
3.3.1. Appearance and optical properties ................................................. 70
3.3.2. Thermal properties ................................................................... 75
3.3.3. Mechanical properties ............................................................... 79
3.3.4. Oxygen absorbing amount of multi-layer ﬁlm ................................... 80

3.4. Summary ...................................................................................... 82
3.5. References .................................................................................... 84
4. DEVELOPMENT OF ACTIVE PACKAGING .......................................... 85
4.1. Introduction .................................................................................... 85
4.2. Materials and methods ....................................................................... 87
4.2.1. Package design .......................................................................... 87
4.2.2. Tube production ......................................................................... 88

4.2.3. Evaluation for residual oxygen in the headspace of packaged products 89
4.2.4. Evaluation for the shelflife ofretinol in products 90
4.2.5. Statistical analysis ....................................................................... 93
4.3. Results and discussions ....................................................................... 94

4.3.1. Oxygen concentration in the headspace of packaged products 94

4.3.2. Shelf life of retinol in packaged products ........................................... 95
4.3.3. Estimation of the extended shelf life of retinol in packaged products .......... 98
4.4. Summary ...................................................................................... 100
4.5. References ..................................................................................... 101

5. RESEARCH FOR THE MIGRATION BEHAVIOR OF OXYGEN

SCAVENGER IN ACTIVE PACKAGING .............................................. 102
5.1. Introduction ................................................................................... 102
5.2. Materials and methods .......................................................................................... 105

5.2.1. Migration components and behaviors ............................................ 105

5.2.1.1. Materials 105
5.2.1.2. Sample preparation .. ................................................................... 105

5.2.1.3. SEM & EDS analysis ......................................................

5.2.1.4. Identiﬁcation of the main elements of oxygen scavenger ............

5.2.2. Quantitative analysis of migration .................................................
5.2.2.1. Film samples ..
5.2.2.2. Food simulants .. ..........................................................................
5.2.2.3. Migration cell and tube experiments ....................................
5.2.2.4. Atomic absorption (AA) spectroscopy ..................................
5.2.2.5. Standard calibration curve .................................................

5.3. Results and discussions ...................................................................
5.3.1. Observation of migration behaviors ..............................................
5.3.1.1. Overall migration behaviors in OS ﬁlms
5.3.1.2. Migration behaviors in the inner layer of OS ﬁlms .....................
5.3.1.3. Migrant behaviors in a tube .............................................
5.3.2. Quantitative analysis of migration by AA spectrometry
5.3.2.1. Migration result for Na and calculation for NaCI
5.3.2.2. Migration result for Ca and calculation for CaClz . . .
5.3.2.3. Migration result for Fe and calculation for Fe203 ..................
5.3.2.4. Results for the sum of migration for main components

in migration vials .........................................................

5.3.2.5. Color change of the ﬁlms after migration test in various
food simulants ...........................................................

5.3.2.6. Comparison of the migration of the main components

in tubes and vials ............. A ............................................................

5.4. Summary ....................................................................................
5.5. References ..................................................................................
6. CONCLUSIONS AND FUTURE WORK ..................................................
6.1 Conclusions ...................................................................................
6.2 Future work ...................................................................................
APPENDICES .....................................................................................
APPENDIX A: Properties and oxygen absorbing amount of multilayer ﬁlm
APPENDIX B: Oxygen and retinol concentration of active packaging ...............
APPENDIX C: Migration data into various food simulants .............................

106
107
114
114
114
115
116
119
I26
127
127
130
I38
141
I41
143
144

146

149

150
152
154

156
156
158

159
I60
180
183

LIST OF TABLES

Table Page

Examples of sachet, label and ﬁlm type absorbing (scavenger) active packaging
systems for preservation and shelf-life extension of foods or improving their

quality and usability for consumers ......................................................................... 15
2. Selected commercial oxygen scavenger systems .............................................. 24
3. Recently issued US patents for oxygen scavenging systems 38
4. Some typical results of the evaluation of the composition of active

packaging systems ...................................................................................................... 44
5. Comparison of overall migration (OM) into water and 3% acetic acid ................... 46
6. Characteristics of the materials selected ....................... . .............................. 59
7. Desirable ﬁlm thicknesses in middle layer ................................................... 62
8. Design for each layer of ﬁlms ................................................................... 63
9. Speciﬁcation of blown ﬁlm line ................................................................. 64
10-1. Condition 1: Processing temperatures for HDPE blended polymers ................. 65
10-2. Condition 2: Processing temperatures for LLDPE blended polymers 65
11. Total thickness ofLLDPE, OS1 and 082 72
12. TGA data for LLDPE, OS1 and 082 ............................................................. 77
13. Mechanical properties in LLDPE (Control), OSI (Film E) and 082 (Film F) ....... 80
14. Amount ofoxygen absorbed .................................................................. 81

15. Trends of oxygen concentration in headspace of both control and active

samples (stored at 23 °C , 65 % RH) ......................................................... 94

xi

16.

17.

18.

19.

20.

2'1.

22.

23.

24.

25.

26.

27.

28.

29.

30.

Retinol contents vs. storage time for the conventional (Control) and active

package (OS) samples ............................................................................................ 97
Atomic absorption: working conditions (Fixed) .......................................... l 18
Atomic absorption: working conditions (variable) ....................................... I I8
Flame emission .............................................................................................. . 118
Migration ofsodium (Na) into food simulants 142

Speciﬁc migration of NaCl as calculated from observed migration of sodium,

Respectively .................................................................................... 142
Migration ofcalcium (Ca) into food simulants ........................................... 143
Speciﬁc migration of CaC 12 as calculated from observed migration of calcium,
respectively .................................................................................................... . 144
Migration ofiron (Fe) into food simulants ................................................. 145
Speciﬁc migration of Fe203 is calculated from observed migration of iron,
respectively .................................................................................... 146
Sum of migration for main elements (Na + Ca + Fe) .................................... 147
Sum of migration for main components (NaCl + CaClz + Fe203) as calculated

from observed migration of sodium, calcium and iron, respectively .................. 148
Comparison of the sums of migrations of main elements (Na, Ca and Fe)

into 3 % acetic acid between tube and vials ............................................... 150
Comparison of the sums of migrations for main components (NaCl, CaC 13

and Fe203) into 3 % acetic acid between tube and vials as calculated
from observed migration of sodium, calcium and iron, respectively 151

Comparison of the sums of migrations for main components (NaCl, CaClg

xii

and Fe203) into 3% acetic acid between tube and vials as calculated

the same total surface, respectively ......................................................... 151
31. UV/VIS spectrometer data ................................................................... 160
32. Film thickness data ....................................................................................... . I76
33. Mechanical properties data .................................................................. 177
34. Oxygen absorbing amount data ............................................................ 179
35. Oxygen concentration in headspace data ....................................................... I80
36. Standard calibration curve data .............................................................. I80
37. Area Response data of retinol in HPLC .................................................... I81
38. Retinol concentration data in cosmetics ......................................................... 181
39. Standard calibration curve data ofNa for 95 % ethanol in AA ......................... 183
40. Standard calibration curve data ofNa for water and 3 % acetic acid in AA 184
41. Standard calibration curve data of Na for olive oil in AA ............................... 185
42. Standard calibration curve data of Ca for 95 % ethanol in AA .................... 186
43. Standard calibration curve data of Ca for water and 3 % acetic acid in AA 187
44. Standard calibration curve data of Ca for olive oil in AA ............................... 188
45. Standard calibration curve data of Fe for 95 % ethanol in AA .......................... 189
46. Standard calibration curve data of Fe for water and 3 % acetic acid in AA 190
47. Standard calibration curve data of Fe for olive oil in AA ................................ I91

xiii

48.

49.

50.

51.

52.

54.

55.

56.

57.

59.

60.

Migration of NaCl into 95 % ethanol as calculated from observed migration

of sodium (Na), respectively ................................................................ 192
Migration of NaCl into water as calculated from observed migration

of sodium (Na), respectively ............................................................... 193

Migration of NaCl into 3 % acetic acid as calculated from observed

migration of sodium (Na), respectively .................................................... 194

Migration of NaCl into olive oil as calculated from observed migration
of sodium (Na), respectively ............................................................... 195

Migration of CaClz into 95 % ethanol as calculated from observed migration

of calcium (Ca), respectively ............................................................... I96

. Migration of CaClz into water as calculated from observed migration

of calcium (Ca), respectively ............................................................... 197

Migration of CaClz into 3 % acetic acid as calculated from observed

migration of calcium (Ca), respectively ......................................................... 198

Migration of CaClz into olive oil as calculated from observed migration
of calcium (Ca), respectively ............................................................... I99

Migration of Fe203 into 95 % ethanol as calculated from observed

migration of iron (Fe), respectively ........................................................ 200

Migration of Fe203 into water as calculated from observed migration
of iron (Fe), respectively .................................................................... 201

. Migration of Fe203 into 3 % acetic acid as calculated from observed

migration of iron (Fe), respectively ................................................................ 202

Migration of Fe203 into olive oil as calculated from observed migration
of iron (Fe), respectively .................................................................... 203

Migration of NaCl into 3 % acetic acid as calculated from observed

xiv

migration of sodium (Na), respectively .................................................... 204

61. Migration of CaClg into 3 % acetic acid as calculated from observed

migration of calcium (Ca), respectively .................................................... 204

62. Migration of Fe203 into 3 % acetic acid as calculated from observed

migration of iron (Fe), respectively ................................................................ 205

XV

LIST OF FIGURES

Images in this dissertation are presented in color

Table Page
1. Metabolization mechanism of the retinol group ........................................................ 5
2. Structure of retinoids .............................................................................. 6

3. A structure oftypical oxygen scavenging multi-layer ﬁlm 22
4. Types of oxygen absorbers ......................................................................... 28
5. Polymeric type oxygen scavenger (iron based) ......................................................... 30
6. Oxyguard ® (tray) 31
7. Oxidation mechanism ofascorbic acid 32
8. Plastic cans incorporated potassium sulﬁte oxygen scavenger 33
9. Performance advantage ofOSPTM injuice packaging 35
10. Co-extrusion blown ﬁlm line (Reifenhéiuser, Germany) 64

11.A pint canningjar to measure the oxygen absorbing capacity 69

12. Agglomerations in various oxygen scavenging ﬁlms .............................................. 71
13. Cross-sectional image of ﬁlm F ............................................................... 73
14. % light transmission of LLDPE, 081 and 082 ...................................... 74

15. Dispersion state and particle sizes of oxygen scavengers in 081
and 082 ﬁlms .................................................................................................. .74

16. DSC chart of OS] and 082 ................................................................... 76

17. TGA chart to compare with LLDPE, 081 and 082 78

xvi

18. Design of active packaging for cosmetics ..................................................... 86

19. Desired structure of active packaging and lamination processes 88

20. Tubing & over-coating process .................................................................. 89

21. The area response in peak ofa working standard solution of retinol in HPLC 91

22. Standard calibration curve of HPLC ...................................................................... 91

23. Oxygen concentration trends in headspace (stored at 23 °C, 65% RH) 95

24. Trends ofthe shelflife ofthe retinol in cosmetics 97

25. Trend line ofthe retinol content in cosmetics (stored at 23 °C, 65% RH) 99

26. Migration from active packaging to cosmetics ............................................. 104
27-1. Microtome ....................................................................................................... 106
27-2. Carbon Coater .................................................................................................. .106
28. SEM & EDS ......................................................................................................... 107

29. Appearance ofa particle ofoxygen scavenger in 081 ﬁlm 108

30. All elements analysis on the site of Spectrum 1 in 081 ﬁlm ............................ 109

31. Appearance ofa particle ofoxygen scavenger in 0S2 ﬁlm 110

32-1. All elements analysis on the site of Spectrum 1 in 0S2 ﬁlm ............................... 110

32-2. A11 elements analysis on the site of Spectrum 2 in 082 ﬁlm ............................... 1 1 1

33. Spectrum sites of LLDPE ﬁlm 112

34-1.A11 elements analysis on the site of Spectrum 1 in LLDPE ﬁlm .......................... 112

xvii

34-2.A11 elements analysis on the site of Spectrum 2 in LLDPE ﬁlm .......................... 113

35.

36.

37.

38.

39.

40.

41.

42.

43.

44.

45.

46.

47.

48.

49.

Atomic absorption (AA) spectrometry ..................................................

Standard calibration curve for Na concentration in 95 % ethanol

Standard calibration curve for Na concentration in distilled water

and 3 % acetic acid ..........................................................................

Standard calibration curve for Na concentration in olive oil ...............................

Standard calibration curve for Ca concentration in 95 % ethanol

Standard calibration curve for Ca concentration in distilled water

and 3 % acetic acid .........................................................................

Standard calibration curve for Ca concentration in olive oil ...............................

..117

.. 120

121

122

122

123

Standard calibration curve for Fe concentration in 95 % ethanol 124
Standard calibration curve for Fe concentration in distilled water
and 3 % acetic acid ............................................................................. 124
Standard calibration curve for Fe concentration in olive oil 125
Structure ofa tube laminated with the OS ﬁlm 126
Overall migration behavior for each element of oxygen scavenger in 081 ﬁlm

by the ‘X-ray Map’ method of SEM & EDS (Magniﬁed 650 times) 128
Overall migration behavior for each element of oxygen scavenger in 082 ﬁlm

by the ‘X-ray Map’ method of SEM & EDS (Magniﬁed 650 times) .............. 129
Observation ofSpectrum 1 sites in the inner layer ofOSl ﬁlm 130
Result of Spectrum 1 (081 ﬁlm; 6 months passed at 23 °C and 65% RH) .......... 131

xviii

50.

51.

52.

53.

54.

55.

56.

57.

58.

59.

60.

Result of Spectrum 1 (081 ﬁlm; stored at 10 days & 40 °C in 3% acetic acid) 132
Result of Spectrum 1 (081 ﬁlm; 6 months passed in room conditions after

ﬁlling cosmetic) .............................................................................. I33
Observation of Spectrum 1 sites in the inner layer of082 ﬁlm 134
Result of Spectrum 1 (082 ﬁlm; 6 months passed at 23 °C and 65% RH) .......... 135
Result of Spectrum 1 (082 ﬁlm; stored at 10 days & 40 °C in 3% acetic acid) 136
Result of Spectrum 1 (082 film; 6 months passed in room conditions after

ﬁlling cosmetic) .............................................................................. 137
Inside of package after 6 months passed in room conditions after ﬁlling

cosmetic ....................................................................................... 138
Spectrum sites for inside ofa tube by the SEM EDS ................................... 139
Result of Spectrum 1 (Seamed parting line in a tube; stored at 10 days

and 40 °C in 3% acetic acid) ............................................................... 139
Result of Spectrum 2 (Inner layer in a tube; stored at 10 days and

40 °C in 3% acetic acid) ..................................................................... 140
Color change ofthe ﬁlms used as migration disks after migration test ............... 149

xix

Abbreviations

AA

AHAs

ATRA

AU

Aw

BHA

BHA

CFSAN

CD

DEF

DMA

DMF

DOT

DRI

DSC

HDPE

HFFS

ECCS

KEY TO ABBREVIATIONS OR SYMBOLS

Atomic absorption

Alpha-hydroxy acids

All-trans retinoic acid

Area response

Water activities

Butylated hyalroxyanisole

Butylated hydroxytluene

Center for Food Safety and Applied Nutrition

Cross direction

Difurylidene erythrito

Dimethyl anthracene

Dimethylformamide

Dioctyl phthalate

Dietary reference intake

Differential scanning calorimetry

High density polyethylene

Horizontal thermoform/ﬁll/seal

European community compliance statement

XX

EGVM

E8 FA

EMCM

EVA

EVOH

FAO

FA P

FCN

FDC

FDA

FSA

GRAS

GSTTC

HSD

1U

LLDPE

MHW

MD

Expert group on vitamins and minerals

European Food Safety Authority

Ethylene methylacrylate cyclohexenyl methyl acrylate

Ethylene vinyl acetate

Ethylene vinyl alcohol

Food and agriculture organization

Food Additive Petition

Food Contact Notiﬁcation

Food, drug and cosmetic

Food and drug administration

Food standards agency

Glucose

Generally recognized as safe

Guideline for Screening Toxicity Testing of Chemicals

Honesty signiﬁcant difference

International unit

Linear low density polyethylene

Ministry of health and welfare

Machine direction

xxi

NAS

0M

08

TGA

PCR

PET

PG

RARs

RDA

RE

RH

RSM

SEM-EDS

STP

TNO

TPP

TSCA

XRF

National Academy of Sciences

Overall migration

Oxygen scavenger

Thermo gravimetric analyzer

Post consumer recycled

Polyethylene terephthalate

Propyl gallate

Retinoic acid receptors

Recommended Daily Amount

Retinal Equivalents

Relative humidity

Response surface methodology

Scanning electronic microscopy for energy-dispersive spectrometry

Standard temperature and pressure

Netherlands Organization for Applied Scientiﬁc Research

Tetraphenyl prophine

Toxic substances control act

X—ray ﬂuorescence

xxii

Symbols

Co
Cst

Csa

Di
Ea

Fe(OAc)2

HAc
HDDi
“In
A Hf?
[3.wa
Ka

L886

Represents an exited state of the species

Core layer ofa ﬁlm
Oxygen uptake capacity (18 ccOz/g)

Retinol concentration of standard solution (mg/100ml)
Retinol concentration of sample solution (g/l 00ml)
Density ofthe middle layer.

New density ofthe blend with LLDPE or HDPE.
Activation energy (cal/mol)

Iron compound mixed with ferric oxide

Interior height of the headspace in the package

Inner layer ofa ﬁlm

Acetic acid

Density of HDPE

Heat of fusion ofthe sample (081)

Heat of fusion of the sample (082)

Heat of fusion of 100% crystalline LLDPE (286.2 J/g)
Arrhenius equation constant

Lanthium hexaboride

xxiii

LLDi

1021
051
082
OS 1 D1

081

08L

Rs

RH

Sh

Tm

Density of LLDPE, and 082Di was the density of 082

Needed weight of oxygen scavenger material (M = 0.061 g)

Weight ofthe blend of LLDPE or HDPE with the oxygen scavenger

Outer layer ofa ﬁlm

Initial 02 concentration in package (= 21% ifair)

Oxygen scavenger 1

Oxygen scavenger 2

Density of 081

Sachet had the form ofa plastic cup

Sachet laminated with paper and plastic

Universal gas constant (1.9872 cal/mol, K)

Regression coefﬁcient oflinear regression analysis

Response area for the sample (area unit: AU)

Relative Humidity

Total interior surface of the package

Interior surface area of the headspace in the package

Absolute temperature (K)

Glass transition temperature

Melting temperature

xxiv

Tmi Desirable ﬁlm thickness ofthe middle layer

Va Air volume ofthe headspace

V0 Volume of oxygen present in the headspace ofthe package

XXV

I. INTRODUCTION
1.1. Advances in cosmeceuticals

The term “cosmeceuticals” is a composite word of “cosmetic” and
“pharmaceutical,” and it was introduced by Albert Kligman 20 years ago at a meeting of
the Society of Cosmetic Chemists, who deﬁned it as topical formulations which lie
between cosmetics and drugs. Some were closer to drugs, such as the alpha-hydroxy
acids — designed to exfoliate the outer, loose stratum corneum, a structural effect —
whereas others were closer to cosmetics, like rouge — designed to give color, a purely
decorative effect (Kligman, 2005). The term “cosmeceuticals” has provoked discussions
among scientists, the industry, and regulating authorities, because the introduction of
cosmeceuticals enabled more precise classiﬁcation of a product with an activity that is
intended to treat or prevent a skin condition. New insights about the function of skin, as
well as the development of new products for skin care, made it necessary to question or
redeﬁne the deﬁnitions of cosmetics and drugs, since the term is regarded as a subclass
within the domain of cosmetics or drugs (Vermer, 2005).

However, according to the Food, Drug, and Cosmetic (FDC) Act, a drug is
deﬁned as an article intended to use in the diagnosis, mitigation, treatment, or prevention
of disease or intended for affect the structure or any function of the body. 0n the contrary,
a cosmetic is deﬁned as an article intended to be rubbed, poured, sprinkled, or sprayed on,
introduced into, or otherwise applied to the human body or any part thereof for cleansing,
beautifying, promoting attractiveness, or altering the appearance without affecting
structure or function, in 21 USC. As a result, the US. Food and Drug Administration
(FDA), in accordance with the Food, Drug, and Cosmetic Act, does not recognize the

term “cosmeceuticals” (FDA, 2000).

To avoid inquiry and punitive action by the United States Federal Trade
Commission, cosmeceuticals are not intended to be regulated as drugs by the FDA are
carefully labeled to avoid making statements which would indicate that the product has
drug properties. Any such claims made regarding the product must be substantiated by
scientiﬁc evidence as being truthful. It is to the ﬁnancial beneﬁt of the cosmeceuticals
manufacturer that their products are not regulated by the FDA as drugs, because the
regulation of a product as a drug requires many elaborate and costly procedures; therefore.
the manufacturer of a product with pharmaceutical activity would prefer to have the
product registered as a cosmetic (Elsner and Maibach, 2005).

The term cosmeceuticals is now commonly used to describe cosmetic products
that are claimed, primarily by those within the cosmetic industry, to have drug-like
beneﬁts, because they contain active ingredients such as vitamins, herbs, enzymes, and
antioxidants (Choi, et a1., 2006; Schwartz, et a1., 2008). Even if the term
“cosmeceuticals” has no meaning under FDA regulations, the demands for these products
have increased with the consequence that the market is expanding rapidly; the US.
cosmeceuticals market will surpass $17 billion by 2010 from $7 billion in 2005; skin care.
such as anti-aging creams and wrinkle remedies, is the largest segment (Granato, 2007).
The global skin care market was valued at $50 billion and annual growth of 7 percent was
expected between 2005 and 2009, making skin care the second-fastest growing cosmetics
category, behind sun care products (MarketWikis, 2007).

New cosmeceutical ingredients which are derived from products with
scientiﬁcally founded beneﬁts in human health and its maintenance, such as vitamin A
(retinol and all-trans retinoic acid named as tretinoin), vitamin C, alpha-hydroxy acids

(AHAs), hydrolyzed proteins (from corn, soy, etc.) and polysaccharides (hyaluronic acid

and beta-glucans), are very remarkable additives (Applegate, 2002). Vitamins and their
derivatives are often found in skincare products. Vitamins C and E have antioxidant
properties. There is some research on the use of topical antioxidants for skin health.
Topical application of vitamins C and E has shown signiﬁcant photo protection against
UV damage, possibly by scavenging reactive oxygen species (Eberlein-Konig, 2005).
Various B vitamins also ﬁnd their way into creams, including niacinamide (B3), which is
said to increase the rate of exfoliation and barrier repair, and panthenol (pro-vitamin BS)
which helps the skin retain its natural moisture. But the big one from an anti-wrinkle
perspective is vitamin A (retinol) and its derivatives. Retinoic acid or tretinoin, which is
the alternative name for all-trans retinoic acid (ATRA), is the strongest prescription. and
the only product indicated for treating photo-damaged skin. The next strongest and
common ingredient in skin cream is retinol itself and also pro-retinol, which are both

involved in the growth and maturation of cells (Houlton, 2004).

1.2. Introduction to retinol
1.2.1. Deﬁnition and properties

Retinol was discovered by Elmer McColIum and Marguerite Davis who identiﬁed
a fat-soluble nutrient in butterfat and cod liver oil in 1913. It was conﬁrmed by Thomas
Osborne and Lafayette Mendel, biochemists at Yale University, in 1913, as a fat-soluble
nutrient in butterfat (Semba, 1999). Vitamin A was ﬁrst synthesized by David Adriaan
van Dorp and Jozef Ferdinand Arens in 1947.

Retinol, the parent vitamin A compound, has the molecular formula 0'fC30H300
and a molecular weight of 286.456 g/mol. As an animal form of vitamin A, it is a fat-
soluble vitamin and has an important role in vision and bone growth. It belongs to the
family of chemical ingredients known as retinoid. Figure I shows active retinoid
metabolites (Chebigen, 2007). Retinol is ingested in precursor forms. One form is of
animal origin, such as liver and eggs, which contain retinyl esters. The other form is
acquired from plants. Particular green plants such as grass, clover, spinach and carrots are
rich in pro-vitamin A carotenoids. Retinyl esters are converted into retinol through
hydrolysis. Decomposition of pro-vitamin A carotenoids, the most well-known being
beta-carotene, results in producing retinal. Retinal, known as retinaldehyde, can be
reversibly reduced to produce retinol or it can be irreversibly chemically oxidized to
produce retinoic acid. The best described active retinoid metabolites are 1 l-cis—retinal

and the all-trans and 9-cis-isomers of retinoic acid (Ball, 2006).

 

B—carotene
Rich in particular green plants such
as grass, clover, luceme and carrots

1

 

 

 

 

 

 

 

 

 

 

 

 

 

 

B-carotene 15, 15’ dioxygenase Liver
(Small amount in intestinal mucosa) l
Forms light I Retinyl ester
receptor .— Retinal {—9 accumulated
rhodopsin in liver
Alcohol : Chemical Chemical Aldehyde
dehydrogenase 1 oxidation oxidation E dehydrogenase
v i t v
Retinoic acid Retinol
(All trans, 9-cis) (Vitamin A)

 

 

 

 
 
       
 

 

 

 

Regulate physiological
function using retinoic
acid receptors (RARs)

Figure 1. Metabolization mechanism of the retinol group
(Source: Chebigen, 2007)

Many kinds of geometric isomers of retinol, retinal and retinoic acid are possible
as a result of either a trans or cis conﬁguration of four of the ﬁve double bonds found in
the polyene chain. A polyene is a poly-unsaturated organic compound that contains one
or more sequences of alternating double and single carbon-carbon bonds. These double
carbon-carbon bonds interact in a process known as conjugation, which results in an
overall lower energy state of the molecule. The cis isomers are less stable and can readily
convert to the all-trans conﬁguration. Nevertheless, some cis isomers are found naturally

and carry out essential functions. For example, the 1 l-cis-retinal isomer is a chromophore

of the vertebrate photoreceptor molecule named rhodopsin. The process of vision relies
on the light-induced isomerization of the chromophore from 1 l-cis to all-trans, resulting
in a change of the conformation and activation of the photoreceptor molecule. Figure 2

shows the structures of retinoids found in foods and ﬁsh-liver oils (Ball, 2006).

(a) all-trans-retinol (Vitamin A 1)

1T 11 2T
17 16 15
\ /
1 7 9 13 CH20H
T/// \\]T’//i§§Sa’// \\\10 ‘\\\12/' \\\14//
3 5
\4/ \18

(b) al1-trans-3-dehydroretinol

CHZOH
(c) l3-cis-retinol
13
\ \ \ \14
CH20H

Figure 2. Structure of retinoids

(d) 9-cis-retinol |
\
\

CHZOH

(e) 9,13-dis-cis-retinol

9
iv %10
g
13
/ XM/

Figure 2. Structure of retinoids (continued)

CHZOH

1.2.2. Applications

All kinds of retinoids in vitamin A are used in cosmetic and medical applications
applied to the skin. Tretinoin, under the alternative name of all-trans retinoic acid
(ATRA), is used in the treatment of acne and keratosis in a topical cream, and is used as
chemotherapy for a subtype of leukemia, because the cells of leukemia are sensitive to
agonists of the retinoic acid receptors (RARs). An isotretinoin is also used for severe or
recalcitrant acne.

In cosmetics, vitamin A derivatives are used as anti-aging chemicals, which are
absorbed through the skin and increase the rate of skin turnover, and give an increase in
collagen giving a more youthful appearance. Although topical vitamin A is not very
effective as a skin care ingredient, other members of retinoid family such as retinol and
retinoic acid have long been used for the treatment of acne and wrinkles. In skin care
products, retinol is the ﬁrst antioxidant to be widely used in nonprescription functional
cosmetics such as wrinkle creams. Antioxidants are substances that neutralize free
radicals - unstable molecules that break down skin cells and cause wrinkles.

According to a new study from the University of Michigan Health System, lotions
containing retinol improve the appearance of skin that has become wrinkled through the
normal aging process, notjust which has been damaged by exposure to sunlight. During
the study, led by doctors at the U. of M. Medical School, 0.4% retinol was applied to 36
subjects with a mean age of 87, up to three times per week. After 24 weeks, the
improvement of retinol-treated skin was dramatic, and clearly visible to the naked eye

(Kaﬁ et a1., 2007).

1.2.3. Nutrition and dietary intake

Vitamin A is protected from being chemically changed by vitamin E in the
intestine. Vitamin A is fat-soluble and can be stored in the body. Most of the vitamin A
after eating is accumulated as retinyl ester in the liver, and when retinol is needed in other
tissues or cells, it is de-esteriﬁed and released into the blood as the alcohol.

When referring to dietary allowances or nutritional science, retinol is usually
measured in international units (1U), which refers to biological activity and therefore is
unique to each individual compound. One IU of retinol is equivalent to approximately 0.3
micrograms (300 nanograms). Amounts of vitamin A are measured in Retinal
Equivalents (RE), and 1 RE is equivalent to 0.001 mg of retinal, or 0.006 mg of beta-
carotene, or 3.3 [U of vitamin A, according to the Food and Agriculture Organization
(FAO) of the United Nations (FAO, 1967). The Dietary Reference Intake (DRI)
Recommended Daily Amount (RDA) for vitamin A for a 25-year old male is 900
micrograms (3,000 IU) per day, and 700 micrograms (2,333 IU) per day for adult females.
The RDA upper limit for both adult males and females is 3,000 micrograms (10,000 IU)
per day, according to the National Academy of Sciences (NAS) in the US. (NAS, 2004).
Synthetic forms prescribed for therapeutic purposes such as certain skin disorders and
multi-vitamin supplements are at levels up to 2,400 micrograms (approximately 8,000
IU) per daily dose, by the Expert Group on Vitamins and Minerals (EGVM) of the Food

Standards Agency (FSA) in the UK (EGVM, 2003).

1.3. Major factor in packaging design

Retinol has attracted considerable attention lately as a new functional ingredient
that plays an important role in epidermal cells to maintain their original capacity.
However, retinol is a group of fat-soluble compounds that has an unstable structure

consisting of a B-ionone ring, a conjugated isoprenoid side chain and a polar terminal

group (-OH). Therefore, it is readily oxidized or isomerized to altered compounds,
especially in the presence of oxidants including air, and inﬂuences such as light and heat.
It is labile toward active components such as silica, strong acids and solvents that have
dissolved oxygen or peroxides (Ball, 2006; EGVM, 2003; Barua and Harold, 1998).

Retinol is easily decomposed by atmospheric oxygen, resulting in an almost
complete loss of biological activity. Even though retinyl esters are somewhat more stable
than retinol, they are also readily oxidized. Retinol is extremely sensitive to acids, which
can cause rearrangement of the double bonds and dehydration. Solutions of all-trans-
retinol or retinyl palmitate in hexane undergo slow isomerization to the lower potency cis
isomers when exposed to white light, but retinyl palmitate is stable in chlorinated
solvents when it is stored in the dark. Vitamin A is easily decomposed by irradiation and
forms inactive structures that cause a yellowish color. While the carotenoids are stable
within natural plant cells, they are apt to be transformed by trans to cis isomerization and
degradation by heat, light, oxygen, acids, and silica (Ball, 2006).

Therefore, the most important factor in developing commercial products and
packaging to contain vitamin A such as retinoids and provitamin A carotenoids, is how to
prevent the decomposition from heat, light, oxygen and other active components (Barua
and Harold, 1998). A great deal of care is required not only in product processing, but

also in all the shelf-life including storage, transportation and distribution channels.

10

This kind of product can be readily oxidized and photo-degraded by the residual
oxygen in the headspace and the transmitted light in or through a conventional plastic
package. In the cosmeceuticals industry, especially, solving this kind of problem is an
increasing issue. For this reason, the manufacturers will have paid an extra charge for
initially putting an excess of the functional ingredients such as retinol into the product.
Therefore, if certain packaging could protect vitamin A against degradation from light

and oxygen, manufacturers are quite willing to pay for an effort to develop the packaging.

11

1.4. References

Applegate, DR. and Julie A. Reynolds, “Rejuvenation of Aging and Photodamaged Skin
Utilizing Fibroblast Conditioned Media,” in New York SCC ’01, 2001 Speaker of the
Year Award, Sep. 24, 2002. http://www.nyscc.org/news/archive/rcch0902.htm

Ball G.F.M., Vitamins in Food: Analysis, Bioavailability, and Stability, C RC Press,
Taylor & Francis Group, Boca Raton, FL, pp. 39-51, 2006.

Barua, AB. and CF. Harold, “Properties of retinols,” Molecular Biotechnology, 10: I67-
182, 1998. http://wwwspringerlink.com/contcnt/b234wu0tlh607182/

Chebigen, “Retinol and retinol derivatives,” undated.
http://www.chebigen.com/english/businessLhtm, (accessed Nov. 23, 2007)

Eberlein-Konig, 8., “Relevance of vitamins C and E in cutaneous photoprotection,”
Journal of Cosmetic Dermatology, 4(1): 4—9, Jan. 2005.

EGVM (Expert Group on Vitamins and Minerals), “Safe Upper Levels for Vitamins and
Minerals,” Food Standards Agency (FSA), UK, PP. 1 10-126, May 2003.
http://wwwfoodgov.uk/muItimedia/pdfs/evm a.pdf

FAO (Food and Agriculture Organization of the United Nations), “Factors for vitamin A
conversion,” FAO Report Ser. No. 41, 1967.
http://www.fao.org/docrep/003/X6877E/X6877E22.htm, (accessed DEC. 27, 2007)

FDA (US. Food and Drug Administration), “Cosmeceutical,” Feb. 24, 2000.
http://www.cfsan.fdagov/~dms/cos-217.html

Granato, H., “Cosmeceuticals: At the Intersection of Nutrition and Beauty,” Natural
Products Insider, June. 4, 2007.
http://www.naturalproductsinsider.com/articles/472/75h318454835771.html

Houlton, 8., “Natural skin science,” Apr. 19, 2004.
http://www.users.globalnet.co.uk/~sarahx/articles/cicosmeceuticaIs.htm

12

Kaﬁ, R., Heh Shin Kwak, E. andy, Schumacher, Soyun Cho, Valerie N. Hanft, Ted A.
Hamilton, Anya L. King, Jacqueline D. Neal, James Varani, Gary J. Fisher, John J.
Voorhees, Sewon Kang, “Improvement of Nationally Aged Skin With Vitamin A
(Retinol),” Arch Dermatol, 143: 606-612, 2007.

MarketWikis, “Anti-Aging Market Research,” Nov. 25, 2007.
http://www.researchbuy.com/,arkctwikis/Anti-Aging_Market_Resarch

NAS (National Academy of Sciences), “Dietary Reference Intakes (DRls):
Recommended Intakes for Individuals, Vitamins”, 2004.
http://www.iom.edu/Obiect.Fi1e/Master/21/372/0.pdf

Semba R.D., “Vitamin A as “Anti-Infective” Therapy, 1920-1940,” Journal of Nutrition,
129: 783-791, 1999.

2. LITERATURE REVIEW

2.1. Active packaging systems
2.1.1. Definition of active packaging

In recent years, new packaging systems have been developed as a response to the
continuing increase in consumer demands for fresh, tasty and convenient food products
with extended shelf-life. Furthermore, changes in retail systems such as centralization of
activity and globalization of markets result in longer distribution distances, required
innovative packaging concepts that extend shelf-life while maintaining the safety and
quality of the packaged product. because traditional systems were not reaching their goal
with regard to further prolongation of the shelf-life of packaged products (De Kruijf et al..
2002). As a consequence, various new packaging technologies or systems were
introduced, named active, smart, clever, or intelligent packaging. The ﬁrst use of the term
‘active packaging’ was at the Icelandic conference on nutritional impact of food
processing in 1987 by Professor Labuza from the University of Minnesota (Labuza and
Breene, 1989), and the term may be deﬁned as packaging which performs some desired
function other than merely providing a barrier to the external environment (Hotchkiss,
1995). More recently, this term was more clearly deﬁned by Robertson as follows:
“Active packaging is that packaging in which subsidiary constituents have been
deliberately included in either the packaging material or the package headspace to
enhance the performance of the package system” (Robertson, 2006).

But, these terms are undeﬁned and often misused in the literature. For this reason,
twelve partners from research and industry organized to deﬁne active and intelligent

packaging systems in 1999 under the name of ‘Actipak project’ in Europe (TNO, 2002).

14

This resulted in the adoption of a new Framework Regulation (1935/2004/EC) in which
the use of active and intelligent packaging systems is now included (De Jong et al., 2005).
According to the deﬁnitions of the Actipak project, active packaging changes the
condition of the packed food to extend shelf-life or improve safety or sensory properties.
while maintaining the quality of the packed food (Rijk et al., 2002).

In the deﬁnition of active packaging, foods undergo various processes that may
affect the shelf-life of packed products: physiological processes such as respiration of
fresh fruit or vegetables, chemical or physical processes such as lipid oxidation or staling
of bread, and other processes such as spoilage by micro-organisms or insects. Through
the application of appropriate active packaging systems, the food condition can be
improved in various ways, and the shelf life of the packaged products will be extended by

reduced food deterioration (De Kruijf et al., 2002).

2.1.2. Active packaging technologies

For preservation and improving quality and safety of products, active packaging
techniques can be classiﬁed as three types of systems: absorbing or scavenging systems
[Table l], releasing systems, and other systems (Ahvenainen, 2003). A scavenging
system is one that removes or absorbs undesired substances such as oxygen, carbon
dioxide, ethylene, humidity or other compounds such as off-ﬂavors or lactose. A
releasing system emits speciﬁc compounds, such as carbon dioxide, antioxidants and
antimicrobial preservatives, into the headspace of the package or the packaged food.

Other systems may have various tasks, such as self-heating and cooling packages.
microwave susceptors, and widgets that produce foams in beer cans (Robertson, 2006;

Bohrer and Brown, 2001).

Table 1. Examples of sachet, label and ﬁlm type absorbing (scavenger) active packaging
systems for preservation and shelf-life extension of foods or improving their quality and
usability for consumers. Oxygen, carbon dioxide, ethylene and humidity absorbers have
the most signiﬁcant commercial use; lactose and cholesterol removers are not yet in use.
(Source: Ahvenainen, 2003)

 

Packaging type

Examples of working
principle/
mechanism/reagents

Purpose

Examples of possible
applications

 

Oxygen absorber
(sachets, labels,
ﬁlms, corks)

Carbon dioxide
absorbers
(sachets)

Ethylene
absorbers
(sachets, ﬁlms)

Humidity
absorbers (drip-
absorbent sheets,
ﬁlms, sachets)

Ferro-compounds,
ascorbic acid,
metal salts,
glucose oxidases,
alcohol oxidase

Calcium hydroxide
and sodium
hydroxide or
potassium hydroxide
Calcium oxide and
silica gel

Aluminum oxide

and potassium
permanaganate
(sachets)

Activated carbon +
metal catalyst (sachet)
Zeolite (ﬁlms)

Clay (ﬁlms)

Oya stone (ﬁlms)

Polyacrylates
(sheets)

propylene glycol
(ﬁlm)

Silica gel (sachet)

Reduction/prevention
of mold, yeast and
aerobic bacteria
growth

Prevention of
oxidation of fats,
oils, vitamins,
colors

Prevention of
damage by worms,
insects and insect

eggs

Removing of carbon
dioxide formed
during storage in
order to prevent
bursting of a package

Prevention of too
fast ripening and
softening

Control of excess
moisture in packed
food

Reduction of water

activity on the surface

Cheese, meat products,
ready-to-eat products.
bakery products,
coffee, tea, nuts,

milk powder

Roasted coffee,
bee f jerky,
dehydrated poultry
products

Fruits such as apples.
apricots, bananas,
mangos, cucumbers,
tomatoes, avocados
Vegetables such as
carrots, potatoes and
brussels sprouts

Meat, ﬁsh, poultry,
bakery products or
fruit and vegetables

Table 1. (continued)

 

 

Packaging type Examples of working Purpose Examples of possible
principle/ applications
mechanism/reagents
Clays (sachet) of food in order to

prevent the growth
of mold, yeast,
and spoilage
bacteria

Absorbers of Cellulose acetate Reduction of Fruit juices

off flavors, ﬁlm containing bitterness in Fish

amines and naringinase enzyme grapefruitjuice Oil-containing foods

aldehydes Ferrous salt and Improving the such as potato chip,

(ﬁlms, sachets)

UV-light
absorbers

Lactose
remover

Cholesterol
remover

citric or ascorbic
acid (sachet)
Specially treated
polymers

Polyoleﬁns like
polyethylene and
polypropylene doped
with a UV absorbent
agent

UV stabilizer in
polyester bottles

Immobilized lactase
in the packaging
material

Immobilized
cholesterol reductase
in the packaging
material

ﬂavor of ﬁsh and
oil-containing food

Restricting light-
induced oxidation

Milk products
for people with
lactose intolerance

Improving the
healthiness of milk
products

biscuits and cereal
products
Beer

Light-sensitive foods
such as ham
Drinks

Milk and other dairy
products

Milk and other dairy
products

 

Absorbers and releasers can be sachet, label or ﬁlm types. While sachets are

placed freely on products in a package, labels are attached to the inside of a package and

generally do not directly contact the food unless the package is turned over. The ﬁlm type

17

is often used in cases where the ingredients impair the function of the system or may

cause migration problems.

2.1.3. Current use and future trends

In the USA, Japan and Australia, active packaging systems are already being
successfully applied to prolong the shelf-life of packaged products. However, there are
only a few commercially signiﬁcant systems on the market. Oxygen absorbers added
separately as small sachets in the package headspace or attached as labels into the lid
probably have the most commercial application in active food packaging at present.
Other commercially signiﬁcant active technologies, such as ethanol emitters or ethylene
absorbers, are less used than oxygen absorbers. In Europe, only a few of these systems
have been developed and are being applied due to the strict European regulations for food
contact materials that have not kept up entirely with technological innovations and
currently prohibit the application of many of these systems.

However, the use of proper packaging materials and methods to minimize food
losses and provide safe and wholesome food products has always been the focus of
packaging. In addition, consumer demands for better quality, fresh-like, and convenient
food products have intensiﬁed during the last decades. The future trend in active
packaging is to use scavenging or releasing compounds incorporated in the packaging
ﬁlm or in an adhesive label to eliminate the requirement for separate objects in the
package, because sachets suffer from inadequate consumer acceptance due to fears of
ingestion by children and accidental consumption with the package contents. These
invisible active scavengers or emitters will be commercialized widely in the near future

(Ahvenainen, 2003; Ozdemir and Floros, 2004).

The market for active packaging ﬁlms was a modest $50 million worldwide in
2003, and was expected to grow rapidly (Ozdemir and Floros, 2004). According to a new
Freedonia Group study, the demand for active packaging will reach $975 million by 201 l
in the U8, driven by 1 1 percent annual growth in innovation and the need to improve
shelf life and safety. Food applications are expected to rise 12 percent a year to $435
million in 201 l, driven by the demand for longer shelf life for processed and packaged
foods. The market for organic products and removal of trans-fats from processed food
will also boost oxygen scavenging packaging. The beverage and beer market for
polyethylene terephthalate (PET) bottles incorporating oxygen scavengers is expected to
reach $395 million in 201 l, with a 15 percent annual increase (Reynolds, 2007). Gas
scavengers were the most used products in the active packaging segment in 2006,
representing over 50 percent of demand. In the pharmaceutical market, compliance
monitoring devices and active reminder products are expected to increase. The demand
for moisture control active packaging is also expected to expand due to pharmaceutical
shipment growth and the increasing number of drugs with high moisture sensitivity

(Bharat, 2007).

2.2. Oxygen scavenger systems

High levels of oxygen present in packed products may facilitate microbial and
insect growth, and accelerate off-ﬂavor development by rancidity as a result of lipid
oxidation; color changes by discoloration of plant pigments such as chlorophyll and
carotenoids; and nutrient losses by oxidation of vitamin E, B-carotene (pro-vitamin A),
and ascorbic acid (vitamin C). Thereby, it may cause signiﬁcant reduction in the shelf-
life of products. The oxygen present may derive from oxygen permeability of the
packaging material, air enclosed in the food and packaging material, or a small amount of
leakage due to poor sealing (Smith et a1. 1986). Therefore, the reduction of the oxygen
level in packed product has an important role in limiting this deterioration and spoilage of
foodstuffs. Oxygen scavenging systems provide an alternative to vacuum and gas
ﬂushing packaging and extend the shelf life, because they can provide removal of oxygen
in packed products using techniques variously called absorption, interception, or

scavenging. In many cases, this is the most important active packaging objective.

2.2.1. Definitions

The terms antioxidants, interceptors, absorbers, and scavengers have been used to
describe the materials employed in the process of removing oxygen or preventing it from
entering the in-package environment of food products subject to undesirable oxidative
reactions. These deﬁnitions do not have clear boundaries, and are often used in

overlapping ways (Brody et al., 2001).

2.2.1.1. Antioxidants

Antioxidants generally are compounds that react with lipid or peroxide radicals,

and that are themselves oxidized to generate what are generally nontoxic compounds.

20

Antioxidants are commonly fat soluble components incorporated into fatty foods to
preferentially react with intermediate oxidation products. These lipid antioxidants include
butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and propyl gallate
(PG), and are often blended with lipids to retard their oxidation. The BHA/BHT
compounds are also often incorporated into polyoleﬁn packaging ﬁlms to retard the
oxidation of the plastic materials themselves. Recently, antioxidants less volatile than
BHT for HDPE and LLDPE, such as polyphenols, have been used in combination with
phosphates. Alpha tocopherol (vitamin E) is also used as an antioxidant for polyoleﬁns

(Selke et al., 2004).

2.2.1.2. Oxygen interceptors

Interceptors are compounds that prevent oxygen from reaching the food product
by themselves being oxidized before the oxygen reacts with the food. The word
interceptor has often been used as a descriptor on food labels to avoid statements about

antioxidants that may have the image to consumers of undesirable chemicals.

2.2.1.3. Oxygen absorbers

Technically, absorbers remove oxygen by physically trapping the oxygen and not
through chemical reaction. However, there are seldom useful materials to remove oxygen
without any chemical oxidation. Therefore, this word is generally used to describe the
systems that remove oxygen to delay or prevent oxidation of foodstuffs. Oxygen
absorbers can be applied as sachets that are ﬁlled with oxygen absorbing components
such as iron particles and salt. They are inserted into the package or adhere to the inner

wall or lid of the package.

21

2.2.1.4. Oxygen scavengers

The oxygen scavenger has been applied to materials incorporated into package
structures that chemically combine with, and thus effectively remove, oxygen from the
inner package environment. In addition, scavengers may remove oxygen from the food
product itself through diffusion resulting from differential partial pressure actions [Figure
3].

. : Oxygen molecules

 

 

 

 

Outer Barrier Oxygen Inner
Layer Layer Scavenging Layer ' l 1
Layer . l

. l

. <::l o E

o o o g 5

<1: o .5

. :1 :

o o 0 i

. \____./ :

 

 

 

 

Figure 3. Structure of a typical oxygen scavenging multi-layer ﬁlm
(Source: Ozdemir and Floros, 2004)

2.2.2. Oxygen scavenging/absorbing technologies

As mentioned in section 2.2.1, oxygen scavenging/absorbing technologies can be
applied as sachets containing oxygen absorbing components. which are inserted into the
package or are tagged onto the inner wall in the package as labels or card types. They can
also be incorporated into the closure liners or containers through compounding with

plastic materials or ﬁxation of oxidizing enzymes in the packaging material.

22

Even though they have higher oxygen absorbing capacity than other oxygen
scavenging systems, these sachet and label types have disadvantages in some commercial
practices. The ﬁrst is that they are not appropriate for liquid products because the direct
contact of the products with the sachet usually causes spillage of the sachet contents.
Secondly, the sachets may accidentally be consumed with the food or may be ingested by
children. Thirdly, they are inappropriate in tube type containers because of inserting or
tagging problems. In addition, although sachets can be considered as secondary
packaging, these practices can increase packaging costs by requiring the operation of an
additional sachet tagging and inspection line. For these reasons, oxygen scavengers of
polymeric type that are incorporated into packaging materials have been introduced as an
alternative to the sachet type.

Another problem in use of iron-based oxygen scavengers is that they generally
cannot pass the metal detectors on the packaging line and are not transparent.
Consequently, organic based oxygen scavenging materials, such as ascorbic acid or
enzyme based materials, have been introduced, because they have good transparency and
allow use of metal detection (Hurrne and Ahvenainen, 1996). Despite these advantages,
their low oxygen scavenging capacity and high cost are innate problems in these systems.

Generally, oxygen scavenging technologies are classiﬁed as enzymatic or
chemical systems, and can utilize one or more of the following mechanisms: iron powder
oxidation, ascorbic acid oxidation, sulﬁte oxidation, photosensitive dye oxidation, ferrous
salts, unsaturated fatty acids and enzymatic oxidation such as glucose oxidase, and
combinations of these (Day, 2000, 2003: Brody, 2001). Table 2 provides a list of some

manufacturers and trade names of oxygen scavengers. The major products are iron based

23

sachet types, and some of these are useful to make ﬁlm or other container types through

incorporating oxygen scavengers into polymeric materials. Especially, Oxyguard® of

Toyo Seikan and Shelf Plus® of Ciba Specialty Chemical have been commercialized as

ﬁlms or trays. Recently, organic oxygen scavengers were commercialized with

development of polyethylene terephthalate (PET) bottles, bottle caps and crowns for beer

and other beverages (Vermeiren et al., 2003).

Table 2. Selected commercial oxygen scavenger systems.
(Source: Vermeiren et al., 2003; Day, 2003)

 

 

Manufacturer Country Trade Scavenger Packaging

Name mechanism Form
Mistubishi Gas Chemical Japan Ageless iron based sachets, labels,
Toppan Printing Japan Freshilizer iron based sachets
Toagosei Chem. Industry Japan Vitalon iron based sachets
Nippon Soda Japan Seagul iron based sachets
Toyo Pulp Japan Tamotsu catechol sachets
Toyo Seikan Kaisha Japan Oxyguard iron based plastic tray, ﬁlm
Multisorb Technologies USA FreshMax iron based labels

F reshPax iron based sachets
Dessicare USA O-Buster iron based sachets
Amoco Chemicals USA Amosorb unknown plastic ﬁlm
Chevron Chemicals USA N/A benzyl acrylate plastic ﬁlm
W.R. Grace and Co. USA PureSeal ascorbate/ bottle crowns

metallic salt
Darex ascorbate/ bottle crowns

24

Table 2. (continued)

 

 

Manufacturer Country Trade Scavenger Packaging
Name mechanism Form
sulphite bottles

Cryovac Sealed Air USA 081000 light activated plastic ﬁlm

Ciba Speciality Chemical Switzerland Shelfplus

CSIRO/Southcorp Australia ZER02
Packaging

CMB Technologies France Oxbar

Standa Industries France ATCO
Oxycap

EMCO Packaging System UK ATCO

Johnson Matthey Plc UK N/A

Alcoa C81 Europe UK 02 displacer
system

Bioka Finland Bioka

iron based

photosensitive
dye/ organic

cobalt catalyst/
nylon polymer

iron based
iron based

iron based

platinum group
metal catalyst

unknown

enzyme based

plastic tray. ﬁlm

plastic ﬁlm
plastic bottles
sachets, labels
bottle crowns

labels

labels

bottle crowns

sachets

 

2.2.2.1. Iron based oxygen scavengers

Among the several active components that absorb oxygen. iron based materials

are most commonly used. Iron power can reduce the oxygen concentration in the

headspace to less than 0.01%, which is much lower than the typical 0.3 to 3.0% residual

oxygen levels achievable by using modiﬁed atmosphere packaging such as vacuum or

gas ﬂushing technologies (Day, 2000).

25

Any oxygen within or entering into the package oxidizes the iron to the ferric
state in the present of moisture drawn from the product or process. This is the basic
mechanism of corrosion or rusting. The reaction mechanism has the following steps

(Vermeiren et al., 2003):

4Fe->4Fe*3+8e‘ (2.1)
2 02 + 4 H20 + 8 e‘ -> 8 (0H)‘ (2.2)
4 Fe+2 + 8 (OH)_ —> 4 Fe(OH)3 (2.3)
4 won)2 + 02 + 2 H20 —> 4 Fe(OH)3 (2.4)
4 Fe(OH)3 —> 2 Fe203 + 6 H20 (2.5)

The stoichiometry of the reaction allows calculation of the amount of oxygen that
reacts with iron. One gram of iron reacts with 0.0136 mol of 02, which is equal to
approximately 330 cm3 of oxygen (STP) (Labuza and Breene, 1989), but the efﬁciency
can be reduced about half by particle agglomeration (Brody et al., 2001).

Several environmental conditions encountered by food packages affect the overall
oxygen absorption (or scavenging) rate of powered iron. The most important factors
include temperature and relative humidity. The effect of temperature on reaction kinetics

can be expressed by the Arrhenius equation:

E
k=k ex ——‘”’- 2.6
. l ,,j i 1

where k is the reaction rate at a given temperature (T), kA is the Arrhenius equation
constant, EA is the activation energy (cal/mol), R is the universal gas constant (1.9872
cal/mol K), and T is absolute temperature (K). If the reaction rates are determined at

several temperatures, then kA and E A can be calculated.

26

Moisture is necessary for the process of oxygen absorption by iron (Equation 2.2),
indicating that relative humidity is an important factor for the reaction. Commercial

oxygen absorbing sachets used in foods are produced for use at different water activities

(a,.,). For an aw greater than 0.85, powdered iron reacts at an acceptable rate for

commercial applications. However, for an aw below 0.85, an additive is needed to bring
moisture into contact with the iron powder.

Another important factor during oxygen absorption by powdered iron is the
presence of a catalyst. NaCl has been used as a catalyst (Klein and Knorr, 1990), because
it allows the ﬁrst two reactions (Equations 2.1 and 2.2) to occur more readily. Klein and
Knorr (1990) reported that 2.0 g NaCl/l 00 g powdered iron gave optimum results for the
maximum oxygen absorption rate. According to Farkas (1998), the oxygen absorption
kinetics of powdered iron containing NaCl as a catalyst were optimized using response

surface methodology (RSM) at 56 °C, 78% RH and 0.8 % NaCl.

’1) Sachet and pad (label and card) type

The ﬁrst major commercial oxygen scavengers, under the trade name of Ageless®.
were from Mitsubishi Gas Chemical Company in 1977. They introduced reduced iron
salts into oxygen permeable sachets, which were placed in sealed gas barrier food
packages. ln-package oxygen absorber sachets are available commercially with the

ability to consume 20 to 2,000 cc of oxygen, based on using packages with oxygen

permeability no greater than 20 cc/mz/day (Robertson, 2006).
After the advent of Ageless® (Japan), the sachet types of oxygen absorbing

systems that have been used the most commonly are as follows: Freshpax® (Multisorb

27

Technologies, Inc., USA). ATCOR’ (Standa Industries, France), and Freshilizers series

(Toppan Printing, Japan). Recently, integrated systems have been developed that include
oxygen-scavenging labels or cards, such as the Freshmaxd" and Agless‘l series, which are
inserted into the package or adhere to the inner wall or lid of the package as sachet. card

and label types [Figure 4].

 

Sachet type Card type Label type

Figure 4. Types of oxygen absorbers

Now, these iron-based oxygen absorbers have the ability to reduce oxygen in
many humidity conditions, including high, intermediate, or low moisture foods or
pharmaceuticals. They can also work at refrigerated conditions. In particular, they have
demonstrated the effectiveness of oxygen removal in various foodstuffs such as bakery,
ﬁsh, pasta, meat, and beverage products such as beer, juice and wine (Gill and McGinnes
I995; Berenzon and Saguy 1998, Vermeiren et al., 1999).

The possible accidental ingestion of the sachet contents by the consumer has been
suggested as a reason for their limited commercial success, particularly in North America

and Europe. As a result, the largest sachet commercially available contains 7 g of ferrous

28

iron, which would amount to only 0.1 g/kg for a 70 kg person, or 160 times less than the
lethal dose for adults. The product has been approved by the Japanese Ministry of Health
and the United States Food and Drug Association (FDA), provided there is a warning

label of “Do not eat” on the package (Brody et al., 2001).

2) Polymeric type

Recently, the incorporation of oxygen scavengers in packaging has been seen as a
better way of resolving sachet related problems even if the speed and capacity of these
systems are lower than those of sachets and labels. Low molecular weight iron based
oxygen scavengers are dissolved or dispersed in plastic materials. The major
commercialized products are as follows: Oxyguard® (Toyo Seikan, Japan), Shelf Plus’R’
(Ciba Specialty Chemicals Corporation, Switzerland), and Ageless® OMAC (Mitsubishi
Gas Chemical, Japan). Mitsubishi Gas Chemical launched a new oxygen scavenger in a
sachet type (Ageless® F8), which no longer uses powdered ingredients. This new, slim
type looks like the current sachet style; it contains an oxygen scavenging plastic sheet
instead of powdered ingredients [Figure 5].

Ageless® F8 is made of a sheet-like label that is mixed with ﬁbrous material,
ferrous iron powder, water, and an electrolyte and is formed by a process similar to paper
making. Ageless® OMAC ﬁlm is ideal for high Aw solid and liquid food, especially for

retorted foods.

29

     

Shelf Plus” (tray) Ageless” OMAC (ﬁlm) Agelessi’ F8 (sheet)

Figure 5. Polymeric type oxygen scavenger (iron based)

Oxyguard® of Toyo Seikan can be used as a therrnoformed tray, a laminated ﬁlm,
or a bottle closure liner, according to their patent (Koyama et al., 1993) [Figure 6]. The
major developments are a heat formable oxygen absorbing resin and an oxygen scavenger.
The resin is a blend of a polyoleﬁn with a water absorbing resin such as a modiﬁed
polyethylene oxide, a vinyl alcohol polymer, a sodium acrylate polymer, or an acrylic
acid/vinyl alcohol copolymer with polyoleﬁn resin. The oxygen scavenger can be mixed
with accelerators such as hydroxides, carbonates, sulﬁtes, halides of alkali metals, and
alkaline earth metals. The particle size of reduced iron ranges from 0.1 to 100 am. The
smaller the particle size of iron, the bigger the oxygen scavenging capacity is. However,
if the particle size is smaller than 1.0 am, a special extrusion system is needed to prevent
explosion due to heat generation during the mixing process. Oxidation promoters used
are chlorides of alkali metals and/or alkaline earth metals such as NaCl or CaClz. The
oxygen scavenger resin is mixed with 7 percent of powdered iron particles by weight. and

the amount of oxidation promoter is 2 to 10 percent of the iron powder weight. Klein and

30

Knorr (1990) reported that 2.0 g NaCl/ 1 00 g powdered iron gave optimum results for the

maximum oxygen absorption rate.

 

Figure 6. Oxyguard ® (tray)

The original technology of Shelf Plusﬁ' of Ciba Specialty Chemicals was
developed from Amoco Chemicals. The composition has not been revealed, but it is an
iron-based oxygen scavenger which is moisture activated. The 02-2400 series is used for
polyethylene carrier resin for blown ﬁlm and the 02-2500 series is intended for
polypropylene carrier resin for retort packages. The oxygen uptake capacity of 02-2400 is
known to be 18 cc Oz/g by their test method and for 02-2500 is 12 cc 02/ g. All contents
were determined to be GRAS (generally recognized as safe) for use in multi-layer food
packaging according to US. FDA regulations. The absorbent layer must be separated
from the product by a sealant layer at least 12.5 am (0.0005 inch) thick in plastic ﬁlm
structures, and 25 11.111 (0.001 inch) thick in multi-layer sheets. Use of these oxygen
scavengers in multi-layer constructions is in compliance with the US. Federal Food,

Drug, and Cosmetic Act and all applicable food-additive regulations (Brody et al., 2001).

31

2.2.2.2. Ascorbic acid oxygen scavenger

The next commercially important oxygen scavenger is ascorbic acid and its
derivatives. The oxidation reaction mechanism of ascorbic acid, which has six carbon
atoms (C6H306), is shown in Figure 7. To convert it to dehydroascorbic acid (C6H606),

metal ions such as iron are needed as a catalyst.

 

HO HO
HO
. ° 0
_, 2 x H" + 2 H20
0 O
Ascorbic Acid Dehydroascorbic Acid

Figure 7. Oxidation mechanism of ascorbic acid
This technology was developed by Toppan Printing in Japan and applied to
packages for ground coffee and bread. The oxygen scavengers of Grace’s Daraformm",
which are ascorbic acid analogues have been used by incorporation into plastic bottle
closure liners (UNCTAD/WTO, 1992). Darex® Container Products (now Grace
Performance Chemicals, USA) developed a new organic oxygen scavenger named
DarEval with Kuraray in Japan, which mixed ethylene vinyl alcohol (EVOH) with this

material, and was designed for PET beer bottles (PET Planet Insider, 2000).

2.2.2.3. Sulﬁte oxygen scavengers
In the late 19505, sulﬁte oxygen scavengers were developed by the Carnation
Company, which used sulﬁte salt with copper sulfate as a catalyst for oxygen absorbing.

In 1980, the Metal Box Company in the UK was granted a patent for an oxygen

32

scavenger in a wine bottle bung or cork using sodium metabisulﬁte plus sodium
carbonate to release sulfur dioxide. The cork or bung was formed by an injection molding
process in which sulfur dioxide, carbon dioxide, and water vapor were produced to ﬁll
voids within the EVA material. This residual 802 and water vapor trapped in the voids

react with entering oxygen (Brody, 2001):

2 so2 + 02 + 2 H20 —> 2 sto.. (2.7)

American National Can Company (now, Pechiney Plastics) developed multi-layer
barrier plastic cans which incorporated potassium sulﬁte oxygen scavenger using a co-
injection blow molding process. This oxygen scavenger can be readily triggered by the
moist high temperature of the retorting process (Farrell and Tsai, 1987). Figure 8 shows
commercialized products using plastic cans incorporating potassium sulﬁte oxygen

scavenger.

 

Figure 8. Plastic cans incorporating potassium sulﬁte oxygen scavenger
(Source: www.hormelfoods.com/brands/hormel/HormelMicrowaveCu s.as IX)

2.2.2.4. Photosensitive dye oxygen scavenger

Photosensitive dye oxidation is an oxygen scavenger system consisting of sealing

a small coil of an ethyl cellulose ﬁlm which contains a dissolved photosensitive dye and a

33

singlet 02 acceptor in a transparent package. By using lights with appropriate
wavelengths, the dye molecules are excited, and then pass their excitation to oxygen as it
diffuses into the ﬁlm from either the package headspace or from the liquid food. The
excited 02 molecules react with the acceptor and then are consumed. While the ﬁlm is
illuminated, the process continues until all the oxygen reacts. The reaction scheme is the

following (Vermerien et al., 1999):

Photon + dye 9 dye* (2.8)
dye* + 02 9 dye + 02* (2.9)
03* + acceptor 9 acceptor oxide (2.10)
02* 9 03 (2.1 I)

where * represents an exited state of the species.

Polyketone can act as a photosensitizer. This photochemical process has some
advantages because it does not need sachets in the food package, is transparent in
packaging, and works regardless of humidity. The ﬁrst dye used was erythrosine, which
is an FDA approved food color additive, plus a color sensitizer that is bleached by light.
For singlet oxygen acceptors, several materials were tested: difurylidene erythrito (DEF),
tetraphenyl prophine (TPP), dioctyl phthalate (DOT), and dimethyl anthracene (DMA).
However, these are not approved for food contact. This type of oxygen scavenger does
not initiate in the dark. Therefore, this technique cannot be used with non-transparent
ﬁlm such as aluminum foil. Examples of light-activated scavengers are Zero:TM (CSIRO.
Australia) and OS 1000 (Cryovac Sealed Air, USA). 08 1000 is trigged when the ﬁlm is
exposed to ultraviolet radiation, and is useful for the horizontal thermoform/ﬁll/seal

(HFFS) process (Brody, 2001). Recently, Cryovac launched a new type of oxygen

34

scavenging ﬁlm named OSP OS 2000 and commercialized it for use in both ﬂexible and
rigid packaging applications. The oxygen scavenger material is based on a blend of
ethylene methylacrylate cyclohexenyl methyl acrylate (EMCM) and was developed by
Chevron Phillips Chemical Company (Brody, 2001). The OSP system was approved by
the US. Food & Drug Administration (FDA) in 2000, with a limitation that it could be
used only as a non-food-contact layer in laminate structures, provided that it is separated
from the food by one or more polymeric layers of a total thickness of at least 6 microns
(0.25 mils) (Solis and Rodgers, 2001). Figure 9 shows the performance advantage of

OSPTM forjuice packaging.

Vitamin C Content

 

 

 

 

 

E

40
.3.
2’ 35 '5', _
v G-ua -\1|
1: ‘x
a 30 ”x-
< ‘G‘~a _____ B
2 ------- «L-E‘_
E 25 “~~-EI
8
2 20

0 20 40 60 80 100 120
Days

 

[ - —o— — Ref. Carton + OSPTM Carton]

 

Figure 9. Performance advantage of OSPTM in juice packaging
(Source: Solis and Rodgers, 2001)

2.2.2.5. Enzyme based oxygen scavengers
Another oxygen scavenger technique uses enzyme reactions. The enzyme
responds with a speciﬁc substance to scavenge incoming 02. Glucose oxidase is a

POPUIar oxygen scavenging enzyme. Glucose oxidase transfers two hydrogens from the

35

-CHOH group of glucose to oxygen with the formation of glucono-delta-lactone and
hydrogen peroxide. The lactone reacts with water to form gluconic acid. The reaction is

the following (Vermeiren et al., 1999):

2(3 + 202 + 2H30 —> zoo + 2H203 (2.12)

where G is glucose.

However, H202 is a highly oxidizing agent and therefore objectionable, so catalase is

introduced to break down the peroxide:

2H202 + catalase --> 2H20 + 03 + catalase (2.13)

From the two reactions above, the original oxygen is reduced by half, and
ultimately it will become zero. The glucose plus catalase enzyme system is very sensitive
to pH, water activity, temperature, and various other factors. Also, it requires water for
activation, so it cannot be used for low humidity products. Another disadvantage is that,
when oxidation occurs. some reactions may generate undesirable odor compounds such
as ketones or aldehydes (Labuza and Breene, 1989). An oxygen scavenger of this type
has been commercialized by Bioka in Finland, which can be easily applied to the surface

of polyoleﬁns (Vermeiren et al., 2003).

36

2.2.3. Recent technologies in oxygen scavengers
Oxygen scavenging technologies are the most developed and most patented of all
active packaging technologies owing to their market success. The global market for
oxygen scavengers was presumed to exceed $200 million, and exceed 10 billion units in
Japan, several hundred million in the USA and tens of millions in Europe in 1996. This
market was estimated at $1 billion by 2001 (Day, 2003). Before 1995, more than 70
patents involving oxygen scavengers had been granted across the world (Ozdemir and
Floros, 2004). Recent US patents issued for oxygen scavenging focus on technologies
that are incorporated into ﬁlm or sandwiched in the structure of bottles. Another trend is
non-metal systems replacing metals. Despite the fact that the speed and capacity of
oxygen scavenging in ﬁlm are fairly low compared to the oxygen absorbing sachets, the
technologies for incorporating into ﬁlm offer several advantages over sachets: useful for
retorting or pasteurizing products using hot water, prevention against distortion or
transformation by sachet contact with products, cost saving by production efﬁciency that
does not need a secondary package, and elimination of inadequate consumer acceptance
due to fear of ingestion. For the sandwiching technologies, FDA approval for use with
post-consumer-recycled polyester (PC R PET) in soft drink bottles has accelerated
introduction of the oxygen scavenging system for beer bottles. This oxygen scavenger
system was developed by Continental PET technologies and is composed of nylon
MXD6/cobalt salt mixed with a 2% blend of polyketones to enhance the oxidation
reaction. It is used as the middle layer in PET bottles (Brody etal., 2001). Constar
I ntemational Inc. developed "MonOxbar Plus", a blend of Constar’s patented “Oxbar”
oxygen scavenger with ultraviolet-1ight-blocking PET. They commercialized it in a 46 oz

monolayer ketchup bottle and a 750 ml wine PET container in 2008 (Constar 2004;

37

Kalkowski, 2008). Table 3 shows recent information about patents in the U8.

Table 3. Recently issued US patents for oxygen scavenging systems

 

 

Company Structure/composition year
BP Amoco Corp. Copolymers comprising polyester segments 2000
+ polyoleﬁn oligomer segments
BP Corp. Oxygen scavenging monolayer bottles 2007
(PET + oxygen scavenger of low migration level)
Chevron Chemical Co. Oxygen scavenger consisting of poly (ethylene-methyl 2003
' acrylate) terpolymer + gable-top carton
Multilayer rigid container having oxygen scavenger 2006
selected cyclic oleﬁnic pendent group
C iba Specialty Chem. Oxygen scavenger for extrusion coating; 2003
oxidizable metal + polymeric resin (metallocene
Polyethylene and styrene-rubber block copolymer)
Cryovac Corp. Zeolite + an oxidizable compound and 2002
a transition metal catalyst + ethylenically
unsaturated hydrocarbon
Oxygen scavenging ﬁlm with cyclic oleﬁn 2007
copolymer + dosage of actinic radiation to trigger
Eastman Chemical Co. Polyamide nanocomposites (silicate material) 2004
with oxygen scavenging capability
Polyester based cobalt concentrates for oxygen 2007
scavenging compositions
Honeywell Polyamide homopolymer + copolymer 2004
International Inc. + an oxidizable polydiene or oxidizable polyether
Kuraray Co. EVOH + transition metal salt (iron. nickel, copper 2003
and cobalt salt)
Mitsubishi Gas Oxygen permeating resin layer + deoxidizing resin 2000

Chemical Co.

layer containing a particulate absorbing composition
+ smoothing layer + gas barrier layer

38

Table 3. (continued)

 

 

Company Structure/composition year
Oxygen absorbing multilayer ﬁlm including 2004
gas barrier epoxy containing xylyenediamine unit
(NCH2C6H4CH3N)

Otsuka Pharmaceutical Oxygen scavenger for pharmaceutically acceptable 2004
salt (tetrazolylalkoxy-dehydrocarbostyril compound)

Toyo Seikan Kaisha Organic oxidizing component (xylylene group 2005
+ polyamide) + transition metal catalyst

W.R. Grace and Co. Carrier material + metal loaded cationic 2000
exchange material
Metal catalyzed ascorbate compounds (D- or L- 2004

ascorbic acid or a salt or a fatty acid) as oxygen
scavenger

 

39

2.3. Regulatory issues

According to the results from the 'Actipak' research project funded by European
Commission (FAIR Project CT-98-4170), at least four types of food safety and regulatory
issues related to active packaging of food needed to be addressed. First, any need for food
contact approval must be established before any form of active packaging is used. Second.
it is important to consider environmental regulations covering active-packaging materials.
Third, there may be a need for labeling in cases where active packaging may give rise to
consumer confusion. Finally, it is proper to consider the effects of active packaging in the
microbial ecology and safety of foods (De Kruijf, 2000).

Legislative demands regarding food packaging and food contact materials include
speciﬁc consumer protection and environmental concerns. In various countries,
legislation related to food contact materials has been framed. However, there are only a
few speciﬁc regulations for these innovative concepts, and the basic criteria for these
regulations differ between countries (Ahvenainen, 2003).

In the USA, components directly introduced in foodstuffs or indirectly introduced
through packaging are regarded as food additives that are deﬁned in Section 321 (s) of
the Federal Food, Drug and Cosmetic Act. Therefore, the active ingredients have to be
evaluated as additives by strict toxicological testing before use according to 21 USC
Section 348 (C) (3) (A). The manufacturer must submit a ﬁling to the Center for Food
Safety and Applied Nutrition (CFSAN) to demonstrate safety (FDA, 2002). If a
manufacturer does not have to ﬁle a Food Additive Petition (FAP) or a Food Contact
Notiﬁcation (FCN) proposed by CFSAN, the manufacturer can seek C FSAN’s agreement

that the substance is generally recognized as safe (GRAS).

40

Recently, FDA has been under increased pressure to regulate the use of
nanotechnology, because research is not widely available to demonstrate the pattern of
migration of active ingredients while the market is rapidly growing (Cole, 2007). The
market using nanotechnology increased more than $860 million in sales worldwide in
2006, and is predicted to be a $30 billion market within 10 years (Helmut Kaiser
Consultant, 2005). Oxygen scavengers using nanocomposites such as silicate or organo-
clay have also been applied in the market (Hildebrandt, 8., 2005; Eastman Chemical Co.,
2004). For this reason, the US. FDA’s Nanotechnology Task Force Team was organized
in 2006 and released a report on the scientiﬁc and regulatory challenges related to the use
of nanotechnology in products regulated by the FDA on July 23, 2007 (FDA News, 2007).
The Task Force reported that the use of nanomaterials in products regulated by the FDA
presents challenges similar to those products using existing technologies and other
emerging technologies.

In Japan, new components must be registered as chemicals according to the
Guidelines for Screening Toxicity Testing of Chemicals. Migration behavior of active
packaging has not been explicitly described in any of this regulation (Day, 2003;
Ahvenainen, 2003).

In Europe, only a few active packaging systems have been applied and the global
market share is relatively small, because EU legislation is stricter than other countries
such as USA and Japan (Climpson, 2005). Active releasing materials were not allowed
before 2004 since the regulations at that time set an overall maximum migration limit of
60 mg/ kg food from the packaging into food for all packaging material including active
packaging. This limit was not appropriate for active releasing materials, since it is often

their aim to release substances above this limit. The active systems that were not limited

41

by the legislation at that time were absorbing materials such as oxygen scavengers and
moisture absorbers, since they complied with the legislation at that time as long as the
toxicological properties and quantities of migration of the active packaging materials
were acceptable (Dongen and Kruijf, 2007).

A new Framework Regulation (l935/2004/EC) including the use of active and
intelligent packaging systems was adopted in 2004, and requires that they shall not
endanger human health. This new Framework Regulation for Food Contact Materials is a
regulation instead of the previous Directive (89/ l 09/EEC), which focused only on food-
contact materials for food packaging and mostly related to plastic materials. All new
active and intelligent packaging systems initially need to be evaluated by the European
Food Safety Authority (EFSA) (Cole and Bergeson, 2007). EFSA said assessments for
the substance migration will focus “on the migration into food of the active or intelligent
substances, and of the substances possibly generated through degradation or reactions, as

well as their toxicological properties” (Byme, 2009).

42

2.4. Migration from active packaging

The key regulatory issue is food-contact approval, because substances may
migrate into the food from active packaging. Such migrants may be intentional or
unintentional. Intentional migrants include antioxidants, ethanol and antimicrobial
preservatives, which require regulatory approval in terms of their identity, concentration
and possible toxicological effects. Unintentional migrants include various metal
compounds or other system components that could enter the food. In most countries,
there are regulations limiting or prohibiting the quantities of such components in the food.
However, no speciﬁc regulations exist on testing the suitability of active and intelligent
packaging systems in direct contact with foods and, in many cases, the testing protocols
used are not necessarily appropriate, being based on those developed for plastic
packaging materials (Robertson, 2006).

In order to solve these problems, in Europe, the Actipak project started in January
1999, and a selection of available active and intelligent systems was made for
compositional analysis and overall migration study. The composition was experimentally
veriﬁed by means of analytical techniques such as GC-MS, atomic absorption (AA)
spectrometry, IR spectrometry, X-ray ﬂuorescence (XRF) spectrometry and scanning
electronic microscopy for energy-dispersive spectrometry (SEM-EDS). For the
determination of the overall migration from the active and intelligent systems to the
various food simulants, the relevant CEN EN 1 186 methods were evaluated by the
Actipak project in Europe (De Kruijf et al., 2002). This is similar to the method (Food-
type as deﬁned in 21 CFR 176.170 (c)) recommended by FDA (FDA, 2002). Evaluation
of OS composition was focused on determining the major active components and relevant

reaction products [Table 4].

43

Table 4. Some typical results of the evaluation of the composition of active packaging
systems (Source: De Kruijf et a1. 2002)

 

 

Packaging system Ingredients identiﬁed
Oxygen scavengers iron powder

silicates

sulphite

chloride

polymeric scavenger
elements: Fe, 81, Ca, Al, Na, Cl, K,
Mg, 8, Mn, Ti, Co, V, Cr, P

Ethylene scavengers plasticizer
permanganate
zeolite
elements: Mg, Al, Si, K, Ca, Ti,
Fe, Mn

Moisture absorbers silicates
plasticizer
cellulose ﬁber
sugars
acids
ethanol
glycerol
surfactant
elements: Mg, Fe, Ca, K, 8, Ti, P, V
Mn, Cr, Zn, Sr, Si, Al, Na

Antimicrobial releasers acids
silicates
ethanol
zinc
elements: Si, Na, Al, 8, Cl, Ca, Mg.
Fe, Pd, Ti

 

More detailed research on the migration of oxygen scavengers was done by
L0pez-Cervantes and other members of the TNO Nutrition and Food Research Institute in

EUI'Ope (Lopez-Cervantes et al., 2003). They studied two commercial oxygen scavenger

44

systems: One (081) had the form ofa cup made of plastic and covered with a porous
plasticized paper seal. The other one (081,) was a sachet laminated with paper and plastic.
The weight and contact area of 081 was 6.28 g and 19.6 cmz. 08L was 56.7 g and 68.0

cmz. Species migrating from 081 and 08L which were stored for 10 days at 40°C

immersed in 200 ml liquid simulant in a hermetically sealed jar were evaluated by XRF
and SEM-EDS. The major elements were identiﬁed by XRF as Na, Cl and Fe. Minor
elements detected were Si, P, Ca and others. SEM-EDS revealed Na, Cl, Fe, C and O as
major elements and minority structures contained Ca and Cl. They concluded that the
main components of the residue were NaCl and iron compounds, and that the main
migrants were therefore NaCl and iron. Samples of the simulant were then taken for
determination of NaC l and iron as well as the overall migration (OM) in water and 3%
acetic acid. From Table 5, it can be seen that the sum of the calculated masses of
migrated NaCl and iron compound [Fe(OAc)2] that was a mixture of ferric oxide, and
ferric and ferrous acetate is close enough to the total migrated mass to be taken as an
acceptable estimate of overall migration. Not only the quantities of overall migration, but
also NaCl migrating into water and 3% acetic acid from 081 and 081, exceed the overall
migration value of 60 mg/kg [12 mg/200 ml] set by EU legislation (European
Commission, 1990). It is disputable how the limit should be applied because neither 081
nor OSL appear suitable for use in direct contact with these kinds of simulants. Even if
they concluded that both systems should be positioned to minimize contact between their
porous surfaces and packaged foodstuffs, it is not easy because oxygen scavenging
systems positioned to minimize contact with food could be in contact with food during
transportation or handling. Furthermore, in the case of a cosmetic which is ﬁlled in a tube,

it is impossible to avoid contact with the contents. Therefore, to avoid or reduce the

45

quantity of migration below the value of 60 mg/kg, a new concept for the packaging
system such as a multilayer ﬁlm which incorporates an oxygen scavenger in the core-
layer structure is needed.

On the other hand, since proper simulants have not been identiﬁed for most of the
pharmaceuticals or cosmetic products, food simulants have been used for

pharmaceuticals and cosmetics (Figge et al., 1978).

Table 5. Comparison of overall migration (OM) into water and 3% acetic acid, as
calculated from total ﬁnal residue mass, with speciﬁc migration of NaCl and Fe (the
latter as Fe(OAc)2), as calculated from observed migration of chloride and iron,
respectively. (Source: Lopez-Cervantes et al., 2003)

 

 

Unit: mg/200ml
OS element Simulant NaCl FC(OAC)2 NaC1+Fe(OAc)2 OM
081 water 88 :l: 6 0 88 i 6 107 :l: 9
3% HAc 72 i 12 654 :l: 67 726 i 68 707 :1: 17
08., water 821 i 8 3 i 0.1 824 :1: 8 898 :1: 6
3% HAc 968 :1: 86 688 :l: 69 1656 :1: 1 10 1263 i 56

 

46

2.5. Advances for active packaging

As mentioned above, active packaging systems are already being successfully
commercialized to extend shelf life in the US. and Japan. However, in Europe and other
countries, only a few of these systems are in use and the global market share is relatively
small (Dongen and Kruijf, 2007). The main reason is that EU regulation was tighter than
those of other countries, and the rest, including Korea, do not have any regulation for this
system. Therefore, when they do the future work not only to remove legislative barriers
or establish proper safety regulations, but also to provide reliable information channels to
consumers and realize economic advantages by using these technologies, many new
opportunities in the food and non-food industries will arise and a bright future for active
packaging can be expected. For the successful accomplishment of this work, some issues
identiﬁed by the Actipak project in Europe are useful for consideration in other countries

as well as in Europe (Robertson, 2006).

2.5.1. Major issues identiﬁed by Actipak

The Actipak project (ACTIPAK-FAIR CT98-4170) was carried out by twelve
people from research institutes such as TNO in. the Netherlands and industrial
development centers to establish active and intelligent packaging systems within the
relevant regulations in Europe (Ahvenainen, 2003; De Kruijf et al., 2002). This resulted
in the adoption of a new Framework Regulation (1935/2004/EC, which was published on
27 October 2004). Some factors Actipak identiﬁed to be considered in the development
of active packaging in the future (De Jong etal., 2005) are:
1) Several legal barriers: Active packaging concepts are already commercialized in many

countries such as the USA and Japan, but they cannot be used widely in Europe yet. due

47

to legislative restrictions.

2) Reliability and effectiveness: All active systems should be thoroughly validated for
each speciﬁc application to be sure that they are effective.

3) Economic issues: In order to expand active packaging. cost reduction is still a very
important issue to solve.

4) Acceptance by consumers, food producers and retailers: it is necessary to provide
reliable information to reduce the consumer resistance, and lack of knowledge about

effectiveness.

2.5.2. Selection of an appropriate oxygen scavenger

As oxygen scavengers are also one of the major components in active packaging,
design of active packaging should satisfy some requirements as well as the considerations
mentioned in the upper section 2.5.1. They should
1) Be harmless to the human body. Especially, in the case of sachets, they should provide
clear information to consumers that oxygen absorbers are not food or food additives
because there is the possibility of accidents.
2) Be designed so that the speed and capacity of the oxygen scavenger are appropriate for
the shelf life of the products.
3) Not produce toxic substances or undesirable gases or off-ﬂavors.

4) Be economically priced.
2.5.3. Package design and process control

In consideration of processing technologies, polymeric materials containing

oxygen scavenging components should have good processability, and be useful to

48

incorporate into appropriate packaging materials, and have high compatibility with
commercialized polymers that are used in packaging design. The oxygen scavenging
materials and packages such as ﬁlm, bottles and other packaging must be kept in a stable
condition and protected from premature activity. The most suitable packaging design is
that the packaging materials and structures, especially the oxygen scavenging layer, are
not deprived of their physical properties after the process of oxygen scavenging.
Moreover, they should not generate any kinds of byproducts that can affect the sensory

qualities such as off-ﬂavor or change in nutritional properties of the packaged products

(Lopez-Rubio, 2004).

49

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50

Climpson, J., “Global markets for active packaging in 2001, 2005, and 2010” in Pira
International Leatherhead report, The Future of A ctive Packaging in Food and Drink
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Cole, Michael F. and Lynn L. Bergeson, “Regulation of new forms of food packaging
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Constar International Inc, “MonOxbarTM,” PET Oxygen Barrier Effectiveness: A
Comparison of Alternatives” in Proceedings of Pack Expo, 2004. www.constar.nct.

 

Cryovac Corp. (Inventors: Rivett, J.W. and D.V. Speer), “Oxygen scavenging ﬁlm with
cyclic oleﬁn copolymer,” US. Patent 7258930, Aug. 21, 2007.

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Technology, Blackwell Pub., London, pp. 282-302, 2003.

Day, B.P.F., “Underlying principles of active packaging technology,” Food Cosmetics
and Drug Packaging, 23: 134-139, 2000.

De Jong, A.R., H. Boumants, T. Slaghek, J. Van Veen, R. Rijk, & M. Van Zandvoort,
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Contaminants, 22: 975-979, 2005.

De Kruijf, N., M. van Beest, R. Rijk, T. Sipilainen-Malm, P. Paseiro Losada and B. De
Meulenaer, “Active and intelligent packaging: applications and regulatory aspects,” Food
Additive and Contaminations, 19: 144-162, 2002.

Dongen, William D., and Nico de Kruijf, “ACTIPAK in Europe” ” in Charles L. Wilson,
ed., Intelligent and Active Packaging for Fruit and Vegetables, CRC Press, Taylor &
Francis Group, Boca Raton, FL, pp. 315-327, 2007.

Eastman Chemical Co. (Inventors: Bernard, L.G., H.Clauberg, M.J. Cyr, W. Gilmer, J .T.
Owens, M.E. Stewart, 8.R. Turner, 8. Basrodia, J. Christopher, Matayabas, Jr.),

“Polyamide nanocomposites with oxygen scavenging capability,” US. Patent 6777479,
Aug. 17, 2004.

51

Eastman Chemical Co. (Inventors: Stewart, M.E., E.E. Sharpe, Jr., B.B. Gamble, S.L.
Stafford, R.N. Estep, J .C. Williams, T.R. Clark), “Polyester based cobalt concentrates for
oxygen scavenging compositions,” US. Patent 7288586, Oct. 30, 2007.

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materials and articles intended to come into contact with foodstuffs.” Official Journal of
European Communities, L349; 26-47, 1990.

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AAT 9953735, 1998.

Farrell, C.J., and BC. Tsai, “Oxygen scavenger,” US. Patent 4702966, Oct. 27, 1987.

FDA (US. Food and Drug Administration), “Guidance for Industry: Preparation of Food
Contact Notiﬁcation: Administrative, FINAL GUIDANCE,” May 2002.
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FDA (US. Food and Drug Administration), “FDA Regulation of Nanotechnology
Products”. www.fda.gov/nanotechnologv/regulation.htm1, (accessed April 10, 2009).

FDA News, “FDA Nanotechnology Report Outlines Scientiﬁc, Regulatory Challenges.”
July 25, 2007. http://www.fda.gov/nanotechnology/taskforce/report2007md f, (accessed.
April 10, 2009).

F igge, K., J. Koch and W. Freytag, “The suitability of simulants for foodstuffs, cosmetics
and pharmaceutical products in migration studies,” Food and Cosmetics Toxicology, 16
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“Oxygen scavenging high barrier polyamide compositions for packaging applications.”
US. Patent 6685861, Feb. 3, 2004.

52

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Hurme, E. and R. Ahvenainen, “Active and smart packaging of ready-made foods,” in
Proceedings of the International Symposium on Minimal Processing and Ready Made
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Insider, “FDA Falls Behind on Nanotech Dietary Supplements,” Jan. 15, 2009.
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53

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Applications,” Food Review International, 20(4): pp. 357-387, 2004.

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54

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55

3. DEVELOPMENT OF MULTILAYER FILM INCORPORATING OXYGEN

SCAVENGER

3.1. Introduction

As mentioned in section 1.3, one of the most important factors in developing
commercial products and packaging to contain vitamin A compounds such as retinol is
how to prevent the decomposition from oxygen (Barua and Hrold, 1998; Ball, 2006).
Oxygen scavenging technology seems to solve the problem because it can effectively
remove oxygen from the inner package environment (Ozdemir and Floros, 2004). Among
the several active components that absorb oxygen, iron based material is most commonly
used. Recently, the incorporation of oxygen scavengers in the middle layer of a
multilayer ﬁlm has been seen as a better way of resolving problems such as that the
oxygen scavengers in a monolayer ﬁlm are direct contact with products and that sachet
types are not appropriate in tube type containers because of inserting or tagging problems
(De Jong etal., 2005; Robertson, 2006).

The research of Foltynowicz shows that small particles of oxygen scavengers tend
to agglomerate. This agglomeration is the clumping together of small particles of oxygen
scavengers, which occurs during the extrusion process. The oxide layer, which forms on
the surface of the agglomerates on exposure to oxygen, hinders further oxygen access to
the bulk scavenger and results in a decrease of oxygen uptake (Foltynowicz, et al., 2002).
It also inﬂuences the mechanical properties because of uneven bubble shape caused by
agglomerations in the ﬁlm during the blown ﬁlm process. Therefore, another major factor
is how to make oxygen scavenging multilayer ﬁlms without any agglomerations, because

they can reduce not only the mechanical and thermal properties but also the oxygen

56

absorbing capacity.
Thus, the ﬁrst objective ofthis study is to develop a multilayer ﬁlm incorporating
iron based oxygen scavenger as follows:
1) To design a proper multilayer structure and process conditions
2) To have the best value for mechanical, optical and thermal properties

3) To evaluate the oxygen absorbing capacity in multilayer ﬁlms

57

3.2. Materials and methods
3.2.]. Experimental work
3.2.1.1. Film design and material selection

The ﬁlm was designed with a three-layer structure and manufactured by a co-
extrusion blown ﬁlm process which has three extruders. The inner and outer layers were
composed of high density polyethylene (HDPE) and the core layers were an oxygen
scavenging material mixed with the same HDPE as used in the inner and outer layers.
Oxygen scavenging materials (081 and 082) were compounded iron powders with
polyethylene as a base resin, and the oxygen uptake capacity (cc Og/g) was designed to
have the same value. They were all commercialized products; 081 was received from a
company in Europe, and 082 was purchased from a Japanese company.

To improve dispersion of oxygen scavenger in the ﬁlm, linear low density
polyethylene (LLDPE) was used instead of HDPE, which had resulted in some
agglomerations during processing the ﬁlm. The polymers selected for the investigation
are all commercialized materials and are listed in Table 6.

The total thickness of the ﬁlm that was designed experimentally was 130 ~ 225 am.
The thickness of the inner and outer layers which consisted of LLDPE or HDPE were
approximately 25 ~ 30 ,um, and the middle layer which consisted of oxygen scavengers
was 75 ~ 175 um. In order that oxygen scavenging materials of the middle layer do not
contact the product directly, the inner layer must be designed to be at
least 12.5 ,um (0.0005 inch) thick (plastic ﬁlm) and 25 um (0.001 inch) thick (plastic

sheet) for the material in the middle to be considered generally recognized as safe

(GRAS) by the US. FDA (Brody etal., 2001).

58

Table 6. Characteristics of the materials selected

 

Material Commercialized Melt Index Density Registration
Country (g/ 10 min) (g/cc)
ASTM D1238 ASTM D1505

 

081 Europe 3.0 1.42 US FDA, US TSCA,
ECCS,

082 Japan 5.0 1.38 MHW, GSTTC

LLDPE Korea 1.0 0.928 US FDA

HDPE Korea 0.07 0.956 US FDA

 

US FDA: United State Food and Drug Administration

US TSCA: United State Toxic Substances Control Act

ECCS: European Community Compliance Statement

MHW: Ministry of Health and Welfare (JAPAN)

GSTTC: Guideline for Screening Toxicity Testing of Chemicals

1) Calculation for weight of oxygen scavenger

Before making the desired oxygen scavenging ﬁlm, it was necessary to calculate
the weight of oxygen scavenger needed in the middle layer of the ﬁlm. In order to
determine the required content of oxygen scavenger, the volume in the headspace of the
package was measured by using a syringe to inject water into the headspace of a
packaged product. The average air volume of the headspace (Va) was 5.2 cc. Then, the
volume of oxygen present in the headspace of the package (Vo) could be calculated as
follows:

Vo=Vax[02]/100 =5.2ccx21/100=l.09cc (3.1)

M=Vo/Co=l.09cc/18cc/g=0.061 g (3.2)
where, [02]: initial 02 concentration in package (= 21% if air)

M: needed weight of oxygen scavenger material

59

Co: oxygen uptake capacity (18 ccOg/g), 081 and 082 had the same values.

2) Calculation for ﬁlm thickness of oxygen scavenging layer

From the equation (3.2), the needed weight of oxygen scavenger materials to
absorb fully the oxygen in the headspace of the package was 0.061 g. In order to
incorporate the materials (0.061 g) in the middle layer of the ﬁlm, the desirable ﬁlm
thickness ofthe middle layer (Tmi) was calculated using the following equation:

M=thmeD (3.3)

Rearranging to solve for Tmi,

Tmi = M / (Sh x D) (3.4)
where Sh is the interior surface area of the headspace in the package.

Sh = 27tr x h = (2 x 3.1416 x 1.22 cm) x 2.0 em

= 7.67 cm x 2.0 cm = 15.34 cm2 (3.5)
where h is the interior height of the headspace in the package (2.0 cm).

Since most of the residual oxygen was located in the headspace of the package,
Sh was calculated instead of 8 (total interior surface of the package). D was the density of
the middle layer.

For ﬁlm having different formulations, such as when the formation of the middle
layer was changed by adding LLDPE or HDPE resin into the oxygen scavenger
material (M = 0.061 g), the desirable ﬁlm thickness (Tmi) was calculated using the
following equation:

Tmi = Mi / (Sh x Di) (3.6)
where M1 is the weight of the blend of LLDPE or HDPE with the oxygen scavenger

material (M = 0.061 g), Di is the new density ofthe blend with LLDPE or HDPE.

60

In the case where HDPE was added 70 wt % into 081 that had 0.061 g of oxygen

scavenger material, the ratio of 081 was 30 wt %, Tmi was calculated as follows:

 

 

M
Tmi 2 M = 55.37;
Sh x Di Sh x [(1 — OSlwt%) x HDDi + OSl.wt% X OS] Di]
0.061g (3.7)
[6.31

 

— (15.34cm2)x[(1-0.3)x 0.956g/cm" + 0.3x 1.42g/cm3]
= 0.01210 cm = 121.0 ,um

where HDDi was the density of HDPE, and OSIDi was the density of 081 .
When LLDPE was added 50 wt % into 082 that has 0.061 g of oxygen scavenger

material, the ratio of 082 was 50 wt %, Tnm was calculated as follows:

 

 

M
Tmi 2 Mi : oszwtu;
Sh x Di Sh x [(1 — 052wt%) x LLDi + 052.18% x 082Di]
0.061g (3.8)
l 0.51

 

z (15.34cm2)x[(1— 0.5) x 0.928g/cm" + 0.5 x 1.38g/cm3]
= 0.00689 em = 68.9 ,um

where LLDi was the density of LLDPE, and 082Di was the density of 082.
When the ratios of 081 or 082 and HDPE or LLDPE were changed, the desirable

ﬁlm thicknesses in the middle layer were changed as shown in Table 7.

61

Table 7. Desirable ﬁlm thicknesses in middle layer

 

 

 

Components of middle layer Di Mi Tmi
Average Middle layer Middle layer

HDPE LLDPE 081 082 Density ﬁlm weight ﬁlm thickness

N0. (wt %) (wt %) ('Wt‘Vo) (wt°/o) (g/Cm’) (8) (tan)

D0 0 100 1.420 0.061 28.0

D1 50 50 1.188 0.122 66.9

D2 60 40 1.142 0.152 87.1

D3 70 30 1.095 0.203 121.0

D4 75 25 1.072 0.244 148.4

D5 50 50 1.174 0.122 67.7

D6 50 50 1.154 0.122 68.9

 

3.2.1.2. Experimental ﬁlm structures

In order to develop a good active package, it is most important to make a good
functional ﬁlm. For this purpose, several kinds of ﬁlms were tested. The ﬁrst step was to
determine the amount of agglomeration in the ﬁlms because this could affect the oxygen
scavenging capacity. The next step was to evaluate the appearance and properties of the
ﬁlms. To determine the agglomeration, HDPE and 081 resin were blended and processed,
and are shown from A to D in Table 8. However, the results of evaluating the samples for
agglomeration were very poor as shown in Figure 12, so the ﬁlms E and F in Table 8
were produced as a second trial. The thickness of ﬁlms using LLDPE was adjusted
slightly from HDPE based ﬁlms, as shown in Table 8. To compare properties of the two
oxygen scavenger materials (081 and 082), the ﬁlms were produced using the same

process conditions.

62

Table 8. Design for each layer of ﬁlms

 

 

 

 

(Unit: pm)

No Inner Layer Core Layer Outer Layer Total

Material Thick. Material Thick. Material Thick. Thick.

MinI Design2

A HDPE 25 *HDPE(50%)+OSI(50%) 66.9 80 HDPE 25 130
B HDPE 25 *HDPE(60%)+OSI(40%) 87.1 105 HDPE 25 155
C HDPE 25 *HDPE(70%)+OSl(30%) 121.0 145 HDPE 25 195
D HDPE 25 *HDPE(75%)+OSI(25%) 148.4 175 HDPE 25 225
E LLDPE 30 LLDPE(50%)+OSI(50%) 67.7 75 LLDPE 30 135
F LLDPE 30 LLDPE(50%)+082(50%) 68.9 75 LLDPE 30 I35

 

 

 

 

 

 

' : Calculated theoretical thickness

2 : Margin-added thickness (~10 - 20% surplus over theoretical thickness)
*: Melt-blending was done in a co-rotating twin screw extruder with a 30 mm screw

diameter and 30:1 L:D ratio outﬁtted with 2 vent ports.

3.2.1.3. Processing conditions

The 6 kinds of ﬁlms in Table 8 were produced using a co-extrusion blown ﬁlm

line that had 3 extruders. The ﬁlm line is shown in Figure 10 and the speciﬁcations of the

ﬁlm line are shown in Table 9. Two process conditions were used. The ﬁrst condition

was used for HDPE blended polymers, and the second for LLDPE blended polymers. The

processing conditions for A, B, C and D in Table 8 are shown in Table 10-1, and E and F

are shown in Table 10-2.

63

Table 9. Speciﬁcation of blown ﬁlm line

 

 

 

Extruder Screw Dia.(mm) Output (kg/hr)
Inner Layer 65 75
Core Layer 90 150
Outer Layer 65 75
Total Output 300

 

 

Figure 10. Co-extrusion blown film line (Reifenhauser, Germany)

64

Table 10-1. Condition 1: Processing temperatures for HDPE blended polymers

 

Barrel in Extruder

 

 

Layer Unit Screen Adapter Die
C1 C2 C3 C4 Changer

Inner °C 145 149 153 157 160 165 163

Core °C 148 154 166 170 170 | 72 163

Outer °C 149 152 154 158 160 165 l 63

 

Table 10-2. Condition 2: Processing temperatures for LLDPE blended polymers

 

Barrel in Extruder

 

 

Layer Unit Screen Adapter Die
C1 C2 C3 C4 Changer

Inner °C 130 133 I36 140 145 150 148

Core °C 133 137 142 I48 153 I60 148

Outer °C 130 133 136 140 145 150 148

 

3.2.1.4. Film preparation and sampling

The LLDPE monolayer ﬁlm and oxygen scavenger (081 and 082) containing

multilayer ﬁlms previously prepared were used for further testing of appearance, optical,

thermal and mechanical properties. All ﬁlms were kept at dry conditions (under 40% RH)

through nitrogen gas purging for 2 min and sealed in aluminum laminated pouches after

they were made. All packaged sample ﬁlms were stored at 23 °C. Each sample was

collected by cutting ﬁve pieces from the ﬁlm after unwinding 2 m of each stored ﬁlm.

65

3.2.2. Evaluation of appearance and optical properties
3.2.2.1. Microscopy

Although the manufacturer claims that '1 g of oxygen scavenger material can
remove 18 cc of oxygen, the efﬁciency can be reduced due to particle agglomeration
(Brody et al., 2001). Therefore, it is necessary to determine the amount or presence of
agglomeration in the ﬁlm before performance tests. The testing method was to count the
numbers of agglomerates in 5 samples (10 cm x 10 cm) which were cut randomly from
the ﬁlm. Agglomerations and the detailed images of the agglomeration were captured
with a stereo microscope (Model SMZ-U, Nikon, Japan) equipped with a 35 mm camera.
A 2x objective lens at 10 x zoom magniﬁcation and 2.5 x camera relay gave a 50 x ﬁnal
magniﬁcation of the samples. A stage micrometer was used to measure sizes of the

images.

3.2.2.2. Scanning electron microscopy (SEM)

A scanning electron microscope (SEM), model 2020 conﬁgured with a lanthium
hexaboride (LaB6) ﬁlament, manufactured by ElectroScan (FEI company, Hillsboro,
Oregon) was used to observe the morphology of multi-layer ﬁlms incorporating oxygen
scavenging material in the middle layer. The acceleration voltage ranged between 10 and
20 KeV, while the water vapor pressure ranged between 2 and 3 Torr. The specimens

were examined in their natural state (no conductive coating).

3.2.2.3. UV/VIS spectrometer
In order to compare the transparency (% light transmission) between oxygen

scavenging ﬁlms, the transmission of visible and UV light was measured with a Perkin

66

Elmer Lambda 25 UV/VIS Spectrometer from Perkin Elmer, Wellesley, MA. The
samples were measured from 190 nm to 800 nm using an integrating sphere, and scan
speed was 480 nm/min. Samples used ﬁlms E and F. LLDPE ﬁlm was used as a control

sample.

3.2.3. Evaluation of thermal properties
3.2.3.1. Differential Scanning Calorimetry

A differential scanning calorimeter (DSC Q 100, TA Instruments, DE) was used
to determine the thermal transitions of ﬁlms E and F containing oxygen scavenging
materials according to ASTM D-3418, and then calculate the % crystallinity, which may
inﬂuence the rate of migration. These experiments were performed at a heating and
cooling rate of 10°C/min from -80 °C to 180 °C using henneticalIy-sealed aluminum pans.
The weight of the samples was approximately 8 mg and the nitrogen gas ﬂow rate was 70 .

ml/min.

3.2.3.2. Thermo Gravimetric Analysis

A thermo gravimetric analyzer (TGA 2950, TA Instruments, DE) was used to
determine the weight of the iron powders in the oxygen scavenging materials in ﬁlms E
and F, and LLDPE ﬁlm was used as a control. The initial weight of the samples was
approximately 3 mg. Experiments were performed in platinum pans at a ramp rate of

10 °C /min under nitrogen purge ﬂow (70ml/min) from room temperature to 600 °C.

3.2.4. Mechanical properties

The tensile strength, modulus of elasticity and the percent elongation of different

.67

ﬁlm samples, which were composed of LLDPE, 081 and 082 ﬁlms, were measured by a
Universal Tester (lnstron) model 5565 (Norwood, MA). Five specimens of each ﬁlm
were used, and the testing procedure was performed in accordance with the ASTM
standard method for thin plastic ﬁlm (D882A - 97). A sample width of 1 inch and initial

grip gap of 2 inches with a grip separation speed of 20 in/min were used.

3.2.5. Oxygen absorbing capacity

Samples that were made of 50/50 (oxygen scavenging material/LLDPE resin),
30/70 and 20/80 blends in the core layer of the ﬁlms were prepared by cutting and
weighing 4.0 g of ﬁlm. The ﬁlm was folded and placed in a clean pint (550 cc) glass
canningjar. A 1 ounce (35 m1) wide mouth vial containing 15 ml of deionized water was
added to produce 100 % relative humidity in the jar. An upper glass bowl was capped
with a sealing lid that contained a septum. The upper bowl and Iowerjar were tightly
sealed to each other with grease oil and a stainless steel band [Figure 1 I]. The oxygen
content in the air on day 0 was tested and recorded by extracting air from the cap through
a septum in the seal lid. The oxygen content in the jar was tested and recorded using an
Oxygen Headspace Analyzer Model-3500 (Illinois Instruments). The jar with the test ﬁlm

and water vial was stored at 22 °C for 30 days.

68

     

Cap with seal lid
containing a septum

l/
.1188 bowl
. ' \ 2‘: 5‘

Figure 1 1. A pint canning jar to measure the oxygen absorbing capacity

3.2.6. Statistical Analysis

Statistical evaluation ofthe data was performed using SPSS (SPSS Inc., 2004).
Signiﬁcance levels were reported at the 95 % conﬁdence level (p < 0.05) using Tukey’s
honestly signiﬁcant difference (HSD) multiple comparison. The results of statistical

analysis are shown as mean values :1: standard deviation.

69

3.3. Results and discussions

3.3.1. Appearance and optical properties
3.3.1.1. Agglomeration in ﬁlms

Since the capacity of oxygen scavengers is affected by the presence of
agglomerates in the ﬁlm, the ﬁrst task was to determine the presence of agglomerations
in the ﬁlms. Agglomerations appeared as black spots in sample ﬁlms.

From Figure 12, it can be seen that the ﬁlms that were made from HDPE resin all
had small or big black spots. The black spots in ﬁlm A were larger and more numerous
than in any other samples. In the center of the picture is shown the agglomeration
magniﬁed 400 times. The black spots in the ﬁlm D that used only 25 % of oxygen
scavenger materials (081) were very small in size, but still present. From the ﬁlms A, B,
C and D, the higher the content of oxygen scavenger materials, the more agglomerations
were generated in the ﬁlms. In case of the ﬁlm B that was made of 60 % HDPE with
40 % oxygen scavenger material (08 l ), small or big black spots were observed, even
after melt-blending the polymer in a co-rotating twin screw extruder for better dispersion
of the oxygen scavenging material. Films E and F were produced at the same production
conditions and same base material (50% of LLDPE resin), but used different oxygen
scavenging materials (081 and 082). While the black spots appeared in ﬁlm E, they

were not observed in ﬁlm F.

70

 

Black spots in O : agglomerations of particles
Figure 12. Agglomerations in various oxygen scavenging ﬁlms

Consequently, it seems that 082 is preferred to make a blown ﬁlm at the selected
conditions. Studies on improving the process conditions or techniques related to 081 are
left for future work. As a result, ﬁlm F was adopted as the oxygen scavenging ﬁlm to

make the active packaging for this project.

3.3.1.2. Total thickness of ﬁlms

The average total thickness of the LLDPE ﬁlms was 135.9 umum and-the standard
deviation was 5.92 am. The thickness of 082 was in the middle as 131.7 i 7.062 11111
among the three ﬁlms, and 081 had the lowest average total thickness, 126.2 um i 12.89

am. While the thickness of 082 was not signiﬁcantly different from either 081 or LLDPE.

71

the thickness of 081 was signiﬁcantly less than that of LLDPE ﬁlm. Moreover, the
standard deviation of 081 was almost two times that of the others (LLDPE and 082)
[Table l 1]. Considering they were made under the same process conditions, the increased
thickness variation of 081 might result from lack of uniform thickness in the bubble

foam due to agglomerations of oxygen scavenging materials in the ﬁlm E.

Table l 1. Total thickness of LLDPE, 081 and 082

 

 

 

Sample Film Total thickness

(mil) (74m)
LLDPE Control 5.35 i 0.233 a 135.9 i 5.92
051 Film E 4.97 i 0.507 b 126.2 d: 12.89
052 Film F 5.17 :1: 0.309 ab 131.7 i 7.06

 

Mean :1: standard deviation, n = 30
Different letters within a column are signiﬁcantly different (p < 0.05)

3.3.1.3. Morphology ofthe ﬁlm
A cross-sectional image of ﬁlm F is shown in Figure 13. The ﬁlm consists of

LLDPE (31 um)/LLDPE + 082 (74 tutti/LLDPE (32 m) and its total thickness was 137
run. This sample was somewhat thicker than the average total thickness of ﬁlm F, but it
was within i lo. The particles of oxygen scavenger were well dispersed in the LLDPE

matrix layer and most of the particle sizes were smaller than 10 ,um.

72

LLDPE / LLDPE-19082 l-LLDPE‘
(31.1m) (73.8741) (3.2.2118)

 

Figure 13. Cross-sectional image of ﬁlm F: The middle layer is 50 wt% of082 resin
mixed with 50 wt% of LLDPE resin.
3.3.1.4. Transparency
LLDPE (Control ﬁlm), 081 (Film E) and 082 (Film F) were scanned from 190
am to 800 nm by a UV/VIS spectrometer. with scan speed of480 nm/min. The value of
each sample is shown in Figure 14. LLDPE shows the highest value in % light
transmission, and the value of 082 was much lower than 081. After 400 nm, while
LLDPE shows around 95 %, 081 shows near 80 % but 082 shows below 40 %.
One more interesting thing is that while the average % light transmission of 081
was a little lower than that of LLDPE, the value of 082 was much lower than that of 081
or LLDPE. It seems that the transparency of 082 was dramatically reduced by the good
dispersion of oxygen scavenger without any agglomeration and the bigger particle sizes

than those ofOSI, which can interrupt the light transmission [Figure 15].

73

 

 

 

 

‘
v-ooon.oo.uoo

 

— LLDPE
OS 1
082

 

 

 

 

 

. w
6‘ ‘
00".” MW
u
1...... x1
00‘.
n- n
_
m m m

gov ooﬁﬁﬁmﬁﬁ.

 

800

700

600

500

400

300

200

Figure 14. % light transmission of LLDPE, 081 and 082

Particle of oxygen scavenger

(Un1t: 10’l um)

 

082 ﬁlm

Figure 15. Dispersion state and particle sizes of oxygen scavengers in 081 and 082 ﬁlm

081 ﬁlm

74

3.3.2. Thermal properties
3.3.2.1. Tg, Tm, and Crystallinity

Using a differential scanning calorimeter (DSC Q 100, TA Instruments, DE), the
Tm was determined. The Tm of 081 was 124.04 C, and Tm of 082 was 123.79 °C [Figure
16]. The values of Tm for the two oxygen scavenging ﬁlms (081 and 082) were nearly
the same. The Tg was not measured because it is below the -80 °C limit of the system.

As crystallinity generally inﬂuences the permeability, the approximate percent
crystallinity of 081 and 082 can be calculated from measurements of the heat of fusion

made using DSC (Selke et a1, 2004). The crystallinity of 081 was 25.6% and for 082

was 30.8%. The equations for percent crystallinity of 081 and 082 are as follows:

 

 

Percent crystallinity of 081 = AHﬂ x100 = 2317- x 100 = 25.6% (3.9)
AHf* 286.2

Percent crystallinity of 082 = AHf2 x100 = ﬂx 100 = 30.8% (3.10)
AHf* 286.2

where, AHfl : Heat of fusion ofthe sample (081)
AHf2: Heat of fusion ofthe sample (082)

AHf * : Heat of fusion of 100% crystalline LLDPE (286.2 J/g)

The value of 081 (25.6%) in percent crystallinity is lower than 082 (30.8%).
This may be related to decrease mechanical orientation due to the inefﬁcient bubble foam

caused by agglomeration in the blown ﬁlm process.

75

 

 

 

 

 

 

 

       
    

 

   

 

 

 

 

 

051.001
.---- 052.001 -
"0'9“: 110.36‘C
(051) (082)
1..
1
103 L
E 1 .
v 1 ' (052) (05')
3 0- Q 115.97°c 119.41°c
u. _ __ _ 88.07Jlg 73.3719
‘66 .._
Q)
I
Melting
-1~
J
124.04°c 123.79%
1
(081) (052)
-2 ...,...,...,...T...,...
-100 -50 0 50 100 150 200

Temperature (°C)

Figure 16. DSC chart of 081 and 082

3.3.2.2. Thermo gravimetric analysis (TGA)
From the TGA data in Table I2 and Figure 17, 0.29% by weight of components in

082 were lost at 444.92 °C , and at 575.09 C only 8.43% (0.242 mg) remained as residue.

The peak gravimetric loss rate was at 530.88 °C (2.461 %/°C ). The residue of 081 was

76

10.63%, but that of the ﬁlm control was 1.42%. Therefore, the residual materials in the
081 and 082 above those of the ﬁlm control (LLDPE) were about 7 ~ 9%. These major
residual materials are assumed to be ferrous components because it is known that the
oxygen scavenging compounds consist of about 7 ~ 10 weight percent of iron
components in a base polymer such as polyethylene or polypropylene (Brody et a1. 2001).
The thermal degradation of LLDPE and other additives started in the range of 400 ~

410 °C and was complete at around 570 °C. The peak points of gravimetric loss in OS 1 ,
082 and the control were located in the range of ~545 - 550 °C and the rates were ~2.2 -

2.5 %/°C.

Table 12. TGA data for LLDPE, 081 and 082

 

 

 

Sample Gravimetric Loss Peak Gravimetric Loss Residue
Size Temp Loss Temp Loss-rate Temp Residue-rate Residue
(mg) (°C) (%) (°C) (%/°C) (°C) (%) (mg)
LLDPE 2.90 448.35 0.25 546.24 2.566 571.22 1.422 0.0374
081 3.90 406.33 0.23 549.36 2.171 574.28 10.630 0.4145
082 2.87 444.92 0.29 550.88 2.461 575.09 8.430 0.2419

 

77

 

 

 

 

Weight (%)
8

 

 

 

 

v 1 1 1 I r r r I 1 r I I

1 100 200 300 '
Temperature (°C)

1) 081 residue: 10.63%
2) 082 residue: 8.43%
3) 08c (LLDPE) residue: 1.422%

Figure 17. TGA chart to compare with LLDPE, 081 and 082

78

 

Deriv. Weight (%/°C)

3.3.3. Mechanical properties

The tensile strength in the cross direction (CD) and machine direction (MD) of
LLDPE ﬁlms, which was used as a control sample to compare with the ﬁlms E and F,
were 385.91 kg/cm2 and 379.41 kg/cm2 respectively, and the break elongation in CD and
MD of LLDPE ﬁlms were 929.7% and 913.9% respectively. Therefore, there were no

signiﬁcant differences between the two directions in LLDPE ﬁlms (p 2 0.05, n = 5).

However, the tensile strength in CD and MD of 081 ﬁlms decreased to 228.95 kg/cm2
and 241.80 kg/cm2 respectively, and the elongation at break in CD and MD of 081 ﬁlms
also decreased to 700.8% and 612.3% respectively. The differences in these values
between LLDPE and 081 were signiﬁcant (p < 0.05, n = 5). For the 082 ﬁlm, the values
of tensile strength in CD and MD were 262.61 kg/cm2 and 309.74 kg/cm2 respectively,
and the average elongation at break in CD and MD were 759.2% and 707%, which were
also signiﬁcantly decreased from those of LLDPE ﬁlms (p < 0.05, n = 5). Consequently,
the decrease of values for 081 and 082 may be inﬂuenced by the presence of inorganic
materials such as ferrous or ferrous oxides in the ﬁlm. One more interesting thing was
that the differences between the values of 081 and 082 for MD were signiﬁcant (p <
0.05, n = 5). The agglomeration in the 081 ﬁlm seemed to affect the decrease of these
values. Break strength also showed similar results, as shown in Table 13.

The decrease of values for 081 and 082 compared with LLDPE might be
inﬂuenced by the presence of inorganic materials such as ferrous compounds in the ﬁlm.

The value of 081 was overall lower than 082, due to the agglomeration in the 081 ﬁlm.

79

Table 13. Mechanical properties in LLDPE (Control), 081 (Film E) and 082 (Film F)

 

Sample Film Tensile Break Break
Direction Strength Strength Elongation
(kg/cmz) (kg/emf") (%)

 

LLDPE CD 385.91 :1: 26.043 a" 344.92 i 26.017aD 929.7 :5 36.143”
MD 379.41 21% 25.237 ‘0 339.13 :1: 24.327 ‘1’ 913.9 i 24.89 ”’

os1 CD 228.95 1: 7.969 bE 189.91 :1: 28.279 b“ 700.8 :1: 10.98 b“
MD 241.80 3: 12.626 3‘3 194.42 3: 12.390 3“ 612.3 1: 11.06 3*

082 CD 262.61 1: 13.355 “3 219.54 :t 13.291 b“ 759.2 3: 20.27“5
MD 309.74 i 16.6403F 264.13 i 19.8143F 707.3 d: 14.66 3“

 

Mean :1: standard deviation, n = 5
Different letters or numbers (a through c for CD; 1 through 3 for MD; D through G for
between CD & MD) within a column are signiﬁcantly different (p < 0.05)

3.3.4. Oxygen absorbing amount of multi-Iayer ﬁlm

The amount of oxygen absorbed was evaluated for 081 and 082 multi-layer ﬁlms
incorporated with 20%, 30% and 50% oxygen scavenging (OS) material. From Table 14,
the 0 day concentration was calculated as 20.9% oxygen, the same as the oxygen
concentration in ambient air. The amount of oxygen in thejar was calculated by
multiplying 20.9% by the volume of the jar. The 30 day concentration was measured by
oxygen headspace analyzer, and the amount of oxygen was also calculated.

After 30 days at room temperature (23 °C) and 100% humidity, the oxygen

absorption was 5.68 cc/g of ﬁlm at 50% 08 content, 3.36 cc/ g at 30% and 2.24% at 20%
in the 081 ﬁlm. This showed that the oxygen absorption increased at almost the same

ratio as the oxygen scavenging content as was expected. The results for the 082 ﬁlm

80

were similar as the average oxygen absorbing amount of 082 was 6.10 cc/g, but it was
signiﬁcantly different (p < 0.05, n = 3) from the value for 081 ﬁlm. It seemed that the

agglomeration of oxygen scavenging material in the 081 ﬁlm reduced the amount of

oxygen absorbed.

Table 14. Amount of oxygen absorbed

 

 

 

 

 

 

 

 

Film 08 0 day 30 day ‘ Absorbed 2 Film 3 Absorbed 4 02
content 02 02 02 weight 0; amount absorb.
amount amount amount /fi|m weight ratio
cc/jar cc/jar cc g cc/ g %
081 50% 201.5 178.7 22.8 4.01 5.68a 50.7
30% 199.1 189.0 10.1 3.01 3.36 29.9
20% 205.0 198.3 6.7 2.99 2.24 20.0
082 50% 201.9 177.5 24.4 4.00 6.101) 50.4
30% 199.3 188.4 10.9 3.00 3.63 30.1
20% 203.3 196.0 7.3 3.02 2.42 20.0

 

 

 

 

 

 

 

 

 

 

I Absorbed 0; amount: 30 day 02— 0 day 02 = 201.5 — 178.7 = 22.8 cc

2 Film weight: The weight of 08 ﬁlm that was inserted in thejar.

3 Absorbed Oz amount/film weight

4 O2 absorb. ratio: It is made to evaluate the change of 02 absorbing ratio to compare
with the change of 08 content.

- The values of absorbed 02 amount per ﬁlm weight in 20% of 081 or 082 are
considered as 20.0% (02 absorb. ratio), the value of absorbed 02 amount per ﬁlm
weight in 50% of 081 is calculated as follows:

081-50% (5.68)/OSl-20% (2.24) x 20% = 50.7%
Different letters (a through b) within a column in 50% of 081 and 082 are signiﬁcantly
different (p < 0.05).

81

3.4. Summary

Development of a multilayer ﬁlm incorporating iron based oxygen scavenger was
done successfully and the 082 ﬁlm was preferred to adopt as an oxygen scavenging ﬁlm
to make an active packaging. The conclusion of development of the project can be
summarized as follows;
1) Agglomeration in the ﬁlm

All ﬁlms except F (082) were observed to have various sizes of agglomeration
generated during the blown ﬁlm process, which increased when the content of oxygen
scavenger was increased or HDPE resin was used instead of LLDPE resin. Therefore,
ﬁlm F, which was made of 082 mixed with LLDPE resin and produced by the blown
ﬁlm process at the selected conditions, was preferred to other ﬁlms based on amount of
agglomeration.
2) Optical properties

LLDPE shows the highest value in % light transmission, and the value of 082
was much lower than 081. After 400 nm, while LLDPE shows around 95 %, 081 shows
near 80 % but 082 shows below 40 %. Especially, the value of 082 was much lower
than that of 081 or LLDPE. It seems that the transparency of 082 was dramatically
reduced due to the good dispersion of oxygen scavenger without any agglomeration and
the bigger particle sizes than those of OS 1 , which can interrupt the light transmission.
3) Thermal and mechanical properties

The value of 081 (25.6%) in percent crystallinity is lower than 082 (30.8%).
This may be related to decrease mechanical orientation due to the inefﬁcient bubble foam
caused by agglomeration in the blown ﬁlm process. From the TGA analysis, the residual

materials in the 081 and 082 ﬁlms were about 7 ~ 9% above the value of residue in

82

LLDPE. These are assumed to be ferrous components because they are major

components in the oxygen scavenger and are not volatilized at 600 °C.

For the mechanical properties such as tensile & break strength and break
elongation, the decrease of value for 081 and 082 compared with LLDPE might be
inﬂuenced by the presence of inorganic materials such as ferrous compounds in the ﬁlm.
The value of 081 was overall lower than 082. It might result from lack of uniform
thickness in the bubble shape due to agglomerations in the blown ﬁlm process.

4) Oxygen absorbing amount

The oxygen absorbing amounts of all 081 and 082 ﬁlms increased at almost the
same ratio as the oxygen scavenging material contents. Therefore, the oxygen scavenging
effects of the ﬁlms were useful even though it had a multilayer structure containing
coextruded LLDPE on the inside of the ﬁlm. The 082 ﬁlm was a little better (p<0.05)
than that of the 081, consuming 6.10 CC/Og per g ﬁlm after 30 days storage at room

temperature (23 °C ) and 100% RH, because agglomeration in 081 ﬁlm resulted in a

decrease of oxygen uptake.

83

3.5. References

Ball G.F.M., Vitamins in Food: Analysis, Bioavailability, and Stability, CRC Press.
Taylor & Francis Group, Boca Raton, FL, pp. 39-51, 2006.

Barua, AB. and CF. Harold, “Properties of retinols,” Molecular Biotechnology, '10: 167-
182, 1998. http://www.springerlink.com/content/b234wu0tl h607 l 82/

Brody, A.L., E.R. Strupinsky, Kline L. R., Active Packagingfor Food Applications.
Technomic Pub., Lancaster, PV, PP. 1 1-86, 2001.

De Jong, A.R., H. Boumants, T. Slaghek, J. Van Veen, R. Rijk, & M. Van Zandvoort,
“Active and intelligent packaging for food: Is it the future?, ” Food Additives and
Contaminants, 22: 975-979, 2005.

Foltynowicz, Z., W. Kozak and R. Fiedorow., “Studies of Oxygen Uptake on O2
Scavengers Prepared from Different Iron containing Parent Substances”, Packaging
Technology and Science, 15: 75-81, 2002.

Ozdemir, M. and JD. Floros, “Active Food Packaging Technologies, ” Food Science and
Nutrition, 44: 185-193, 2004.

Selke, Susan. E.M., John D. Culter, Ruben J. Hernandez, Plastic Packaging, 2nd Hanser
Pub., Munich, pp. 63-72, 2004.

Robertson, G.L., Food Packaging: Principles and Practice, 2nd ed., Taylor & Francis/
CRC Press, Boca Raton, FL, pp. 285-31 1, 2006.

84

4. DEVELOPMENT OF ACTIVE PACKAGING

4.1. Introduction

In recent times, co-extruded multilayer containers that incorporate ethylene vinyl
alcohol (EVOH) or other plastic barrier tubes have been widely used in food, health care
and cosmetic packaging. However, EVOH has some limitations for moist products due to
its sensitivity to humidity, and plastic barrier materials such as SiOx or A1203 coated ﬁlm
also have some limitations at protecting from photo-degradation caused by UV light
(Rooney and Yarn, 2007). Furthermore, they have critical problems that are the presence
of oxygen in the product itself and the residual oxygen of the headspace in the package
(Brody at al., 2001). In particular, it is extremely difﬁcult to control or remove the
oxygen in the headspace by nitrogen gas ﬂushing during a ﬁnishing process such as tube-
sealing in the cosmetics industry.

The oxygen in the headspace of the packaging and in the product itself or
transmitted light can cause not only reduction of retinol content, but also off-ﬂavor, color
change, and increased microbial growth (Ball, 2006; Barua and Harold, 1998). For these
reasons, packaging containing aluminum foil was designed, instead of plastic barrier
materials, to protect perfectly from the sunlight and the outside oxygen. Additionally, as
active packaging, a ferrous based oxygen scavenger material that is incorporated into the
core-layer of a three-layer blown ﬁlm was contrived to solve the problem in conventional
co-extruded multi-layer barrier containers or other passive packaging through absorbing
the oxygen inside the packaging [Figure 18]. Thus, the ﬁrst objectives of this study are:
1) Development of an oxygen scavenging ﬁlm

- To set up a proper multilayer structure and process conditions

85

- To have the best value for mechanical, optical and thermal properties
2) Development of an active package for cosmetics
- To evaluate the performance of the oxygen scavenger in reducing oxygen
concentration in the headspace of active packages, compared with conventional
packages

- To evaluate extension of shelf life through the evaluation of retinol content in

 

 

 

 

 

 

 

 

 

 

 

 

 

cosmetics.
Conventional Passive Packaging Active Packaging
Outside Inside Outside Inside
02 B 02 02 B if?-
ﬁ’éi . A L/» . B A; 841$
IR! \\j[ . / R __
1F 0 . I 02
. ' . ‘ R
0 R O 0 a
Light F . C ‘3
. _ 0 E . 11
1%. P 3 Light 7 M
B 0 H P ' P
O: . 51* 0 iii 0
9 I 0
Oxygen
Scavenger

EVOH: Ethylene Vinyl Alcohol
PO: Polyoleﬁns group

Figure 18. Design of active packaging for cosmetics

86

4.2. Materials and methods
4.2.1. Package design

Figure 19 shows the structure of the package designed for this project. In order to
perfectly protect against degradation of retinol components by light and oxygen from
outside conditions and keep moisture in the inside of the package for activation of the

oxygen scavenger, 16 ,um thickness of aluminum foil was used as a barrier material in the

active packaging system. The 082 ﬁlm was selected for the active component, because it
did not have any agglomerations, so it was expected to have better printability,
mechanical properties and oxygen scavenging capacity. For good sealing, a mono-layer

LLDPE ﬁlm, thickness 30 um, made by a blown extrusion ﬁlm line, was co-extruded on

both the outer layer and the inner layer. The LLDPE ﬁlm of the outer layer and the
adjacent PET ﬁlm as well as the PET ﬁlm and the aluminum foil were dry laminated
(Okazaki, Japan) with a polyurethane based adhesive (AD® 502, Toyomorton). The
aluminum foil was extrusion laminated (Sumitomo, Japan) to the coextruded oxygen
scavenger ﬁlm with an adhesive that is a copolymer of ethylene and acrylic acid

(Nucrel® 30707, DuPont). The 25 um biaxially oriented polyester ﬁlm (Hyosung, Korea)

was used to obtain the desired stiffness. The design of the active packaging and laminated
structure can be found in the patent for “laminate for cosmetic tube with oxygen

absorbing function” (Shin, et al., 2006).

87

  
 

I.I.I)PF. — ()utcr (30pm)

Dry Lamination 1

 

 

Q PET (251m) .
5 2:35., Dry Lamination 2
Aluminum (161ml)
EAA (25m) Extrusion
Lamination

LLDPE (30pm)

 

LLDPE- Inner (30 um)

Figure 19. Desired structure of active packaging and lamination processes

4.2.2. Tube production

The roll of active packaging in Figure 20 was printed with a 6 color offset printer
(Komori, Japan) using UV inks (Toyo Ink, Japan). The second step was to make a tube
by folding the roll and sealing the seam area, and then the mouth part was inserted into
the tube and sealed. The next step was an external coating with 150 to 200 ,um of
polyethylene on the ‘LLDPE-Outer’ layer in Figure 18. Then ﬁnally a closure was

attached to the tube in the customer’s packaging line.

88

 

   

Tubing machine (Aisa. Switzerland) Final product

Figure 20. Tubing & over-coating process

4.2.3. Evaluation for residual oxygen in the headspace of packaged products

The trends in reduction of oxygen concentrations in the headspace of packages
that were ﬁlled with real cosmetic products were measured as an evaluation method for
performance of the oxygen scavenger. The oxygen concentration was measured at the tail
of the tube, and samples were withdrawn at a rate of 40 ml/min, and then passed by the
oxygen sensor using an Oxygen Headspace Analyzer Model-3 500 (Illinois Instruments).
Two kinds of packages were evaluated. One was a package that was laminated with the
082 ﬁlm, the other sample (control sample) was made of LLDPE mono-layer ﬁlm
instead of the oxygen scavenging ﬁlm (082). Samples were all stored in a chamber at
23 °C. 65 % RH. Tests were performed at 7, 30, 60, 90, 120, 150 and 180 days after

ﬁlling with real cosmetic products.

89

4.2.4. Evaluation of the shelf life of retinol in products
4.2.4.1. Reagents and apparatus

The products containing retinol were supplied by Amore Paciﬁc. Standard retinol
(99.0 %), 2-propanol, dimethylformamide (DM F), and methanol were obtained from
Sigma. Distilled water used was HPLC grade from J .T. Baker. A 100 ml amber
volumetric ﬂask, 10 ml pipet, sonicator and magnetic stirrer were also used. An HPLC
system (Waters Corporate, Watford, UK) consisting of a separation module (Waters
2695) with UV detector (Waters 2487), C18 column with inside dimensions of 150 x 5

mm (Waters) and 0.45 pm micro-ﬁlter (Fisher Scientiﬁc, PA), were used for analysis of

the sample solutions.

4.2.4.2. Sample handling
As retinol is easily degraded by sunlight, heat and oxygen, all handling and
experimental procedures were carried out away from direct sunlight, and samples were

stored at under 4°C in a refrigerator. All experiments were replicated ﬁve times.

4.2.4.3. Calibration of standard solution

Stock solutions of standard retinol were prepared by dissolving 10 mg in 100 ml
of 2-propanol in an amber volumetric ﬂask. Working standard solutions were prepared by
dissolving each volume (1 , 4, 10 and 30 ml) from the stock solution in 100 ml of 2-
propanol as the I", 2'”, 3rd and 4th working standard solutions. Using the 2nd working
standard solution, the exact concentration was determined spectrophotometrically
(UV/V18 Spectrometer from Perkin Elmer, Wellesley, MA) at 325 nm. After testing the

four working standard solutions by H PLC, the standard calibration curve was constructed

90

by calculating the area response (AU) of the peak [Figure 21] for each working standard

solution (mg/100ml). The standard curve is shown in Figure 22.

 

    

 

 

 

 

1
0.0025 -1 3338
(AU)
0.0020 1 I
1
0.0015 . j
:3. j I 1‘
< 51 1
0.0010 . I l
l
l j I
00005 . - , l
I '° °‘.
0 . c. a - ,
‘ ' ' T I Y 7 f‘ I Y Y W Y I ﬁ' 1 T f I T I v Y r v V V Y I v T v v I
min 1.00 2.00 3.00 4.00 5.00 6.00 7.00

Figure 21. The area response in peak ofa working standard solution of retinol in HPLC

 

 

 

 

 

40000
y = 11294..- + 919.79
30000 _ R2 = 0.9997
0’
(I)
C
O
3' 20000
2 r-
(0
0
h
<
10000 -
0 1 1 1
0 1 2 3

Concentration (m 9” 00m L)
Figure 22. Standard calibration curve of retinol in HPLC

91

4.2.4.4. Sample extraction

Stock solutions of real products (samples) containing retinol were prepared by
dissolving approximately 2 g in 20 ml of dimethylformamide (DMF) in an amber 100 ml
volumetric ﬂask, because DMF is very useful for dissolving cream products that contain
lots of oil or wax mixed with retinol. After dissolving the stock solutions for 10 minutes
with a sonicator, a working solution was prepared by dilution to 100 ml with HPLC grade

methanol, and mixing by magnetic stirrer for 30 minutes. The sample solutions were all

prepared to inject into empty amber glass bottles using a 0.4 pm syringe ﬁlter.

4.2.4.5. Calculation for content of retinol in sample solutions
Retinol in the sample solutions was analyzed using a Waters’ HPLC system. The

mobile-phase solution was methanol and distilled water (93:7), with injection volume
10 7d, and ﬂow rate 1.0 ml/min. The retinol concentration was determined using a UV

detector at 325 nm. The content of retinol in sample solutions was determined by the

following equation:

(Rs 1819.79)
Cst x 3333(lU/mg) _ 11234

Csa 2

x3333

 

 

 

Content of retinol (lU/g) = (4.1)

where Cst = retinol concentration of standard solution (mg/100ml)
Csa = retinol concentration of sample solution (g/100m1)
R5 = response area for the sample (area unit: AU)

1 mg retinol = 3333 1U, l 1U = 0.300 ug

92

4.2.5. Statistical Analysis
Statistical evaluation of the data was performed using SPSS (SPSS Inc., 2004).
Signiﬁcance levels were reported at the 95 % conﬁdence level (p < 0.05) using Tukey’s

honestly signiﬁcant difference (HSD) multiple comparison. The results of statistical

analysis are shown as mean values i standard deviation.

93

4.3. Results and discussions
4.3.1. Oxygen concentration in the headspace of packaged products

Figure 23 shows the trend of oxygen concentration in the headspace of packages
ﬁlled with a real cosmetic product during 180 days at room temperature. The
conventional packaging samples (Control: LLDPE) consisted of packages laminated with
linear low density polyethylene monolayer ﬁlms, and active packaging samples (Active:
08) were made of packages laminated with the ﬁlm F that contained oxygen scavenger.
While the average oxygen concentration in the headspace of OS was rapidly reduced to
3.42 % at 7 days and reached 0.00 % within 30 days, that of LLDPE had a much higher
level of over 12.58 % at 30 days and 9.50 % at 150 days. Furthermore, the value ofOS
continued to be at 0.00 % to 120 days and was only 0.01 % at 150 days. This means that
08 was effective in oxygen scavenging. Table 15 shows the oxygen concentration data

for LLDPE and OS and results of statistical analysis.

Table 15. Trends of oxygen concentration in headspace of both control and active
samples (stored at 23 °C , 65 % RH)

 

Sample 0 day 7 day 30 day 60 day 90 day 120 day 150 day 180 day

 

LLDPE Avg 20.07 16.68 12.58 10.63 10.07 9.79 9.50 9.29
(Control) Std 0.125 0.374 0.589 0.423 0.342 0.325 0.275 0.235

Dev a1 a2 a3 a4 a4,5 a4,5 a5 a5
08 Avg 20.12 3.42 0.00 0.00 0.00 0.00 0.01 0.01
(Active) Std 0.120 0.540 0.000 0.000 0.000 0.000 0.012 0.010

Dev a 1 b 6 b 7 b 7 b 7 b 7 b 7 b 7

 

Different letters (a through b) within a column are signiﬁcantly different (p < 0.05).
Different letters (1 through 5) within a row are signiﬁcantly different (p < 0.05). n = 3

94

25

 

 

 

 

 

 

 

 

+08
20 -O—LLDPE
S
8151
a
g
5
010-
C
O
U
C
01 5-
5"
>
X
0
o-
'5 I I I I I I I I T

 

O 20 40 60 80 100 120 140 160 180 200

Storage ﬁme (day)
Figure 23. Oxygen concentration trends in headspace (stored at 23 °C, 65 % RH);

08 was rapidly reduced to 3.42 % at 7 days and reached 0.00 % within 30 days, but
LLDPE had a much higher level of over 12.58 % at 30 days and 9.50 % at 150 days.

4.3.2. Shelf life of retinol in packaged products

For determination of the shelf life of real products containing retinol, active
packages were compared with conventional packages under the same conditions as
control samples. Figure 24 shows the trends of retinol content in cosmetics in both
conventional packages (Control: LLDPE) and active packages (Active: 08) which were
stored for 1, 2, 4, 8, l2 and 24 weeks at room temperature.

From Table 16, it can be seen that there were no significant differences between

the LLDPE and 08 samples in the ﬁrst and second week (p < 0.05, n = 3). However, at

95

four weeks, the difference between the two samples was signiﬁcant (p < 0.05, n = 3).
Moreover, at 24 weeks, the difference between the LLDPE and 08 sample was over 500
1U. Furthermore, the average value in OS of 3,019 IU at 24 weeks was more than that of
the LLDPE sample at 12 weeks. Therefore, it can be concluded that the shelf life of
retinol in the cosmetic was signiﬁcantly extended by the active package.

As it mentioned in the section of 1.3., retinol is a group of fat-soluble compounds

that has an unstable structure consisting of a B-ionone ring, a conjugated isoprenoid side

chain and a polar terminal group (-OH). Therefore, it is readily oxidized or isomerized to
altered compounds, especially in the presence of oxidants including air, and inﬂuences
such as light and heat. It is labile toward active components such as silica, strong acids
and solvents that have dissolved oxygen or peroxides (Ball, 2006; EGVM, 2003; Barua
and Harold, 1998).

From Figures 22 and 23, in spite of the fact that oxygen concentration in the OS
tube was maintained at 0.0% from 30 days to 180 days after 30 days, the retinol content
was still decreased. It seems that retinol was degraded not only by oxygen, but also by
acids in cosmetics additives, which can cause rearrangement of the double bonds and
dehydration. Silica, which is in direct contact with retinol, in additives of cosmetics or in
the inner layer of the OS tube and long storage conditions (6 months) at room

temperature (23 °C) also seems to cause the loss of retinol.

96

 

 

 

 

 

 

 

 

4000
+ OS
-0- LLDPE
3500 a
i
2':
C
0
E
O 3000 -
0
‘6
.E
H
O
D:
2500 -
2000 I I I I I
0 5 10 15 20 25 30

Storage time (week)

Figure 24. Trends for the loss of retinol content in cosmetics;
the difference between the LLDPE and 08 sample was over 500 IU at 24 weeks.

Table 16. Retinol contents vs. storage time FOR the conventional (Control) and active
package (08) samples. The structure of Control was LLDPE/PET/AL/LLDPE, and OS
was LLDPE /PET/AL/LLDPE +08 + LLDPE.

 

Sample 1 week 2 weeks 4 weeks 8 weeks 12 weeks 24 weeks

 

LLDPE 3,464 i 60 3.341 :t 56 3.245 :t 59 3,213 i 66 2,866 i 46 2,51 1 i 43

(Control) a 1.2 a 1,2,3 a 3 a 3 a 5 a 6
08 3,498 :t 58 3,458 3: 64 3,420 i 60 3,306 i 63 3,173 :t 56 3,019 3: 59
(Active) 3 1 a 1,2 b 1,2 a 2,3 b 3,4 b 4,5

 

Mean i standard deviation, n = 3, Unit : 1U

Different letters (a through b) within a column are signiﬁcantly different (p < 0.05).
Different letters (I through 6) within a row are signiﬁcantly different (p < 0.05).

97

4.3.3. Estimation of the extended shelf life of retinol in packaged products

To determine the effects of the extended shelf life of an active packaging using
oxygen scavenger, the trend line equation and R2 value was calculated using Micro Excel
of MS Ofﬁce 2004 program. Among the six types of trend lines (linear, logarithmic,
polynomial, power, exponential and moving average), the power equation was selected as
the best model. The best ﬁt equations and corresponding R2 value of the LLDPE and 08
samples are shown in Figure 25.

The end of shelf life is considered a retinol concentration of 2,500 IU. According
to the regulations of the FDA in Korea for functional cosmetics such as retinol cream, the
retinol cream should contain more than 90.0 % of the listed content of the retinol
(C20H300) as a major component, and the standard for a retinol cream by the Korean
FDA (2007-44) is 2,500 IU.

Therefore, the expiration data of the product in a conventional package (LLDPE)
is less than 6 months. The calculated time to reach 2,500 IU using the 08 package is 51.6

weeks (361 days), using the following equations:

—0.0065 x
y = 3496 e , and y = 2,500 IU (42)
2500
I" 3496
= — = 51 .6weeks (4-3)
— 0.0065

98

Retinal content (IU)

4000

 

     
 

 

 

 

 

 

 

 

-‘F-IDS
- -{F-LLDPE
y = 3496 e 0'00“"
35°° ' R2 = 0.9674
I . . . .
.
I I I . . . . .
3000 ~ ' . .
250° . y = 3469.8 9 .
R = 0.969
2000 l l I T- a
D 5 10 15 20 25 30

Storage time (week)

Figure 25. Trend line ofthe retinol content in cosmetics (stored at 23 °C , 65% RH)

99

4.4. Summary

Development and evaluation of the active packaging for cosmetics was done
successfully. While development of an active packaging was executed by converting
processes such as dry and extrusion laminating, evaluation was carried out through an
analysis for the oxygen concentration in the headspace of packaged products and
evaluation of the shelf life for retinol in the cosmetic. The conclusion of development of
the project can be summarized as follows;
1) Oxygen concentration in the headspace of packaged products

Oxygen in active packages was rapidly reduced compared to conventional
packaging, reaching 0.0% from the original 20.9% within 30 days when stored at 23 °C
and 65% RH, while the value in conventional packages still remained near 10.0% after
180 days.
2) Shelflife of retinol in cosmetics

While the retinol contents in conventional packages were rapidly reduced from
3,464 IU to 2,51 1 1U after 24 weeks when stored at 23 °C and 65 % RH, the value in
active packages reminded over 3,000 IU after 24 weeks. The percentage loss of retinol
was only 16.1 % after 24 weeks in active packages, but it was almost 2 times as much
30.3% after 24 weeks to compare with initial content (0 week) in conventional packages.

A shelf life of 51.6 weeks is estimated, based on reduction of retinol to 2,500 1U.

100

4.5. References

Amore Paciﬁc Corp., “Test method of retinol in product,” in test method (APTM 0189)
of R&D Center, 2006.

Ball G.F.M., Vitamins in Food: Analysis, Bioavailability, and Stability, CRC Press,
Taylor & Francis Group, Boca Raton, FL, pp. 39-51, 2006.

Barua, AB. and CF. Harold, “Properties of retinols,” Molecular Biotechnology. 10: 167-
182, 1998. http://www.springerlink.com/content/b234wu0t1h607182/

Brody, A.L., E.R. Strupinsky, Kline L. R., Active Packagingfor Food Applications,
Technomic Pub., Lancaster, PV, pp. 48-75, 2001.

EGVM (Expert Group on Vitamins and Minerals), “Safe Upper Levels for Vitamins and
Minerals,” Food Standards Agency (FSA), UK, PP. 1 10-126, May 2003.
http://wwwfood.gov.uk/multiinedia/pdfs/canapdf

Shin, Y.J., M.I. Kim and J.Y. Kim, “laminate for cosmetics tube with oxygen absorption
function,” Korean Application Number: 20-2006-0004013, 2006.

Rooney, M. L., and K. L. Yam, “Novel Food Packaging,” in J. Smith, 2nd ed., Technology
of Reduced Additive Foods, Blackwell Pub., Oxyford, UK, pp. 61-83, 2007.

101

5. RESEARCH FOR THE MIGRATION BEHAVIOR OF OXYGEN

SCAVENGER IN ACTIVE PACKAGING

5.1. Introduction

Consumers require to be assured that packaging is fulﬁlling its function of
protecting the integrity, freshness and safety of products. To guarantee and improve the
performance of the packaging, innovative active packaging concepts are being
successfully introduced and applied in the USA and Japan. However, in Europe, the
development and application of active packaging systems have been limited because of
legislative restrictions and fear of consumer resistance (De Kruijf et al., 2002). In other
countries such as Korea, there are not any regulations for these concepts and there is a
lack of knowledge about consumer acceptance of the systems. Furthermore, despite the
food or cosmetics industries’ concerns about whether the active ingredients migrating
from packages might be harmful, there are no regulations to limit their development.

The key regulatory issue is food-contact approval. It is often required because
active packaging may affect foods in two ways. Active packaging substances may
migrate into the food or may be removed from it. Migrants may be intended or
unintended. Intended migrants include antioxidants, ethanol and antimicrobial
preservatives which require regulatory approval in terms of their identity, concentration
and possible toxicology effects. Unintended migrants include various metal compounds,
such as iron based oxygen scavengers, that could enter foods. Food additive regulations
require identiﬁcation and quantiﬁcation of any such unintended migration (Day, 2003).
However, no speciﬁc regulations exist on testing the suitability of active packaging

systems in direct contact with foods and, in many cases, the testing protocols used are not

necessarily appropriate, being based on those developed for plastic packaging materials
(Robertson, 2006).

Currently, the most widely used active packaging system is probably the oxygen
absorber (Smith et al., 1995). This may be used in sachets, as adhesive labels,
incorporated in packaging such as ﬁlm, trays or other forms (Teumac, 1995: Brody et al.,
2001). Sachets containing active substances are often in contact with packaged foods,
giving rise to the possibility that their migration into the foodstuff might be signiﬁcant,
especially in the case of moist, fatty and/or acid foodstuffs (Ahvenainen and Hurme,
1997). Although there are many research papers that have been published on the
migration of plastic monomers and/or additives into foods or alternative food simulants
(e.g. Alnafouri and Franze 1999; O’Brien et al., 1999; Gilbert et al., 2000; O’Brien and
Cooper 2001; Riquet et al., 2001), there is only a small amount of literature on the
determination of migration from active packaging (Lopez-Cervantes et al., 2003).
Furthermore, it is even more lacking in the cosmetics and medical ﬁelds. Thus, the
second objectives of this work are:

1) To investigate the migration behavior of the oxygen scavenger incorporated in the
middle layer of multilayer ﬁlm, which is not in direct contact with the food simulants
in active packaging [Figure 26].

2) To quantify migration into a variety of alternative simulants.

103

Active Package

09900

   
  
 
   
 
    
   
 
  

Out Layer

   
 
     

NaCl
——>

08 LZII'H‘ F e(OH)2 + 1%: 02 + 1/2 H20

Fe(OH)2

 

 

Migration of Fe,
Na, C1 and other
components

Oxygen
Scavenger

  

Product

Figure 26. Migration from active packaging to cosmetics

104

5.2. Materials and methods
5.2.]. Migration components and behaviors
5.2.1.1. Materials
To investigate the various migration components and behaviors resulting from
activating of iron based oxygen scavengers, three samples were selected. The ﬁrst sample

was the 08 ﬁlm which had been stored for 6 months at room conditions of 23 °C and

65% RH, because the maximum stock period for empty packages is generally 6 months
before ﬁlling on the customers’ production line. According to the research by Lopez-
Cervantes for evaluating the migration of ingredients from active packaging and
development of dedicated methods: a study of two iron based oxygen absorbers (Lopez-
Cervantes J. et al., 2003), the migrant main elements were identiﬁed as Na, Cl and Fe,
and overall migration of them into 3% acetic acid was greater than into any other food
simulants such as 95% ethanol, olive oil and distilled water. Therefore, the second sample
was selected from the 08 ﬁlm after migration test with 3% acetic acid, which was stored

for 10 days at 40 °C after 6 months passed in room conditions of 23 °C and 65% RH.

Finally, an active package ﬁlled with real cosmetics, retinol cream, was selected after 6

months storage at room conditions after ﬁlling.

5.2.1.2. Sample preparation
All specimens were cut on the cross-section by Microtome (Model RMC Power

Tome XL, Boeckeler Instruments Inc., Tucson, AZ) [Figure 27-1] for SEM & EDS

analysis. The cutting operation was done by ﬂushing liquid N2 gas at - 120 °C, and the

operating temperature of the knife was - 55 °C. A glass type knife was used for cutting

the tube and a diamond knife was used for the ﬁlm. All cutting speeds were 0.7 mm/sec.

'1 05

After microtoming, the surface of the samples was coated with carbon—sputter by
a Carbon Coater (Model EFFA Mkll. Ernest F Fullam Inc., Latham, NY) [Figure 27-2].
This was used instead of the gold coating method that is generally used in analysis of
polymer, because the samples contained metal components in oxygen scavenger and gold
would make the analysis difﬁcult by absorbing a high percentage of the X-rays produced

and adding strong X-ray peaks to the spectrum.

   

Figure 27-1. Microtome Figure 27-2. Carbon Coater

5.2.1.3. SEM & EDS analysis

Scanning electron microscopy (SEM) and energy dispersive X-ray (EDS)
microanalysis was used to analyze the main components ofthe oxygen scavenger in the
specimens and observe migrant behavior in the inner layer which is in direct contact with
the food simulants or cosmetic, adjacent to the core layer in the specimens. after 6
months at room temperature. The SEM was model JSM - 6400 (JEOL. Japan) conﬁgured
with a lanthium hexaboride (LaB6) ﬁlament, and INCA X-sight 6506 (Oxford. England)

[Figure 28]. To get the best image SEM, Snapshot 3 was used, preconﬁgured to collect a

106

4096 x 3072 pixel image with a 50 11s pixel dwell time. The acceleration voltage was15

kV and vacuum was 10 '7 Torr. For EDS, the Analyzer Mode-quantitation was used with

an accelerating voltage of 20 Kv.

 

Figure 28. SEM & EDS

5.2.1.4. Identiﬁcation ofthe main elements of oxygen scavenger

Figure 29 and Figure 31 show a particle of oxygen scavenger in the cross section
of 081 and 082 ﬁlm, which were laminated in packages that had been stored for 6
months at room conditions (23 °C and 65% RH) after ﬁlling with real product. From the
sites of ‘Spectrum 1’ in the two ﬁgures, carbon (C), oxygen (0) iron (Fe), sodium (Na),
chloride (Cl), phosphorus (P), silica (Si) and potassium (K) were revealed [Figure 30 and
32-1]. To clarify the main elements, several analyses were executed, and calcium was
revealed additionally on the site ‘Spectrum 2’ in 082 ﬁlm [Figure 33-2].

Si was present in both 081 and 082 but in very small amounts as impurities and

107

was also detected in LLDPE ﬁlm without oxygen scavenger [Figure 33, 34-1 and 34-2]. P
was present only in 081, and Ca was present only in 082 [Figure 32-2]. Therefore, Fe,

Na and CI, in addition to C and O, are the main elements in these oxygen scavengers.

 

 

' 2011-111" ' 2 site 01 Interest 2 500x

Figure 29. Appearance of a particle of oxygen scavenger in 081 ﬁlm

108

 

3 3

3

1“-

aid 5

 

 

 

 

 

 

 

 

'081135235356055556691'75
mac-mi morn-0.1a (47a)

 

 

 

 

 

 

 

 

 

 

 

 

Element App Intensity Weight % Weight % Atomic %
Cone. Comp. Sigma

C K 56.38 0.5244 35.66 0.44 50.86
0 K 67.80 0.6462 34.78 0.33 37.24
Na K 5.37 0.5695 3.12 0.08 2.33
Si K 0.18 0.7841 0.08 0.02 0.05
P K 20.32 1.1957 5.64 0.07 3.12
CI K 0.60 0.7772 0.26 0.03 0.12
K K 0.32 1.0487 0.10 0.02 0.04
Fe K 51.00 0.8309 20.36 0.20 6.24
Total 100.00

 

 

 

 

 

 

 

Figure 30. All elements analysis on the site of Spectrum 1 in 081 ﬁlm

109

 

 

' pom ' SI site of interest 2 5000x
Figure 31. Appearance ofa particle of oxygen scavenger in 082 ﬁlm

 

500011111

935

3

 

 

 

V I V Y Y I I V V I V

, as 1 is 2 as 3 as i is s 55 6 es
1119:!th mom 0125124613] w

I
7

 

 

 

Figure 32-1. All elements analysis on the site of Spectrum 1 in 082 ﬁlm

110

 

 

 

 

 

 

 

 

 

Element App Intensity Weight °/o Weight % Atomic %
Conc. Comp. Sigma

C K 29.65 1.2621 71.04 0.49 78.55

0 K 29.23 0.3639 24.29 0.50 20.17
Na K 0.69 0.7534 0.28 0.05 0.16

Si K 0.39 0.9042 0.13 0.04 0.06
CI K 0.90 0.8301 0.33 0.04 0.12
Fe K 10.20 0.7847 3.93 0.13 0.94
Total 100.00

 

 

 

 

 

 

 

Figure 32-1. (Continued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

r Wm:

m- .11

m-

ml

2m:

im-

1”- F.

O
”1 Fe
00 c- c. "
'o'sla'sizkia'so'tsis'sés‘sir'sé
Edﬂmcﬂm 8153 (1068! W
Element App Intensity Weight % Weight % Atomic %
Conc. Comp. Sigma

C K 35.47 1.3744 81.82 0.34 89.81

0 K 9.86 0.3131 9.99 0.34 8.23

CI K 0.40 0.8355 0.15 0.02 0.06

Ca K 0.32 0.9986 0.10 0.02 0.03

Fe K 19.71 0.7873 7.94 0.12 1.87
Total 100.00

 

 

 

 

 

 

Figure 32-2. All elements analysis on the site of Spectrum 2 in 082 ﬁlm

111

 

1 Inner layer (LLDPEi)
Core layer (LLDPEc)

Outer layer (LLDPEo)

 

Figure 33. Spectrum sites of LLDPE ﬁlm

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Satchuhl
ml
am
mo-
“1
1W<
1M‘
1» 0
9
"3'; his 5'23 5"a's'1'i's é é's 6 5'5 i'fs 3
mammograms: £33m] IW
Element App Intensity Weight % Weight % Atomic %
Conc. Comp. Sigma
C K 49.39 1.8499 90.43 0.35 92.69
0 K 7.63 0.2747 9.41 0.35 7.24
Si K 0.44 0.9728 0.15 0.02 0.07
Total 100.00

 

Figure 34-1. All elements analysis on the site of Spectrum 1 in LLDPE ﬁlm

112

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

1 p WW2
mi
1031
2500:
m4
1
1
1W4
10131
5031 ‘ °
04%;.”.21-:::€::LVT-.J:V,.L.T3;ZW
05115225334455556657758
[11 Sub mamma- 3153 man w
Element App Intensity Weight % Weight % Atomic %
Cone. Comp. Sigma
C K 52.00 1.8747 90.20 0.34 92.46
0 K 8.31 0.2758 9.80 0.34 7.54
Total 100.00

 

 

 

 

 

 

 

Figure 34-2. All elements analysis on the site of Spectrum 2 in LLDPE ﬁlm

113

 

5.2.2. Quantitative analysis of migration
5.2.2.1. Film samples
Experiments were carried out using LLDPE, OS1 and 082 ﬁlms having three

layer structures produced by co-extrusion as shown in Figure 10 and Table 10-2. All

ﬁlms were stored at room conditions of 23 °C. and 65% RH after being sealed into an

aluminum laminated pouch which was ﬁlled with nitrogen gas to prevent/reduce the

activation by residual oxygen in the pouch.

5.2.2.2. Food simulants

Even though there are no special cosmetic simulants, retinol is a fat-soluble
compound and creams in the product generally contain wax / oil components. The inner
layer of the OS tubes, which directly contacts the product, is made of linear low density
polyethylene (LLDPE) in the polyoleﬁn group. Therefore, the appropriate alternative
food simulants recommended by FDA were selected to quantify the major migrant
components from the oxygen scavenger in the OS ﬁlm or tube. The recommended
simulants are deﬁned in 21 CFR 176, 170 (c) Table 1 (FDA, 2002) and Appendix 1 as
follows:
1) Water and 2) 3% Acetic Acid: From “Food-Type as deﬁned in 21 CFR 176.170 (C)
Table 1,” the recommended simulant is generally 10% ethanol for aqueous & acidic
foods (Food types 1, 11, NB, VlB, and V113) and how or High Alcoholic Foods (Food
Types VIA and VIC). However, when food acidity is expected to lead to signiﬁcantly
higher levels of migration than with 10% ethanol, or if the polymer or adjuvant is acid-
sensitive, separate extractions in water and 3 % acetic acid inlieu of 10% ethanol should

be conducted. when food acidity is expected to lead to signiﬁcantly higher levels of

114

migration than 10% ethanol, or if the polymer or adjuvant is acid-sensitive. 10% Ethanol
is used for Aqueous & Acidic Foods (Food Types 1, 11, NB, VlB, and VllB) Water used
was HPLC regent grade (J .T. Baker, Phillipsburg, NJ), and the absolute (100%) acetic
acid, Glacial (Mallinckrodt Baker Inc., Phillipsburg, NJ) was diluted with water to make
the 3 % solution.

3) Food oil for Fatty Foods (Food Types lll, IVA, V, VllA, and 1X): Olive oil (100%

pure & natural with no preservatives added) was used as a fatty food simulant. The oil,

(FlLlPPO BERlO®), which was imported from Italy, was purchased at Meijer.

4) 95% Ethanol: An Effective Fatty-Food Simulant for Polyoleﬁns: The absolute
(100%) ethanol (ethyl alcohol, HPLC grade, Sigma-Aldrich,Milwaukee, W1) was diluted

with water (HPLC regent grade, J .T. Baker, Phillipsburg, NJ) to make the 95% solution.

5.2.2.3. Migration cell and tube experiments
1) Migration cell

Migration experiments were performed in accordance with ASTM D 4754-98,
“Standard Test Method for Two-sided Liquid Extraction of Plastic Materials Using FDA
Migration Cell” (ASTM, 1998). The migration cell was prepared as follows: 14 plastic
test specimens in the form of round disks, 17.5 mm diameter for each disk, were punched
out from the ﬁlm samples. The total surface area of 14 specimens was calculated as 68.39
cmz. Then the test specimens were threaded onto a stainless steel wire with alternating
glass beads to prevent the specimens from overlapping each other. The threaded
specimens on the wire were placed in a 40 ml amber glass vial with a screw top. The food
simulant was added into the vial to soak the specimen, a volume of 30 ml. Four vials

were prepared for each liquid extractant. Assembled migration cells were stored in a

115

controlled atmosphere chamber maintained at 40 °C for 10 days, following FDA’s

recommended migration protocols when foods are used at temperatures above the glass
transition of polyoleﬁns or room temperature ﬁlled and stored without any thermal
treatment in the container (FDA/CFSAN, 2007).
2) Migration tube

Migration experiments using tubes were also performed, because of concern that
the oxygen scavenger would mainly migrate from the exposed seam in the tube. 3%
acetic acid was used as a food simulant, and added into the tube, a volume of 30 ml. Four
sets of tubes were heat sealed and coated over-seal with silicone. Total surface area of the
inside of tubes in contact with 3% acetic acid was measured and calculated as 52.13 cmz.
Assembled migration tubes were stood up in a holder case and stored in a controlled

atmosphere chamber maintained at 40 °C for 10 days.

5.2.2.4. Atomic absorption (AA) spectrometry
Quantitative analysis for migrated major components of oxygen scavengers, such

as Na, Ca and Fe, in migration cell with food simulants after being stored at 40 °C during
10 days was performed using an AA spectrometer (Model Spectr AA-200, Varian,
Australia) [Figure 35].
1) Selection of migrant main components

The results of the SEM EDS from Figure 28 and Figure 30 showed that the main
components of the residue were NaCl and iron compounds and the main migrants were
identiﬁed therefore as Na, C1 and Fe. From Figure 32-2, Ca was a minority component
but added because it could act to produce the migration of chloride (C l) as CaClg.

2) Preparation of standard stock solutions

116

As standard materials, sodium chloride (NaCl; 99.99%, J .T. Baker, Phillipsburg.
NJ), calcium carbonate (CaCO3; AA grade, PerkinElmer) and iron (Fe; AA grade,
PerkinElmer) were prepared. 2.542 g of dried NaCl was dissolved in distilled water
(HPLC grade, J.T. Baker, Phillipsburg, NJ) and then diluted to 1 liter to give 1,000 ﬂg/ml
Na. 2.497 g of dried calcium carbonate in a minimum volume of 1 :4 nitric acid was
dissolved, and diluted to 1 liter to give 1,000 ug/ml Ca. The solution of iron was
prepared by dissolving 1,000 g of iron powder in 20 ml of 1:1 hydrochloric acid and

diluting to 1 liter to give 1,000 ,ug/ml Fe.

 

Figure 35. Atomic absorption (AA) spectrometry

3) Instrument parameters

The instrument parameters for the Varian Spectr AA-200 Flame AA Spectrometer,
atomic absorptions for ﬁxed and variable working conditions and ﬂame emissions for
analysis ofNa, Ca and Fe are shown in Table 17, Table 18 and Table 19. The pressures in
the gas cylinders were 1 1 psi for acetylene and 50 psi for air. Fuel ﬂows were all [.5

L/min. The sample aspiration rate was 5 ml/min, and it took 13 seconds to aspirate 1 ml

117

ofdistilled water.

Table 17. Atomic absorption: working conditions (Fixed)

 

 

Parameters Na Ca Fe

Lamp current 5 mA 10 mA 5 mA

Fuel acetylene acetylene acetylene

Support air nitrous oxide air

Flame stoichiometry oxidizing reducing; red cone oxidizing
1 — 1.5 cm high

 

Table 18. Atomic absorption: working conditions (variable)

 

 

Major components Wavelength Slit width Optimum working range
nm nm ug/ml

Sodium (Na) 589.0 0.5 0.002 — 1.0
589.6 1.0 0.01 — 2.0
330.2 0.5 2 — 400

Calcium (Ca) 422.7 0.5 0.01 - 3

Iron (Fe) 248.3 0.2 0.06 - 15

 

Table 19. Flame emission

 

 

Parameters Na Ca Fe
Wavelength 589.0 nm 422.7 nm 372.0 nm
Slit width 0.1 nm 0.1 nm 0.1 nm
Fuel acetylene acetylene acetylene
Support air nitrous oxide air

 

118

5.2.2.5. Standard calibration curve
1) Sodium (Na) analysis
Working standard solutions for sodium analysis were prepared by dissolving each

volume from the standard stock solution as follows: 0, 1, 3, 5, 8 and 10 ppm (mg/ml) for

95% ethanol; 0, l, 3, 5, 10, 15 and 20 ppm for distilled water and 3 % acetic acid; 0. l, 3,
5 ppm for olive oil. After testing the working standard solutions by the AA spectrometer,
the standard calibration curve was constructed by calculating the average absorbance of
the peaks analyzed three times for each working standard solution. Figure 36 shows the
curve for 95% ethanol, Figure 37 shows results for distilled water and 3% acetic acid, and
Figure 38 shows olive oil. The best ﬁt equations and corresponding R2 values for the
standard calibration curves for sodium analysis are also shown in Figure 36, 37 and 38.
While the R2 values for 95% ethanol, distilled water and 3% acetic acid were over 0.99,

the value for olive oil was a little lower than 0.97.

119

 

1.2

1.0 -

0.8

0.6

Absorbance

0.4

0.2

 

  

y = 0.1096 x + 0.0127
R2 a 0.9950

 

 

0.0

 

PPm
Figure 36. Standard calibration curve for Na concentration in 95% ethanol

 

1O

Absorbance

 

0?

y = 0.4008 x + 0.3603

R2 = 0.9953

1

10

1313'“

 

l l

15 20

 

25

Figure 37. Standard calibration curve for Na concentration in distilled water and 3%

acetic acid

120

 

1.6

1.4 *-
y = 0.2373 x + 0.0883

1.2 , R2 = 0.9647

Absorbance

 

 

 

PPm

Figure 38. Standard calibration curve for Na concentration in olive oil

2) Calcium (Ca) analysis

Working standard solutions for calcium analysis were prepared by dissolving each
volume from the standard stock solution as follows: 0, 1, 3, 5, 8, and 10 ppm (ﬁg/ml) for
95% ethanol, distilled water and 3% acetic acid, and 0, 1, 3, 5 and 10 ppm for olive 011.
Figure 39 shows results for 95% ethanol, Figure 40 for distilled water and 3% acetic acid
and Figure 41 for olive oil. The best ﬁt equations and corresponding R2 values for the

standard calibration curves for calcium analysis are also shown in Figures 39, 40 and 41.

121

 

3O

15

Absorbance

10

05

 

p
O
9

  
 

y = 0.2622 x + 0.1175
R2 = 0.9949

 

l L l L

8 10 12 14

ppm

Figure 39. Standard calibration curve for Ca concentration in 95% ethanol

 

12

10 e

06

Absorbance

04

.02

 

   

y = 0.0116 x + 0.0106
R2 = 0.9975

 

l l J. J

8 1O 12 14

mm

Figure 40. Standard calibration curve for Ca concentration in distilled water and 3%

acetic acid

122

 

0.20

y = 0.02351- + 0.0117
0-15 r R2 = 0.9397

Absorbance
o
8

 

 

 

0.05 ~ :
omt 1 1 1 1 l 1
0 1 2 3 4 5 6 7

Figure 41. Standard calibration curve for C: Ic)(')‘r'1centration in olive oil
3) Iron (Fe) analysis
Working standard solutions for iron analysis were prepared by dissolving each
volume from the standard stock solution as follows: 0, 1, 2, 3, 5, 10 and 20 ppm (pg/ml)
for 95% ethanol, distilled water and 3% acetic acid; and 0, 1, 5 and 10 ppm for olive 011.
Figure 42 shows results for 95% ethanol, Figure 43 for distilled water and 3% acetic acid
and Figure 44 for olive oil. The best ﬁt equations and corresponding R2 values for the

standard calibration curves for iron analysis are also shown in Figures 42, 43 and 44.

123

 

35

y = 0.0157 x - 0.0201
2.5 - R2 = 0.9988

Absorbance

 

 

 

J l

0 5 10 15 20 25

99'"
Figure 42. Standard calibration curve for Fe concentration in 95% ethanol

 

0L)

 

 

 

 

 

3

C

CB
.0

L-

o

m
.o
<(

0.0 1 1 1 1
O 5 10 15 20 25
PPm
Figure 43. Standard calibration curve for Fe concentration in distilled water and 3%
acetic acid

124

0.20

0.15

0.10

Absorbance

0.05

Figure 44. Standard calibration curve for Fe concentration in olive oil

 

 

y = 0.0222\- - 0.0030
R2 = 0.9862

 

 

ppm

125

 

5.3. Results and discussions

In order to observe the migration behavior and evaluate the quantitative analysis
of migration for the multilayer oxygen scavenging ﬁlms, as a ﬁrst step, the main elements
of oxygen scavengers in OS] and 082 ﬁlms were identiﬁed. The next step was
observation of migration behaviors in the inner layer, which was in direct contact with
food simulants or cosmetic, adjacent to the core layer in the specimens and the exposed
seam in the tube [Figure 45] using SEM. Finally, the quantitative analysis of migration
for the main components of oxygen scavenger in the migration cells was executed using

AA spectrometer and compared with tube and sachet type.

Particles of
oxygen scavenger PET

Food simulants
or cosmetic

Inner layer
(LLDPEi)
Core layer

(os+ LLDPEc) ’ ' '

Outer layer
(LLDPEo)

 

Aluminum —'

Figure 45. Structure ofa tube laminated with the OS ﬁlm

126

5.3.1. Observation of migration behaviors
5.3.1.1. Overall migration behaviors in OS ﬁlms

Figure 46 shows the overall migration behavior for each element of oxygen
scavenger in 051 ﬁlm that consisted ofthree layer (LLDPEi/OS1+LLDPEc/LLDPEO).
which was snapshotted by the ‘X—ray Map’ method of SEM EDS and magniﬁed 650
times. The observed elements in 051 ﬁlm were iron, silica, chlorine, phosphorus and
sodium except carbon and oxygen. The particles of Fe, P. Na and Cl were clearly
observed in the core layer (081 + LLDPEc) of OS] ﬁlm, but they were not seen at all in
the inner layer (LLDPEi) or outer layer (LLDPEo). Si was observed both in the core and
outer layer. Figure 47 also shows the overall migration behavior for elements (Fe. Si, C1
and Na) of oxygen scavenger in 082 ﬁlm, which was snapshotted by same method. The
particles of Fe, Si and Cl were observed clearly in the core layer of 052 ﬁlm, but they
were not seen in the inner or outer layer. In the case of Na, it was not seen even in the
core layer. As a result, the main elements (Fe, Na and CI) of oxygen scavenger were not

observed in the inner layer of OS] and 082 ﬁlms by SEM-EDS.

Inner layer (LLDPEi)

Core layer (081 + LLDPEc)

 

I Outer layer (LLDPEo)

Figure 46. Overall migration behavior for each element of oxygen scavenger in 081 ﬁlm
by the ‘X-ray Map’ method of SEM & EDS (Magniﬁed 650 times).

127

   

Fe 11:11 311m

   

011431 P111131

 

Na Kat _2

Figure 46. (continued)

128

Inner layer (LLDPEi)

Core layer (OSZ + LLDPEc)

Outer layer (LLDPEo)

 

 

Fe Kat 811431

 

CW3”: Nai’aij

Figure 47. Overall migration behavior for each element ofoxygen scavenger in 082 ﬁlm
by the ‘X-ray Map‘ method of SEM & EDS (Magniﬁed 650 times).

129

5.3.1.2. Migration behaviors in the inner layer ofOS ﬁlms
1) Migration behavior into the inner layer of 081 ﬁlms

To identify more clearly the migrant behaviors into inner layer for the main
elements of oxygen scavenger in the core layer of 081 ﬁlms, quantitative analysis at the
site of‘Spectrum 1‘ [Figure 48] in the inner layer. which was in direct contact with food
simulants or cosmetic, was executed by the ‘Oxford INCA’ system of SEM EDS. Figure
49. 50 and 51 shows the result of ‘Spectrum 1’ in three kinds ofOSl ﬁlms. As a result,
any main elements such as Fe, Na and Cl except C and 0 from the ‘Spectrum 1’ in the
inner layer of these ﬁlms were not detected. Furthermore, they were not observed even in
3% acetic acid [Figure 50]. which shows the most powerful migration result among food
simulants as it mentioned in 5.2.1.]. It means that the main elements ofoxygen scavenger
in the core layer of 081 ﬁlm did not pass through the inner layer and did not contact the

food simulants and cosmetic.

Spectrum 1

. Inner layer (LLDPEi)
. ___ ,. 2 _..‘ ’

Core layer (081 + LLDPEc)

\ Particle of oxygen
scavenger

 

81) um

 

Figure 48. Observation of Spectrum 1 sites of the inner layer of 081 ﬁlm

130

 

0'7

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

05 1 15 2 25 3 35 I 1.5 5 55 5 55 7 75 8
mummmnam [1761) IN
Element App Intensity Weight °/o Weight % Atomic %
Conc. Comp. Sigma
C K 64.72 1.8519 89.32 0.32 91.76
O K 1 1.66 0.2790 10.68 0.32 8.24

Total 100.00

 

 

Figure 49. Result ofSpectrum 1 (081 ﬁlm; 6 months passed at 23 °C and 65% RH)

131

 

 

 

 

 

  

      

 

 

 

 

 

 

 

 

 

 

. I smut
run]
1
1
W?
15101
m1
1m:
1m;
”1
1 ° 9
01L H.-- .,---::.;:-.;7fmr
05152253351!!!)5555657750
[mammary-11.153 (1111:) w
Element App Intensity Weight % Weight % Atomic %
Cone. Comp. Sigma
C K 46.20 1.8571 91.20 0.35 93.31
0 K 6.37 0.2719 8.59 0.35 6.60
Si K 0.57 0.9752 0.21 0.03 0.09
Total 100.00

 

 

 

 

 

 

 

 

Figure 50. Result of Spectrum 1 (OSI ﬁlm; stored at 10 days & 40 °C in 3% acetic acid)

132

 

 

 

 

 

 

 

 

 

 

 

 

_ .1 a , '
m:
MI
W:
mi
1910-:
1m:
1
m1 0
0511.52253354155555557155
faunsmmuomaay W
Element App Intensity Weight % Weight % Atomic %
Conc. Comp. Sigma
C K 45.55 1.9081 91.42 0.35 93.42
0 K 0.61 0.2713 8.58 0.35 6.58
Total 100.00

 

 

 

 

 

 

 

Figure 51. Result of Spectrum 1 (OSI ﬁlm; 6 months passed in room conditions after

ﬁlling cosmetic)

133

 

2) Migration behavior into the inner layer of 032 ﬁlm

Observations of migration behaviors into the inner layer of 0S2 ﬁlms were
executed by the same method as that for OSl ﬁlm in Figure 52. As can be seen in
Figures 53, 54 and 55, no migration ofthe main elements (Fe. Na and Cl) ofoxygen
scavenger into the inner layer (site of ‘Spectrum 1’) was observed. This was the same
result as that of OS], and it means that the main elements of oxygen scavenger in the core
layer of OSZ ﬁlm did not pass through the inner layer and did not contact the food
simulants and cosmetic. Si was seen in both inner layers, which were made of LLDPE, in
OS] and 082 ﬁlm as a minor element, which might be due to silicone oil from screen

changers in the blown ﬁlm process or additives in the polymer.

Spec! um I T

. MA- . Inner layer (LLDPEi)

,1
1]

Core layer (082 + LLDPEc)

- it
t 1'5 .

Particle of oxygen
scavenger

 

Figure 52. Observation of Spectrum 1 sites of in the inner layer of 082 ﬁlm

134

 

I]

AAAALAA‘AAAAAALAAJJALAAALA. AAL“AA-L

5

§

 

 

 

‘5’

 

 

 

W1

 

 

 

 

 

 

 

 

 

 

 

 

 

05 1 15 2 25 3 3S 4 45 55 5 65 7 15 5
M Sci! 1955123011111 1123 (12d!) 12V
Element App Intensity Weight % Weight % Atomic %
Cone. Comp. Sigma
C K 43.54 1.7854 86.65 0.35 89.63
O K 1.09 0.2892 13.35 0.35 10.37
Total 100.00

 

 

Figure 53. Result of Spectrum I (082 ﬁlm; 6 months passed at 23 °C and 65% RH)

135

 

 

 

 

 

 

 

 

 

 

 

 

 

1 [:1 W1
m1
1
1
m:
1
m1
1
ml
1
1
15101
1
1
1M;
1
me
o.‘
05115225335115 555552755
[ummsmm 3.1233261) 11v
Element App Intensity Weight % Weight % Atomic %
Cone. Comp. Sigma
C K 54.18 1.8476 89.15 0.33 91.63
O K 1.00 0.2796 10.85 0.33 8.37
Total 100.00

 

 

 

 

 

 

 

 

Figure 54. Result of Spectrum l (082 ﬁlm; stored at 10 days & 40 °C in 3% acetic acid)

I 36

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

, 1; 500051111
25001
1
2000;
15w:
1
1M1
1
1
as 1 15 2 25 3 as 1 15 s 55' '1‘ .33.--.i---.7,s.---;
ruwmmmaram (mm m
Element App Intensity Weight °/o Weight % Atomic °/o
Cone. Comp. Sigma
C K 55.46 1.8909 90.81 0.34 92.94
O K 8.12 0.2736 9.19 0.34 7.06
Total 100.00

 

 

 

Figure 55. Result of Spectrum I (082 ﬁlm; 6 months passed in room conditions after

ﬁlling cosmetic)

137

5.3.1.3. Migration behaviors in a tube

As is shown in Figure 45 in Section 5.3, the inside of a tube containing food
simulants or cosmetic mostly consisted of the inner layer (LLDPEi) of OS ﬁlms, but the
seamed parting line of the tubes also contacted the simulants. This means that the oxygen
scavengers in the seamed parting line had a possibility to be exposed directly to the
simulants [Figure 56]. Therefore, the migration behaviors in the inner layer and the
seamed parting line in a tube were observed by SEM & EDS. From Figure 57, ‘Spectrum
1’ was the seamed parting line and ‘Spectrum 2’ was the inner layer in a tube which was
stored at 10 days and 40 “C aﬁer ﬁlling with 3% acetic acid. While the main elements
such as Fe, Na and CI could be observed in ‘Spectrum 1’ [Figure 58], these elements
were not seen in “Spectrum 2’ [Figure 59]. Therefore, the main elements of oxygen

scavenger migrated through the seamed parting line in a tube exposed directly to the

simulants.

Seamed parting
line of tubes

 

Figure 56. Inside of package after 6 months passed in room conditions aﬁer ﬁlling
cosmetic; the seamed parting line of 081 and 082 packages are darker than the other
inside area because it is more oxidized by directly contacting the oxygen in the cosmetic
or headspace of a package. This means that main components of oxygen scavenger in the
seamed parting line are able to migrate more easily to simulants.

138

- M'F$§ir 5

k

Spectrum 1

‘ xgegmcd parting line in a tube . I M’\:.“

_.

Spectrum 2

(Inner layer in u tube)

 

 

5501 C SunSpednmi

 

 

 

 

 

 

........,....,...r,....,...........,,.,.....,..............,”.51...
D5 1 15 2 25 3 35 4 4.5 5 55 6 85 7 75 8 85
IlSWSS‘dsCusorllmSGdes) It:

 

 

Figure 58. Result of Spectrum 1 (Seamed parting line in a tube; stored at 10 days and
40 °C in 3% acetic acid)

139

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Element App Intensity Weight % Weight °/o Atomic %
Conc. Comp. Sigma
C K 55.80 1.8313 91.32 0.59 93.60
0 K 7.31 0.2716 8.06 0.58 6.20
Na K 0.22 0.9068 0.07 0.06 0.04
Si K 0.35 0.9731 0.1 l 0.04 0.05
CI K 0.22 0.8422 0.08 0.04 0.03
Fe K 0.91 0.7712 0.36 0.08 0.08
Total 100.00
Figure 58. (continued)
550; . SunSpe-ctm
900%
1
.1;
mi
1
3501
1
30°:
1
m1
1
200%
1503
1
103-:
501 o '5‘
01%
0.5 15 2 2.5 3 3.5 C 4.5 S 5.5 6 6.5 7 8 85
Ft] Scale 564 as 0:90: 0008 (3473015) rev
Element App Intensity Weight % Weight °/o Atomic %
Conc. Comp. Sigma
C K 49.34 2.0007 95.80 1.10 96.86
0 K 2.68 0.2566 4.06 1.10 3.08
Si K 0.34 0.9879 0.13 0.10 0.06
Total 100.00

 

 

 

 

 

 

 

Figure 59. Result of Spectrum 2 (Inner layer in a tube; stored at 10 days and

40 °C in 3% acetic acid)

140

 

 

 

5.3.2. Quantitative analysis of migration by AA spectrometry

Throughout the observation of migration behaviors in the OS ﬁlms and tube by
SEM & EDS, the main elements of oxygen scavenger were migrated from the seamed
parting line to expose directly to the simulants. This appearance seems to be able to occur
in the migration vials because the edge of core layer of the ﬁlm sample, which contains
oxygen scavenger, also directly exposed to the simulants. Therefore, quantitative
analysis of migration to the migration vials and tubes in various food simulants was

executed using AA spectrometry.

5.3.2.1 Migration result for Na and calculation for NaCl

Table 20 shows the values (11g) of sodium which migrated into various food
simulants in the migration vials, and Table 21 shows the migration value of NaCl as
calculated from observed migration of sodium. OSI has much higher values for water
(17.8 rig/30 ml in migration of sodium) and 3% acetic acid (17.4/1g/30 ml in migration of
sodium), which are more than 6 times than those of LLDPE. The values of 082 are
overall less than 5 /zg/30 ml in migration of sodium or 0.4 mg/L in migration of sodium
chloride for all food simulants. LLDPE has some migration values that are not 0. This
may be due to additives in the polymer. As a whole, the migration values in 95% ethanol,

water and 3% acetic acid are signiﬁcantly different between OS 1, 082 and LLDPE, but

the value in olive oil is not signiﬁcantly different between them.

141

Table 20. Migration of sodium (Na) into food simulants
(Unit: tug/30 ml)

 

 

Sample 95 % Ethanol Water 3% Acetic Acid Olive Oil
OS 1 Ave 3.489 17.805 17.408 0.497
Std 0.170 0.229 0.384 0.249
Dev 1a 2a 3a 4a
082 Ave 1.199 3.608 4.273 0.427
Std 0.100 0.254 0.238 0.064
Dev 1b 2b 3b 4a
LLDPE Ave 0.521 2.145 2.831 0.513
Std 0.074 0.186 0.246 0.210
Dev 1c 2c 3c 4a

 

n = 12; 4 specimens x 3 replicates
Different numbers in different columns and different letters within a column are
signiﬁcantly different (p < 0.05).

Table 21. Speciﬁc migration of NaCl as calculated from observed migration of sodium,
respectively.
(Unit: mg/L)

 

 

Sample 95 % Ethanol Water 3% Acetic Acid Olive Oil
OS 1 Ave 0.297 1.508 1.476 0.043
Std 0.014 0.019 0.032 0.021
Dev 1a 2a 3a 4a
082 Ave 0.100 0.305 0.363 0.034
Std 0.007 0.022 0.019 0.007
Dev 1b 2b 3b 4a
LLDPE Ave 0.045 0.181 0.239 0.043
Std 0.005 0.017 0.021 0.018
Dev Ic 2c 3c 4a

 

n = 12; 4 specimens x 3 replicates
Different numbers in different columns and different letters within a column are
signiﬁcantly different (p < 0.05).

142

Speciﬁc migration of NaCl is calculated from observed migration of sodium as follows:

ppmNa + x 58.44 ———- gg,
moleNaCl (5. l )

23 - __g__
moleNa +

ppmNaCl =

 

5.3.2.2. Migration result for Ca and calculation for C3C12
Table 22 shows the values (11g) of calcium which migrated into various food

simulants in the migration vials, and Table 23 shows the migration value of CaClg as

calculated from observed migration of calcium. OS] and LLDPE have very low level that

are less than 0.5 11g/30 ml or 0.05 mg/L in migration ofcalcium or calcium chloride for
all food simulants, but OSZ shows much higher values in migration than other two for

water, 3 % acetic acid and olive oil. The highest value of OSZ is 4.507 [Lg/30 ml in

migration of calcium or 0.418 mg/L in migration of calcium chloride for 3% acetic acid.

Table 22. Migration ofcalcium (Ca) into food simulants
(Unit: pig/30 ml)

 

 

Sample 95 % Ethanol Water 3% Acetic Acid Olive Oil
OSl Ave - 0.382 0.049 0.302 0.492
Std 0.01 1 0.018 0.038 0.471
Dev 1a 2a 3a 4a
0S2 Ave - 0.371 0.630 4.507 1.320
Std 0.010 0.326 0.371 0.569
Dev 1a 2b 3b 4b
LLDPE Ave - 0.342 0.297 0.326 0.484
Std 0.010 0.116 0.1 19 0.250
Dev la 23b 33 4a

 

I43

n = 12; 4 specimens x 3 replicates

Different numbers in different columns and different letters within a column are
signiﬁcantly different (p < 0.05).

Negative values less than 1 ppm can be considered 0 as a test error.

Table 23. Speciﬁc migration of CaClg as calculated from observed migration of calcium,
respectively.
(Unit: mg/L)

 

 

Sample 95 % Ethanol Water 3% Acetic Acid Olive Oil
081 Ave - 0.037 0.001 0.028 0.045
Std 0.005 0.003 0.004 0.045
Dev la 2a 3a 4a
082 Ave - 0.033 0.020 0.418 0.123
Std 0.005 0.034 0.034 0.054
Dev la 2b 3b 4b
LLDPE Ave - 0.030 0.009 0.029 0.047
Std 0.000 0.014 0.013 0.024
Dev la 2ab 3a 4a

 

n = 12; 4 specimens x 3 replicates

Different numbers in different columns and different letters within a column are
signiﬁcantly different (p < 0.05).

Speciﬁc migration of CaClz is calculated from observed migration of calcium as follows:

 

ppmca“ x111.0' _g ,5
pmeaCl 2 = max“ I 2 (5.2)
40- — g .
moIeCa H

5.3.2.3. Migration result for Fe and calculation for Fe203
Table 24 shows the values (11g) of iron which migrated into various food

simulants in the migration vials. and Table 25 shows the migration value of Fe303 as

144

calculated from observed migration of iron. 081 is the highest value (17.176 peg/30 ml)
for 3 % acetic acid, which are almost two orders of magnitude greater than that of
LLDPE (0.295 rug/30 ml). The values of 082 is 3.072 ng/30 ml in migration ofiron and
calculated 0.818 mg/L in migration of iron oxide for 3% acetic acid. LLDPE has some
migration value but less than 0.3 x1g/30 ml, it may be due to impurities from the

extrusion process or punching to make disks in migration vials. As a whole, the migration
values in 3% acetic acid are signiﬁcantly different between OS 1 , OS2 and LLDPE, but

the values in 95% ethanol and olive oil are not different between them.

Table 24. Migration of iron (Fe) into food simulants
(Unit: /zg/30 ml)

 

 

Sample 95 % Ethanol Water 3% Acetic Acid Olive Oil
081 Ave 0.136 1.811 17.176 0.299
Std 0.008 0.257 1.735 0.333
Dev 1a 2a 3a 4a
OS2 Ave 0.138 - 0.004 3.072 0.185
Std 0.009 0.021 0.168 0.161
Dev la 2b 3b 4a
LLDPE Ave 0.143 - 0.019 0.295 0.225
Std 0.008 0.018 0.022 0.056
Dev la 2b 36 4a

 

n = 12; 4 specimens x 3 replicates

Different numbers in different columns and different letters within a column are
signiﬁcantly different (p < 0.05).

Negative values less than 1 ppm can be considered 0 as a test error.

145

Table 25. Speciﬁc migration of F6203 is calculated from observed migration of iron,

respectively.

 

 

(Unit: mg/L)
Sample 95 % Ethanol Water 3 % Acetic Acid Olive Oil
OS 1 Ave 0.010 0.028 0.818 0.015
Std 0.000 0.042 0.083 0.015
Dev 1a 2a 3a 4a
082 Ave 0.010 0.000 0.148 0.009
Std 0.000 0.000 0.009 0.009
Dev la 2b 3b 4a
LLDPE Ave 0.010 0.000 0.012 0.01 1
Std 0.000 0.000 0.004 0.003
Dev la 2b 3c 4a

 

n = 12; 4 specimens x 3 replicates

Different numbers in different columns and different letters within a column are

signiﬁcantly different (p < 0.05).

Speciﬁc migration of F0303 is calculated from observed migration of iron as follows;

pmee H” x159.7~

_. 4% ____
IeFe 203

 

pmee203 =

111.7 __.
moleFe

(5.3)

5.3.2.4. Results for the sum of migration for main components in migration vials

The sum of migration in the migration vials for the main elements (Na + Ca + Fe)

are compared in Table 26. As a whole, the migration values in 3% acetic acid are the

highest and the next are those in water, among the food simulants. The migration values

in 95% ethanol, water and 3% acetic acid are signiﬁcantly different between OSI, OS2

and LLDPE, but the value in olive oil is not signiﬁcantly different between them. OSI

has the highest value (34.885 [lg/30 ml) for 3% acetic acid, which is almost 10 times

146

greater than that of LLDPE (3.452 mtg/30 ml) and near to 3 times that of 082 (I 1.852

[lg/30 ml). The sum of migration (19.665 11g/30 ml) of OSI for water also has a very high
value.

The sum of migration for NaCl + C3C12 + F6203 from Table 27, OSI is 2.322
mg/L for 3 % acetic acid, which is the highest value among the food simulants. However.

it is less than the EU limit for total migration of60 mg/L (90/128/EEC).

Table 26. Sum of migration for main elements (Na + Ca + Fe)
(Unit: tut/30 ml)

 

 

Sample 95 % Ethanol Water 3% Acetic Acid Olive Oil
OSI Ave 3.243 19.665 34.885 1.288
Std 0.168 0.435 1.441 0.612
Dev la 2a 3a 4a
082 Ave 0.966 4.234 1 1.852 1.932
Std 0.097 0.509 0.357 0.631
Dev 1b 2b 3b 4a
LLDPE Ave 0.322 2.423 3.452 1.223
Std 0.073 0.159 0.316 0.328
Dev 1c 2c 3c 43

 

n = 36; 4 specimen x 3 replicates x 3 elements

Different numbers in different columns and different letters within a column are

signiﬁcantly different (p < 0.05).

147

Table 27. Sum of migration for main components (NaCl + CaClg + F0303) as calculated

from observed migration of sodium, calcium and iron, respectively.

 

 

(Unit: mg/L)
Sample 95 % Ethanol Water 3% Acetic Acid Olive Oil
OSI Ave 0.270 1.538 2.322 0.102
Std 0.017 0.047 0.062 0.046
Dev la 2a 3a 4a
OS2 Ave 0.078 0.325 0.928 0.167
Std 0.009 0.043 0.036 0.056
Dev lb 2b 3b 4a
LLDPE Ave 0.025 0.190 0.280 0.100
Std 0.005 0.022 0.028 0.030
Dev 1c 2c 3c 4a

 

n = 36; 4 specimen x 3 replicates x 3 components
Different numbers in different columns and different letters within a column are

signiﬁcantly different (p < 0.05).

Speciﬁc migration of NaCl, CaClz and Fe203 is calculated from the observed migration

of sodium, calcium and iron as follows;

+ g
mNa x 58.44 —— 7 ~
pp moleNaC'l

23 -- - g—---
moleNa ‘

 

ppmNaCl =

)mCa xlll.0-— ~ 5
Pl moleCaCl 2

40 —-« -3“
moIeCa H

 

ppm CaCl 2 =

pmee +++ x 159.7 — _g_ -~
moleFezOz

111.7 “.3.——
mole/79+”

 

pmeezO3 =

148

5.3.2.5. Color change of the ﬁlms aﬁer migration test in various food simulants

Figure 60 shows the changed color of the ﬁlms used for migration tests in various
food simulants. While OSI in 3% acetic acid was the most changed, to dark red from a
gray color, and the sample of OS2 in 3 % acetic acid looked like mixed 3 dark red color
in its original black color to compare with other samples, samples of LLDPE were
transparent and not changed in color. The reason that the migration value was high in 3%
acetic acid and in distilled water is that they are hydrophilic (polar) protic solvents.
Especially, acetic acid (CH3COOl-I) is a week, effectively monoprotic acid in aqueous
solution. The hydrogen (H) atom in the carboxyl group (-COOH) in carboxylic acids such
as acetic acid can be given off as an H+ ion (proton), giving them their acidic character.
Due to this chemical property, acetic acid is corrosive to metals including iron or metal
salts in oxygen scavenger and results in a deeply red color as a iron (III) chloride solution

(Cambridge Encyclopedia, 2009).

- V ' m b"
L Control sample: Non treatment In food sunulants

-. 14%. ﬁg: .l: _

1 .

r"

”V

95% ethanol: 40'Cand 10 days

:1;
' .. -:; 5 In a:
.st. .

D1 tiledmwcandiodays ' ,
Olive oil: 40'Cand 10 days

Figure 60. Color change of the ﬁlms used as migration disks after migration test

 

149

5.3.2.6. Comparison of the migration of the main components in tubes and vials
The sums of migrations for tubes and vials that were made of OSZ for the main
elements (Na, Ca and Fe) and the main components (NaCl, CaClg and F8203) are

compared in Tables 28 and 29. The values are only evaluated in 3 % acetic acid because

ofits highest value among other food simulants. The sum is 5.131 ﬂit/30 ml for migrated

main elements and 0.398 mg/L for migrated main components in tubes. In cells, the sum

is 1 1.852 1114/30 ml for migrated main elements and 0.928 mg/l, for migrated main
components. For Table 30, the inside area of the tube in contact with 3% acetic acid was
calculated as 52.13 cm2, and the total surface of migration samples in a vial was
calculated as 68.39 cmz. Ifthe inside area ofthe tube is recalculated as the same as the
total surface of the migration samples, the value of migrated main components from the
inside ofthe tube would be 0.522 mg/L. This means that the value of from the migration
samples in the vials (0.928 mg/L) is near to 2 times that ofthe tubes.

Table 28. Comparison ofthe sums ofmigrations ofthe main elements (Na, Ca and Fe)
into 3% acetic acid between tube and vials

(Unit: 1115/30 ml)

 

 

Sample Na Ca Fe Sum
Tube Ave 1.655 2.088 1.389 5.131
(082) Std 0.444 0.350 0.232 0.495

Dev 1a 2a 3a 4a
Cells Ave 4.273 4.507 3.072 1 1.852
(052) Std 0.238 0.371 0.168 0.357

Dev 1b 2b 3b 4b

 

n= 12 for cells; 4 specimen x 3 replicates
Different numbers in different columns and different letters within a column are
signiﬁcantly different (p < 0.05).

150

Table 29. Comparison of the sums of migrations for the main components (NaCl, C3C12
and Fe203) into 3% acetic acid between tubes and vials as calculated from observed
migration of sodium, calcium and iron, respectively.

 

 

(Unit: mg/L)

Sample NaCI CaClz FezO3 Sum
Tube Ave 0.139 0.194 0.065 0.398
(OSZ) Std 0.038 0.033 0.009 0.050

Dev 1a 2a 3a 4a
Cells Ave 0.363 0.418 0.148 0.928
(OS2) Std 0.019 0.034 0.009 0.036

Dev lb 2b 3b 4b

 

n= 12 for cells; 4 specimen x 3 replicates
Different numbers in different columns and different letters within a column are
signiﬁcantly different (p < 0.05).

Table 30. Comparison of the sums of migrations for the main components (NaCl, CaC 12
and FezO3) into 3% acetic acid between tubes and vials including calculated values
normalized to the same surface area

 

 

Sample Total surface Sum of migration
Cells 68.39 cm2 '1 0.928 mg/L
Tube 52.13 cm2 2’ 0.398 mg/l.
Normalized 68.39 cm2 0.522 mg/L”

 

1)21tr. x ht = 2 x 3.1416 x1.22 cm x 6.8 em = 52.13 cm2
2) 14 pieces x(1tr22x 2 + 2an x hc)=14 x (3.1416 x 0.875 cm2 x 2 + 2 x 3.1416 x 0.875
cm x 0.0135 em) = 68.39 cm2
3) 0.398 mg/L x (68.39 cm2/52.13 cmz) = 0.522 mg/L
This seems to be due to the fact that the total area of the exposed edge of the

migration samples in the vial that contacts the food simulants was larger than that of the

seamed parting line in the tube.

151

5.4. Summary

This investigation of the migration behavior of the oxygen scavenger in active
packaging can be summarized as follows:
I) From the observation of overall migration in the OS ﬁlm for the main elements (Fe,
Na and C1) of the oxygen scavenger by the ‘X-ray Map’ method of SEM EDS, the main
elements were observed clearly in the core layer of OS ﬁlm, but they were not seen in the
inner and outer layers.
2) Throughout the observation of the migration behavior for the main elements by the
SEM & EDS, no migration of any of these main elements was detected in the inner layer
adjacent to the core layer containing oxygen scavenger of the OS multilayer ﬁlms (OSI
and 082), which was direct contact with food simulants or cosmetic. This means that the
main elements of oxygen scavenger in the core layer of the OS ﬁlms did not pass through
the inner layer and did not contact the food simulants and cosmetic.
3) From another analysis by SEM & EDS for the seamed parting line in a tube that was

stored at 10 days and 40 °C. in 3% acetic acid, the main elements (Fe, Na and Cl) could be

observed. However, the main elements were not detected on the non seamed area in the
inside of a tube. Therefore, the main elements of oxygen scavenger migrated from the
seamed parting line that was exposed directly to the simulants.

4) From the quantitative analysis of migration of the main components
(NaCl+CaC12+Fep_O3) from migration vials into various food simulants by AA
spectrometer, the migration values in 3% acetic acid were the highest and the next were
the values in water among the food simulants. The migration value of OSI in 3% acetic
acid was as 2.322 mg/L, 082 was 0.928 mg/L and LLDPE was 0.280 mg/L. However,

these values are much less than the EU limit for total migration of 60 mg/L (90/128/EEC).

152

5) From the quantitative analysis for the sums of migration in 3% acetic acid between
tubes and cells which were made of OSZ ﬁlm, the value of migrated main components
(NaCl+CaClg+ F6203) in the tube was 0.398 mg/L, and the value in migration cells was
0.928 mg/ L. If the inside area of the tube is recalculated as the same as the total surface
of migration cells, the value of migrated main components from the inside of the tube
would be 0.522 mg/L. This means that the value in the migration cells (0.928 mg/L) is

near to 2 times than that of the tubes.

153

5.5. References

Ahvenainen, R., and E. Hurme, “Active and smart packaging for meeting consumer
demands for quality and safety, Food Additives and Contaminants, 14: 753-763, 1997.

Alnafouri, A..l., and R. Franz, “A study ofthe equivalence of olive oil and the EU ofﬁcial
substitute test media for migration testing at high temperatures,” Food Additives and
Contaminants, 16: 419-431, 1999.

ASTM-D4754-98, Standard Test Method for Two-sided Liquid Extraction of Plastic
Materials Using FDA Migration Cell, Vol. 8.03, pp 174-177, 1998

Brody, A.L., E.R. Strupinsky, Kline L. R., Active Packagingfor Food Applications,
Technomic Pub., Lancaster, PV, PP. 12-14, 2001.

De Kruijf, N., M. van Beest, R. Rijk, T. Sipilainen-Malm, P. Paseiro Losada and B. De
Meulenaer, “Active and intelligent packaging: applications and regulatory aspects,” Food
Additive and Contaminations, 19: 144-162, 2002.

Cambridge Encyclopedia, “Acetic acid — Chemical properties, Biochemistry, Production.
Applications, Safety,” htgﬂ/cncyclgpedia.stateuniversitycom/pages/SI 1/acetic-acid.html,
(accessed Apr. 15, 2009).

European Commission, “Directive 82/71 l/EEC of 23 February 1990 relating to plastic
materials and articles intended to come into contact with foodstuffs,” Oﬂicial Journal of
the European Communities, L349, 26-47, 1990.

FDA (US. Food and Drug Administration), “Guidance for Industry: Preparation of Food
Contact Notiﬁcation: Administrative, FINAL GUIDANCE” May 2002.
http://wwwcfsan.fda.gov/~dms/opa2pmna.html#Il—B

FDA/CFSAN, Guidance for Industry — Preparation of Premarket Notiﬁcation, pp. 1-38,
2007. www.cfsan.fdagov/~dms/opa2pmnc.htm|

Gilbert, .1., C. Simoneau, D. Cote and A. Boenke, “An internet compendium of analytical
methods and spectroscopic information for monomers and additives used in food
packaging plastics,” Food Additives and Contaminants, 17: 889-893, 2000.

154

Lopez-Cervantes, .1., D.I. Sanchez-Machado, S. Pastorelli, R. Rijk and P. Paseiro-Losada,
“Evaluation the migration of ingredients from active packaging and development of
dedicated methods: a study of two iron-based oxygen absorbers,” Food additives and
contaminants, 20: 291-299, 2003.

O’Brien, A., A. Goodson and 1. Cooper, “Polymer additive migration to foods-a direct
comparison of experimental data and values calculated from migration models for high
density polyethylene (HDPE),” Food Additives and Contaminants, 16: 367-380, 1999.

O’Brien, A., and I. Cooper, “Polymer additive migration to foods-a direct comparison of
experimental data and values calculated from migration models for polypropylene,” Food
Additives and Contaminants, 18: 343-355, 2001.

Riquest, A.M., V. Bosc and A. Feigenbaum, “Tailoring fatty food simulants made from
solvent mixtures (1 ): comparison of methanol, ethanol and isopropanol behavior with
polystyrene,” Food Additives and Contaminants, 18: 165-176, 2001.

Smith, J .P., .1. Hoshino and Y. Ave, “Interactive packaging involving sachet technology,”
in M. L, Rooney, ed., Active Food Packaging, Blackie Academic & Professional Pub.,
London, pp. 143-173, 1995.

Teumac, F.N., “The history of oxygen scavenger bottle closure,” in M. L, Rooney, ed.,
Active Food Packaging, Blackie Academic & Professional Pub., London, pp. 193-202,
1995.

155

6. CONCLUSIONS AND FUTURE WORK

6.1. Conclusions

Development of multilayer ﬁlm incorporating iron based oxygen scavenger was
done successfully and the 082 ﬁlm was preferred to adopt as an oxygen scavenging ﬁlm
to make an active package, because it did not have agglomerations, and therefore it was
superior to OSI in mechanical properties such as tensile & break strength. For oxygen
scavenging, the ﬁlms were useful even though that had a multilayer structure containing
coextruded LLDPE on the inside ofthe ﬁlm. The OS2 ﬁlm was a little better than the

OS 1 , consuming 6.10 cc 0; per g ﬁlm after 30 days storage at 23 °C and 100% RH.

In the development of active packaging for cosmetics, the active packaging
rapidly reduces the oxygen concentration of the headspace compared with conventional
packaging. It reached 0.0% from 20.9 % within 30 days and stayed lower than 0.1% for
I 80 days, while conventional packaging remained near 10.0% after 180 days stored at

23 °C and 65% RH. In evaluating the shelf life of retinol in cosmetics, the concentration

in the conventional packaging was rapidly reduced from 3,464 IU to 2,51 l lU after 24
weeks stored at 23 °C and 65% RH, while the concentration in the active packages

remained over 3,000 IU after 24 weeks. A shelflife of51.6 weeks is estimated, based on
rEduction of retinol to 2,500 IU.
From SEM & EDS analysis, the main elements of oxygen scavenger in the core
l"113/er ofa multilayer ﬁlm were identiﬁed as iron (Fe), sodium (Na) and chloride (Cl).
Throughout the observation of the migration behavior for the main elements by
the SEM & EDS, no migration of any of these main elements was detected in the inner

layer adjacent to the core layer containing oxygen scavenger of the OS multilayer ﬁlms

156

(OSI and OS2), which were in direct contact with the food simulants or cosmetic. This
means that the main elements of oxygen scavenger in the core layer of the OS ﬁlms did
not pass through the inner layer and did not contact the food simulants and cosmetic.
However, from another analysis by SEM & EDS of the seamed parting line in a tube that

was stored at 10 days and 40 °C in 3% acetic acid, the main elements could be observed.

while the main elements were not detected on the non seamedarea in the inside of a tube.
Therefore, the main elements of oxygen scavenger seem to be migrating through the
seamed parting line which was exposed directly to the simulants.

Quantitative analysis of migration of the main elements into various food
simulants was conducted using an atomic absorption (AA) spectrometer for both types of
oxygen scavengers. For the sums of main migrant components (NaCl + CaClg + F6203).
the migration values in 3% acetic acid were the highest and the next were the values in
Water among the food simulants. The migration value of OSI in 3% acetic acid was as
2.322 mg/L, 082 was 0.928 mg/L and LLDPE was 0.280 mg/L. However, these values

are much less than the EU limit for total migration as 60 mg/L (90/128/EEC).

157

6.2. Future work

The positive effect of an active packaging system to extend the shelf life was
observed, and the migration value of main components from oxygen scavenger system
was evaluated as smaller than the EU limit. The next step will apply this kind of active
packaging system to cosmetics and then pharmaceuticals. However, there are some
problems as a future work to reduce the quantity of Si (silicate) and the agglomeration
during ﬁlm and packaging processing and how to protect against the migration from the
seamed parting line of the package before commercializing.

Recently, in order to increase the shelf life of products more than ever, oxygen
scavengers using nano-composites such as silicate or organo-clay have also been applied.
The oxygen scavenger of nano-size may migrate much more easily to products compared
with micro-size such as the iron based oxygen scavenger that is currently used. Therefore,
this analytical method will be useful in developing this kind of active packaging as

another future work.

158

APPENDICES

159

 

APPENDIX A: Properties and oxygen absorbing amount of multilayer ﬁlm

Table 31. UV/VIS spectrometer data

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
190 13.221 190 16.533 190 56.143
191 11.241 191 23.715 191 59.665
192 21.918 192 5.499 192 71.812
193 17.801 193 16.879 193 54.75
194 4.646 194 1.821 194 33.409
195 -2.158 195 -3.15 195 34.103
196 27.967 196 16.136 196 42.647
197 0.28 197 17.24 197 13.649
198 -5.222 198 19.776 198 7.242
199 1.589 199 20.803 199 7.26
200 20.435 200 27.774 200 4.322
201 -2.587 201 34.642 201 -6.034
202 12.192 202 27.366 202 7.051
203 0.508 203 18.751 203 0.601
204 8.83 204 30.442 204 0.872
205 ' 6.453 205 24.64 205 3.032
206 7.714 206 18.731 206 9.907
207 6.953 207 17.347 207 3.204
208 6.352 208 13.01 1 208 12.866
209 13.255 209 15.062 209 20.485
210 15.821 210 11.679 210 15.794
211 14.637 211 20.17 211 18.566
212 22.148 212 18.419 212 22.085
213 23.483 213 26.716 213 20.861
214 23.874 214 26.168 214 19.508
215 26.106 215 26.703 215 17.853
216 26.306 216 32.326 216 17.532
217 26.864 217 32.697 217 16.541
218 29.51 218 36.054 218 18.422
219 33.634 219 34.027 219 15.761
220 31.654 220 32.678 220 16.984
221 31.354 221 32.579 221 18.952
222 37.441 222 28.617 222 17.207
223 34.721 223 32.175 223 16.776
224 39.887 224 30.131 224 16.096
225 41.562 225 33.223 225 16.14

 

 

 

160

Table 31.(continued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI 082

nm Transmittance nm Transmittance nm Transmittance
226 41.348 226 36.41 1 226 16.064
227 42.554 227 35.142 227 16.185
228 43.382 228 37.4 228 18.092
229 46.139 229 37.079 229 19.159
230 45.325 230 39.702 230 19.318
231 48.55 231 39.548 231 21.432
232 52.347 232 38.419 232 21.763
233 54.085 233 43.152 233 22.315
234 58.022 234 45.785 234 26.261
235 61.81 235 50.664 235 27.724
236 66.294 236 55.755 236 28.713
237 70.66 237 61.874 237 30.914
238 75.037 238 66.175 238 32.979
239 80.48 239 72.032 239 35.181
240 84.163 240 76.652 240 36.58
241 85.845 241 77.888 241 38.098
242 87.905 242 80.34 242 37.898
243 89.751 243 81.757 243 38.375
244 92.728 244 82.793 244 39.1 14
245 94.179 245 82.803 245 39.238
246 94.238 246 82.335 246 38.33
247 95.75 247 82.49 247 39.328
248 97.372 248 82.886 248 40.283
249 97.318 249 83.354 249 38.6
250 98.913 250 83.23 250 40.585
251 98.508 251 82.004 251 39.937
252 97.08 252 83.882 252 39.381
253 96.919 253 85.369 253 38.453
254 95.94 254 82.553 254 40.016
255 93.255 255 81.739 255 38.258
256 91.385 256 81.13 256 38.648
257 91.61 257 80.125 257 36.749
258 89.459 258 80.335 258 37.301
259 89.485 259 79.06 259 35.394
260 88.325 260 78.334 260 35.607
261 87.754 261 78.216 261 35.49
262 _87.046 262 77.827 262 35.891
263 85.144 263 76.61 1 263 34.506
264 86.813 264 77.136 264 34.741
265 85.33 265 74.137 265 34.078

 

 

 

 

161

 

 

Table 31.(continued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
266 85.822 266 74.164 266 34.06
267 86.58 267 73.971 267 34.657
268 86.28 268 74.086 268 33.424
269 86.459 269 72.268 269 33.785
270 84.555 270 72.097 270 32.74
271 86.167 271 72.389 271 33.594
272 85.352 272 72.788 272 33.362
273 82.971 273 69.424 273 33.052
274 83.991 274 69.06 274 32.446
275 82.244 275 68.92 275 31.155
276 83.922 276 69.413 276 32.838
277 84.1 12 277 71.285 277 32.43
278 83.792 278 73.205 278 33.661
279 86.049 279 74.639 279 34.389
280 85.97 280 75.419 280 36.199
281 87.277 281 76.445 281 36.09
282 85.519 282 77.713 282 37.343
283 86.934 283 77.095 283 37.719
284 86.939 284 76.932 284 36.06
285 86.51 285 78.72 285 34.943
286 89.315 286 77.86 286 35.795
287 91.291 287 77.262 287 35.537
288 92.793 288 79.024 288 36.107
289 94.034 289 78.517 289 35.434
290 94.204 290 78.935 290 35.693
291 95.079 291 78.663 291 35.542
292 96.171 292 80.023 292 35.531
293 97.173 293 80.147 293 36.439
294 97.778 294 81.859 294 35.763
295 96.353 295 82.827 295 37.424
296 95.488 296 82.718 296 37.302
297 95.335 297 83.076 297 36.933
298 95.607 298 83.207 298 37.375
299 95.158 299 82.887 299 37.387
300 95.378 300 82.699 300 37.8
301 95.288 301 81.3 301 37.548
302 95.231 302 83.047 302 36.769
303 95.421 303 81.078 303 38.689
304 96.159 304 82.437 304 37.67
305 94.962 305 80.514 305 37.369

 

 

 

 

162

Table 3 l . (continued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
306 95.999 306 80.433 306 37.378
307 94.955 307 80.434 307 37.262
308 94.196 308 78.736 308 36.98
309 94.87 309 78.659 309 36.056
310 95.376 310 79.117 310 35.915
311 94.788 311 78.845 311 34.777
312 93.178 312 79.206 312 35.706
313 93.576 313 79.549 313 35.146
314 93.327 314 82.357 314 35.331
315 93.651 315 81.698 315 35.382
316 95.942 316 82.133 316 35.561
317 94.792 317 83.809 317 35.434
318 96.62 318 82.145 318 35.398
319 96.62 319 82.794 319 35.201
320 96.638 320 83.644 320 36.193
321 95.89 321 83.528 321 36.216
322 94.586 322 80.797 322 35.917
323 95.168 323 81.986 323 36.495
324 93.247 324 80.652 324 35.883
325 93.288 325 79.078 325 36.283
326 93.492 326 78.694 326 35.538
327 93.084 327 78.781 327 35.555
328 91.543 328 87.557 328 41

329 94.692 329 86.049 329 41.896
330 95.972 330 85.391 330 41.136
331 98.004 331 83.184 331 38.818
332 98.566 332 82.425 332 37.955
333 96.461 333 78.62 333 37.088
334 97.893 334 78.049 334 37.179
335 97.484 335 78.265 335 32.061
336 96.693 336 79.744 336 35.272
337 94.764 337 77.475 337 34.737
338 92.642 338 79.214 338 34.905
339 91.339 339 80.353 339 35.376
340 91.419 340 80.1 15 340 35.999
341 92.083 341 82.566 341 37.296
342 93.458 342 82.025 342 38.597
343 93.866 343 84.137 343 39.354
344 94.859 344 83.874 344 39.345
345 94.901 345 83.661 345 39.694

 

 

163

 

Table 3 l.(continued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
346 93.606 346 82.171 346 40.084
347 93.992 347 80.852 347 39.449
348 93.531 348 81.754 348 38.48
349 92.764 349 79.932 349 36.593
350 94.23 350 80.107 350 36.247
351 93.414 351 81.189 351 35.568
352 95.594 352 82.063 352 36.436
353 96.248 353 81.879 353 38.222
354 96.971 354 81.684 354 38.546
355 95.723 355 82.97 355 38.83
356 96.01 356 81.143 356 39.745
357 98.084 357 82.277 357 39.158
358 94.817 358 81.456 358 38.049
359 94.248 359 79.991 359 38.038
360 94.386 360 80.402 360 36.759
361 92.431 361 79.054 361 36.384
362 91.9 362 79.67 362 35.979
363 92.138 363 78.922 363 36.144
364 92.481 364 78.117 364 35.745
365 91.375 365 79.433 365 35.901
366 92.647 366 77.967 366 35.65
367 93.226 367 77.742 367 36.913
368 93.84 368 78.877 368 35.844
369 94.272 369 79.65 369 36.224
370 94.59 370 79.77 370 36.061
371 95.916 371 79.795 371 36.096
372 94.668 372 79.267 372 36.686
373 95.161 373 79.483 373 35.991
374 95.543 374 79.959 374 36.596
375 93.023 375 80.563 375 36.123
376 94.206 376 79.545 376 36.764
377 95.528 377 80.976 377 35.554
378 93.921 378 81.278 378 37.441
379 95.291 379 82.838 379 37.811
380 92.845 380 81.971 380 37.741
381 92.324 381 81.407 381 37.333
382 95.212 382 81.708 382 36.741
383 91.93 383 79.658 383 34.621
384 92.983 384 78.889 384 36.264
385 93.416 385 79.351 385 36.297

 

 

 

 

164

 

 

Table 3 l.(continued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
386 93.715 386 79.433 386 36.174
387 93.733 387 79.481 387 36.338
388 93.57 388 79.527 388 36.264
389 93.579 389 79.512 389 36.505
390 93.629 390 79.519 390 36.421
391 93.546 391 79.324 391 36.561
392 93.688 392 79.499 392 36.801
393 93.517 393 79.325 393 36.778
394 93.553 394 79.401 394 36.814
395 93.481 395 79.547 395 36.865
396 93.153 396 79.252 396 36.831
397 93.172 397 79.032 397 36.617
398 93.274 398 79.151 398 36.617
399 93.257 399 79.028 399 36.681
400 93.41 400 79.227 400 36.534
401 93.333 401 79.243 401 36.527
402 93.37 402 79.25 402 36.51 1
403 93.38 403 79.399 403 36.358
404 93.643 404 79.438 404 36.412
405 93.531 405 79.616 405 36.433
406 93.421 406 79.632 406 36.545
407 93.563 407 79.717 407 36.528
408 93.418 408 79.592 408 36.587
409 93.388 409 79.564 409 36.622
410 93.524 410 79.398 410 36.639
41 1 93.26 41 1 79.309 41 1 36.764
412 93.215 412 79.252 I 412 36.657
413 93.2 413 79.155 413 36.721
414 93.344 414 79.164 414 36.637
415 93.295 415 79.214 415 36.657
416 93.397 416 79.19 416 36.601
417 93.376 417 79.161 417 36.475
418 93.29 418 79.157 418 36.497
419 93.417 419 79.253 419 36.57
420 93.519 420 79.496 420 36.551
421 93.399 421 79.378 421 36.584
422 93.431 422 79.819 422 36.505
423 93.022 423 79.224 423 36.312
424 92.945 424 79.001 424 36.409
425 92.933 425 78.949 425 36.175

 

 

 

 

 

 

 

165

 

Table 31.(c0ntinued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
426 92.765 426 78.766 426 36.235
427 92.918 427 78.947 427 36.204
428 92.821 428 79.051 428 36.23
429 92.872 429 78.817 429 36.562
430 92.983 430 79.093 430 36.603
431 93.081 431 79.393 431 36.661
432 93.231 432 79.312 432 36.934
433 93.101 433 79.228 433 36.726
434 93.359 434 79.556 434 36.893
435 93.203 435 79.524 435 37.076
436 93.119 436 79.554 436 37.024
437 93.451 437 79.624 437 37.058
438 93.406 438 79.688 438 36.949
439 93.51 439 79.643 439 37.025
440 93 .743 440 79.626 440 36.971
441 93.538 441 79.683 441 36.773
442 93.416 442 79.691 442 36.814
443 93.429 443 79.648 443 36.599
444 93.426 444 79.519 444 36.587
445 93 .409 445 79.471 445 36.668
446 93 .304 446 79.342 446 36.715
447 93.523 447 79.308 447 36.593
448 93.238 448 79.363 448 36.55
449 93 .241 449 79.262 449 36.769
450 93.167 450 79.343 450 36.812
451 93.109 451 79.274 451 36.746
452 93.027 452 79.274 452 36.857
453 93.029 453 79.312 453 36.821
454 93.019 454 79.168 454 36.896
455 93.1 455 79.241 455 36.799
456 93.095 456 79.241 456 36.813
457 93.391 457 79.507 457 36.643
458 93.285 458 79.428 458 36.745
459 93.385 459 79.415 459 36.734
460 93.417 460 79.578 460 36.732
461 93.475 461 79.657 461 36.762
462 93 .406 462 79.7 462 36.919
463 93.396 463 79.66 463 36.935
464 93.275 464 79.723 464 36.999
465 93.139 465 79.73 465 36.995

 

 

 

 

 

 

 

166

 

Table 3 l.(continuea')

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
466 93.195 466 79.587 466 37.032
467 93.219 467 79.814 467 37.046
468 93.188 468 79.668 468 36.969
469 93.176 469 79.564 469 37.1 12
470 93.16 470 79.571 470 36.955
471 93.324 471 79.506 471 37.091
472 93.347 472 79.347 472 37.07
473 93.208 473 79.432 473 37.025
474 93.325 474 79.463 474 36.988
475 93.397 475 79.47 475 37.024
476 93.38 476 79.474 476 36.952
477 93.325 477 79.627 477 36.98
478 93.219 478 79.587 478 37.057
479 93.329 479 79.774 479 36.961
480 93.319 480 79.813 480 37.037
481 93.289 481 79.635 481 36.985
482 93.296 482 79.815 482 36.975
483 93.221 483 79.806 483 36.939
484 93.213 484 79.784 484 37.066
485 93.21 485 79.646 485 37.076
486 93.164 486 79.604 486 37.006
487 93.307 487 79.662 487 37.183
488 93.24 488 79.742 488 37.176
489 93.314 489 79.764 489 37.156
490 93.21 1 490 79.685 490 37.147
491 93.207 491 79.622 491 37.183
492 93.268 492 79.657 492 37.295
493 93.255 493 79.765 493 37.304
494 93.274 494 79.741 494 37.306
495 93.289 495 79.83 495 37.21
496 93.159 496 79.678 496 37.178
497 93.176 497 79.71 497 37.082
498 93.253 498 79.793 498 37.172
499 93.356 499 79.876 499 37.188
500 93.36 500 79.941 500 37.09
501 93.382 501 79.938 501 37.335
502 93.436 502 79.924 502 37.267
503 93.401 503 79.962 503 37.29
504 93.406 504 79.985 504 37.345
505 93.455 505 80.041 505 37.413

 

 

 

 

 

 

167

 

Table 3 l . (continued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI 082
nm Transmittance nm Transmittance nm Transmittance
506 93.315 506 79.994 506 37.402
507 93.253 507 80.001 507 37.394
508 93.208 508 79.935 508 37.433
509 93.364 509 80.009 509 37.348
510 93.278 510 79.867 510 37.484
51 1 93.226 51 1 79.944 51 1 37.489
512 93.295 512 79.947 512 37.448
513 93.238 513 79.876 513 37.447
514 93.285 514 79.852 514 37.41
515 93.258 515 79.912 515 37.355
516 93.218 516 79.877 516 37.34
517 93.222 517 79.892 517 37.335
518 93.265 518 79.875 518 37.307
519 93.174 519 79.936 519 37.268
520 93.24 520 79.966 520 37.315
521 93.331 521 79.945 521 37.336
522 93.201 522 79.987 522 37.289
523 93.205 523 79.978 523 37.339
324 93.289 524 79.871 524 37.399
525 93.252 525 79.918 525 37.414
526 93.201 526 79.838 526 37.45
527 93.31 I 527 79.855 527 37.544
528 93.367 528 79.972 528 37.519
529 93.281 529 80.033 529 37.523
530 93.222 530 80.001 530 37.533
F531 93.239 531 80.19 531 37.601
532 93.216 532 80.239 532 37.654
533 93.07 533 80.15 533 37.634
534 93.275 534 80.18 534 37.627
535 93.211 535 80.17 535 37.618
536 93.272 536 80.151 536 37.602
537 93.19 537 80.001 537 37.558
538 93.257 538 80.111 538 37.577
539 93.191 539 80.022 539 37.511
540 93.232 540 79.968 540 37.552
541 93.16 541 79.926 541 37.545
542 93.155 542 79.99 . 542 37.54
543 93.242 543 80.008 543 37.73
544 93.248 544 80.044 544 37.636
545 93.236 545 80.073 545 37.731

 

 

 

 

168

 

Table 31.(continued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
546 93.15 546 80.084 546 37.719
547 93.148 547 80.056 547 37.714
548 93.1 14 548 80.064 548 37.71 1
549 93.18 549 80.195 549 37.751
550 93.152 550 80.158 550 37.789
551 93.216 551 80.213 551 37.802
552 93.151 552 80.116 552 37.834
553 93.387 553 80.122 553 37.808
554 93.31 554 80.215 554 37.776
555 93.238 555 80.184 555 37.793
556 93.245 556 80.144 556 37.828
557 93.25 557 80.219 557 37.775
558 93.124 558 80.195 558 37.811
559 93.152 559 80.314 559 37.915
560 93.121 560 80.21 560 37.939
561 93.169 561 80.222 561 37.924
562 93.172 562 80.291 562 37.874
563 93.125 563 80.214 563 38.023
564 93.1 14 . 564 80.067 564 37.935
565 93.056 565 80.102 565 37.959
566 93.192 566 80.1 566 38.009
567 93.241 567 80.17 567 38.009
568 93.163 568 80.208 568 38.078
569 93.168 569 80.179 569 37.984
570 93.184 570 80.2 570 38.006
571 93.289 571 80.252 571 37.98
572 93.171 572 80.238 572 38.033
573 93.127 573 80.389 573 38.103
574 93.228 574 80.386 574 38.025
575 93.23 575 80.388 575 38.075
576 93.247 576 80.415 576 38.036
577 93.337 577 80.466 577 38.124
578 93.293 578 80.388 578 38.092
579 93.296 579 80.402 579 38.057
580 93.341 580 80.334 580 38.129
581 93.271 581 80.296 581 38.05
582 93.216 582 80.23 582 38.069
583 93.137 583 80.145 583 38.109
584 93.303 584 80.241 584 38.1
585 93.039 585 80.118 585 38.14

 

 

 

 

 

 

'1 69

 

 

Table 3 l . (continued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
586 93.147 586 80.125 586 38.115
587 93.11 587 80.164 587 38.181
588 93.093 588 80.177 588 38.217
589 93.098 589 80.23 589 38.254
590 93.157 590 80.3 590 38.26
591 93.136 591 80.356 591 38.295
592 93.171 592 80.391 592 38.319
593 93.173 593 80.354 593 38.312
594 93.199 594 80.41 594 38.241
595 93.154 595 80.402 595 38.307
596 93.231 596 80.435 596 38.263
597 93.152 597 80.43 597 38.221
598 93.1 15 598 80.309 598 38.227
599 93.068 599 80.244 599 38.25
600 93.151 600 80.271 600 38.25
601 93.171 601 80.266 601 38.298
602 93.155 602 80.262 602 38.31 1
603 93.163 603 80.247 603 38.286
604 93.215 604 80.348 604 38.35
605 93.173 605 80.332 605 38.371
606 93.212 606 80.378 606 38.408
607 93.193 607 80.446 607 38.415
608 93.206 608 80.38 608 38.448
609 93.249 609 80.412 609 38.42
610 93.271 610 80.492 610 38.461
61 1 93.257 61 1 80.429 61 1 38.486
612 93.305 612 80.458 612 38.494
613 93.264 613 80.441 613 38.469
614 93.241 614 80.477 614 38.442
615 93.22 615 80.339 615 38.422
616 93.324 616 80.404 616 38.457
617 93.216 617 80.461 617 38.482
618 93.192 618 80.357 618 38.453
619 93.211 619 80.409 619 38.496
620 93.138 620 80.386 620 38.466
621 93.147 621 80.359 621 38.563
622 93.121 622 80.327 622 38.535
623 93.098 623 80.332 623 38.592
624 93.141 624 80.492 624 38.636
625 93.09 625 80.358 625 38.604

 

 

 

170

 

Table 3 l.(continued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OS 1 OS2

nm Transmittance nm Transmittance nm Transmittance
626 93.084 626 80.384 626 38.542
627 93.127 627 80.444 627 38.626
628 93.162 628 80.443 628 38.63
629 93.16 629 80.463 629 38.625
630 93.263 630 80.452 630 38.673
631 93.231 631 80.535 631 38.639
632 93.24 632 80.553 632 38.641
633 93.246 _633 80.577 633 38.641
634 93.202 634 80.591 634 38.656
635 93.296 635 80.561 635 38.699
636 93.254 636 80.56 636 38.598
637 93.276 637 80.553 637 38.661
638 93.261 638 80.539 638 38.694
639 93.193 639 80.452 639 38.615
640 93.095 640 80.389 640 38.662
641 93.036 641 80.355 641 38.605
642 93.045 642 80.392 642 38.656
643 93.063 643 80.436 643 38.639
644 93 644 80.494 644 38.72
645 93.049 645 80.489 645 38.705
646 93.079 646 80.638 646 38.799
647 93.1 1 647 80.566 647 38.87
648 93.095 648 80.578 648 38.84
649 93.203 649 80.72 649 38.866
650 93.179 650 80.647 650 38.871
651 93.136 651 80.605 651 38.904
652 93.08 652 80.54 652 38.896
653 93.107 653 80.513 653 38.914
654 93.151 654 80.527 654 38.856
655 93.043 655 80.389 655 38.954
656 93.143 656 80.46 656 38.913
657 93.034 657 80.41 657 38.836
658 93.145 658 80.423 658 38.784
659 93.129 659 80.478 659 38.894
660 93.101 660 80.428 660 38.845
661 93.151 661 80.477 661 38.787
662 93.14 662 80.567 662 38.831
663 93.176 663 80.555 663 38.865
664 93.143 664 80.524 664 38.912
665 93.165 665 80.51 665 38.938

 

 

 

 

 

 

171

 

 

Table 3 l.(c0ntinued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
666 93.164 666 80.577 666 39.03
667 93.183 667 80.677 667 39.02
668 93.199 668 80.644 668 39.03
669 93.275 669 80.717 669 39.026
670 93.197 670 80.718 670 39.101
671 93.273 671 80.718 671 39.134
672 93.249 672 80.763 672 39.151
673 93.299 673 80.71 1 673 39.108
674 93.26 674 80.69 674 39.089
675 93.124 675 80.573 675 39.008
676 93.135 676 80.601 676 39.047
677 93.181 677 80.653 677 39.081
678 93.229 678 80.571 678 39.05
679 93.106 679 80.556 679 39.053
680 93.149 680 80.654 680 39.041
681 93.122 681 80.646 681 39.082
682 93.042 682 80.664 682 39.023
683 92.996 683 80.549 683 39.065
684 93.069 684 80.686 684 39.033
685 93.055 685 80.716 685 39.101
686 93.135 686 80.636 686 39.165
687 93.185 687 80.579 687 39.161
688 93.137 688 80.545 688 39.178
689 93.154 689 80.603 689 39.203
690 93.138 690 80.617 690 39.213
691 93.173 691 80.637 691 39.243
692 93.108 692 80.689 692 39.224
693 93.139 693 80.696 693 39.251
694 93.109 694 80.7 63 694 39.239
695 93.171 695 80.788 695 39.229
696 93.134 696 80.822 696 39.289
697 93.1 697 80.771 697 39.219
698 93.153 698 80.726 698 39.213
699 93.141 699 80.665 699 39.243
700 93.13 700 80.624 700 39.188
701 93.122 701 80.55 701 39.156
702 93.1 13 702 80.588 702 39.229
703 93.135 703 80.592 703 39.167
704 93.141 704 80.614 704 39.215
705 93.1 19 705 80.666 705 39.22

 

 

 

 

 

 

172

 

Table 3 l.(c0ntinued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OS 1 082

nm Transmittance nm Transmittance nm Transmittance
706 93.109 706 80.733 706 39.279
707 93.072 707 80.761 707 39.216
708 93.097 708 80.744 708 39.298
709 93.144 709 80.768 709 39.322
710 93.12 710 80.734 710 39.319
711 93.142 71 1 80.798 71 1 39.346
712 93.149 712 80.842 712 39.397
713 93.115 713 80.794 713 39.407
714 93.262 714 80.786 714 39.406
715 93.234 715 80.748 715 39.426
716 93.104 716 80.667 716 39.41
717 93.08 717 80.691 717 39.459
718 93.128 718 80.607 718 39.34
719 93.06 719 80.666 719 39.454
720 93.098 720 80.637 720 39.435
721 93.127 721 80.671 721 39.508
722 93.022 722 80.606 722 39.492
723 93.068 723 80.693 723 39.467
724 93.1 14 724 80.692 724 39.48
725 93.077 725 80.745 725 39.551
726 93.04 726 80.758 726 39.508
727 93.172 727 80.869 727 39.571
728 93.149 728 80.847 728 39.524
729 93.087 729 80.823 729 39.464
730 93.046 730 80.782 730 39.396
731 93.073 731 80.763 731 39.473 _
732 93.02 732 80.746 732 39.431
733 93.056 733 80.731 733 39.445
734 93.048 734 80.742 734 39.47
735 93.054 735 80.826 735 39.467
736 93.04 736 80.788 736 39.447
737 93.068 737 80.754 737 39.435
738 93.139 738 80.865 738 39.556
739 93.148 739 80.93 739 39.598
740 93.155 740 80.804 740 39.597
741 93.194 741 80.928 741 39.661
742 93.276 742 80.865 742 39.626
743 93.235 743 80.82 743 39.69
744 93.251 744 80.883 744 39.681
745 93.221 745 80.839 745 39.736

 

 

 

 

 

 

173

 

 

Table 31.(c0ntinued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
746 93.188 746 80.81 746 39.592
747 93.151 747 80.748 747 39.649
748 93.1 19 748 80.716 748 39.587
749 93.146 749 80.737 749 39.537
750 93.195 750 80.694 750 39.552
751 93.107 751 80.781 751 39.584
752 93.097 752 80.66 752 39.551
753 93.099 753 80.682 753 39.633
754 93.101 754 80.809 754 39.608
755 93.055 755 80.817 755 39.635
756 92.95 756 80.835 756 39.617
757 92.987 757 80.785 757 39.669
758 92.996 758 80.878 758 39.684
759 92.943 759 80.802 759 39.696
760 92.969 760 80.809 760 39.766
761 92.96 761 80.893 761 39.719
762 92.968 762 80.836 762 39.812
763 93.1 16 763 80.87 763 39.827
764 93.106 764 80.94 764 39.816
765 93.127 765 80.862 765 39.815
766 93.14 766 80.914 766 39.879
767 93.244 767 80.892 767 39.904
768 93.148 768 80.908 768 39.864
769 93.258 769 80.835 769 39.828
770 93.175 770 80.787 770 39.873
771 93.17 771 80.848 771 39.827
772 93.147 772 80.767 772 39.743
773 93.208 773 80.776 773 39.775
774 93.068 774 80.817 774 39.684
775 93.145 775 80.816 775 39.73
776 92.985 776 80.786 776 39.77
777 93.088 777 80.882 777 39.826
778 93.02 778 80.961 778 39.909
779 93.152 779 80.94 779 39.91
780 93.107 780 80.851 780 40.046
781 93.05 781 81.066 781 39.924
782 93.208 782 81.043 782 40.039
783 93.103 783 81.044 783 40.013
784 93.096 784 81.085 784 39.97
785 93.079 785 81.047 785 40.042

 

 

 

 

174

 

 

Table 3 1 . (continued)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

LLDPE OSI OS2

nm Transmittance nm Transmittance nm Transmittance
786 93.066 786 81.031 786 39.943
787 93.127 787 81.021 787 39.946
788 93.008 788 80.848 788 39.936
789 93.002 789 80.835 789 39.869
790 93.052 790 80.804 790 39.924
791 93.015 791 80.759 791 39.884
792 93.1 15 792 80.809 792 39.845
793 93.1 18 793 80.814 793 39.848
794 93.094 794 80.75 794 39.831
795 93.079 795 80.783 795 39.87
796 93.1 7 796 80.824 796 40.074
797 93.223 797 80.953 797 40.034
798 93.154 798 80.936 798 40.032
799 93.317 799 81.129 799 40.116
800 93.359 800 81.156 800 40.253

 

 

 

 

 

175

 

Table 32. Film thickness data

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

1)LLDPE
CD-LLDPE Sample 1 2 3 4 5
1 5.5 5.5 5.5 5.0 5.0
2 5.0 5.5 5.0 5.0 5.5
3 5.5 5.5 5.5 5.5 5.0
Ave 5.33 5.50 5.33 5.17 5.17
Std 0.29 0.00 0.29 0.29 0.29
MD-LLDPE Sample 1 2 3 4 5
1 5.5 5.5 5.5 5.5 5.5
2 5.5 5.5 5.5 5.5 5.0
3 5.5 5.0 5.5 5.0 5.5
Avg 5.50 5.33 5.50 5.33 5.33
Std 0.00 0.29 0.00 0.29 0.29
2) OS]
CD—OSI Sample 1 2 3 4 5
1 5.0 4.0 4.5 5.5 5.0
2 4.5 6.0 5.5 4.0 5.5
3 5.0 5.0 4.5 ' 5.0 4.5
Ave 4.83 5.00 4.83 4.83 5.00
Std 0.29 1.00 0.58 0.76 0.50
MD-OSI Sample 1 2 3 4 5
1 4.5 5.5 4.5 5.0 5.5
2 5.5 4.5 5.5 5.5 5.0
3 5.0 5.0 . 5.5 4.5 4.5
Ave 5.00 5.00 5.17 5.00 5.00
Std 0.50 0.50 0.58 0.50 0.50

 

 

 

 

 

 

 

176

 

 

3) 082

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

CD-OS2 Sample 1 2 3 4 5
| 5.0 5.5 5.0 5.5 5.5
2 5.5 5.0 5.0 5.5 5.0
3 4.5 5.5 5.0 5.0 5.0
Ave 5.00 5.33 5.00 5.33 5.17
Std 0.50 0.29 0.00 0.29 0.29
MD-OS2 Sample 1 2 3 4 5
1 5.0 5.5 5.0 5.0 5.0
2 5.0 5.5 5.0 5.0 5.5
3 5.5 5.0 5.5 5.5 5.0
Ave 5.17 5.33 5.17 5.17 5.17
Std 0.29 0.29 0.29 0.29 0.29
L—
Table 33. Mechanical properties data
1) LLDPE
Sample No. Maximum Tensile Break Break
Load Strength Strength Elongation
kgf kg/cm2 kg/cm2 (%)
CD-LLDPE 1 15.22 421.19 374.88 949.9
2 12.74 352.68 306.31 880.5
3 13.53 374.38 338.07 913.3
4 13.77 381.01 343.96 929.2
5 14.46 400.31 361.39 975.8
Ave 13.94 385.91 344.92 929.7
Std 0.941 26.043 26.017 36.14
MD-LLDPE 1 14.00 421.19 374.88 949.9
2 14.00 352.68 306.31 880.5
3 14.04 374.38 338.07 913.3
4 13.94 371.93 336.07 907.3
5 14.12 376.85 340.29 918.7
Ave 14.02 379.41 339.13 913.9
Std 0.065 25.237 24.327 24.89

 

177

 

 

2) OSI

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sample No. Maximum Tensile Break Break
Load Strength Strength Elongation

kgf kg/cm2 kg/cm2 (%)
CD-OSI 1 6.56 217.32 163.87 681.3
2 6.84 226.49 181.97 705.3
3 7.20 238.39 238.39 704.6
4 7.06 233.82 181.54 707.7
5 6.91 228.71 183.79 705.2
Ave 6.91 228.95 189.91 700.8
Std 0.241 7.969 28.279 10.98
MD-OSI 1 7.88 260.91 21 1.55 609.7
2 7.80 244.86 192.91 614.3
3 7.29 228.19 179.98 630.2
4 7.43 232.98 186.44 605.4
5 7.72 242.07 201.21 601.8
Ave 7.62 241.80 194.42 612.3
Std 0.253 12.626 12.390 1 1.06

3) 082
Sample No. Maximum Tensile Break Break
Load Strength Strength Elongation

kgf kg/cm2 kg/cm2 (%)

CD-OS2 l 8.97 267.43 222.55 761
2 9.35 278.76 237.09 777.4
3 8.08 242.06 199.99 724.6
4 8.87 264.26 217.20 764.3
5 8.74 260.52 220.87 768.5
Ave 8.80 262.61 219.54 759.2
Std 0.463 13.355 13.291 20.27
MD-OSZ 1 9.46 293.14 240.91 694.1
2 9.72 301.27 256.41 699.6
3 10.85 336.29 294.08 732.1
4 10.14 314.21 270.71 704.1
5 9.91 303.81 258.55 706.4
Ave 10.01 309.74 264.13 707.3
Std 0.529 16.640 19.814 14.66

 

 

 

 

 

 

 

178

 

 

Table 34. Oxygen absorbing amount data

1) The value of 50 % - OSI and OS2

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Film SAMPLE 0 DAY 30 DAYS 02 FILM WT 02
Absorb Absorb
OS 1 - No. (cc) (cc) (cc) (g) (cc/ g)
50% 1 205.0 183.1 21.9 3.99 5.49
2 198.3 175.2 23.1 4.01 5.76
201.2 177.9 23.3 4.02 5.80
Ave 201.5 178.7 22.8 4.01 5.68
Std 3.36 4.02 0.76 0.02 0.17
OS2- 1 199.8 175.2 24.6 4.01 6.13
50% 2 202.5 178.2 24.3 3.97 6.12
3 203.3 179.1 24.2 4.01 6.03
Ave 201.9 177.5 24.4 4.00 6.10
Std 1.83 2.04 0.21 0.02 0.05
2) The value of 20 %, 30 %, 50 % - OS1 and 052
O2
Film OS 0 0 30 30 02 Film 02 Absorb
Content Day Day Day Day Absorb Wt. Absorb Content
(%) (CC) (%) (CC) (%) (CC) (g) (CC/g) (%)
OS1 *50 201.5 20.9 178.7 18.5 22.8 4.01 5.68 50.7
30 199.1 20.9 189.0 19.8 10.1 3.01 3.36 29.9
20 205.0 20.9 198.3 20.2 6.7 2.99 2.24 20.0
OS2 *50 201.9 20.9 177.5 18.4 24.4 4.00 6.10 50.4
30 199.3 20.9 188.4 19.8 10.9 3.00 3.63 30.1
20 203.3 20.9 196.0 20.1 7.3 3.02 2.42 20.0

 

 

 

 

 

 

 

 

 

 

 

*50: Average ofthree specimens of OSI - 50% and OS2 - 50 % on Table 22 — 1

179

 

 

APPENDIX B: Oxygen and retinal concentration of active packaging

Table 35. Oxygen concentration in headspace data

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Day 0 7 30 60 90 '1 20 150 180
Control 20.060 16.750 12.500 10.570 10.020 9.780 9.520 9.290
20.200 17.020 13.200 1 1.080 10.430 10.120 9.770 9.520
19.950 16.280 12.030 10.240 9.750 9.470 9.220 9.050
Ave 20.070 16.683 12.577 10.630 10.067 9.790 9.503 9.287
Std 0.125 0.374 0.589 0.423 0.342 0.325 0.275 0.235
OS2 20.120 2.980 0.000 0.000 0.000 0.000 0.000 0.010
20.240 4.020 0.000 0.000 0.000 0.000 0.020 0.000
20.000 3.250 0.000 0.000 0.000 0.000 0.000 0.020
Ave 20.120 3.417 0.000 0.000 0.000 0.000 0.007 0.010
Std 0.120 0.540 0.000 0.000 0.000 0.000 0.012 0.010—ﬂ
Table 36. Standard calibration curve data
Unit: AU
Sample 0.1mg/100m1 0.4mg/100m1 1mg/100m1 3mg/100m1
1 1,225 5,543 1 1,983 32,923
2 1,273 5,922 13,427 34,477
3 1,349 5,471 12,245 36,647
4 1,309 5,884 12,649 33,896
Ave 1,289 5,705 12,576 34,486
Std 52.8 231.0 630.0 1577.0
Error rate (%) 4.093 4.050 5.010 4.573
Error rate (%) = id x 100
Ave

180

Table 37. Area Response data of retinol in HPLC

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Unit: AU
Sample No. 1 week 2 weeks 4 weeks 8 weeks 12 week 24 week
1 24.505 24,261 24,031 23,246 22,243 21,140
05 2 24,1 12 23.787 23,544 22,758 21,959 20,937
3 24,898 24,647 24,356 23,604 22,71 1 21,709
Ave 24,505 24,232 23,977 23,203 22,304 21,262
51“ 393 431 409 425 380 400
' 23,835 23,036 22,365 22,122 19,874 17,490
Contm' 2 24,370 23,503 22,860 22,589 20,469 17,937
3 24,627 23,787 23,151 23,015 20,327 18,039
Ave 24,277 23,442 22,792 22,575 20,223 17,822
Std 404 379 397 447 31 1 292
Table 38. Retinol concentration data in cosmetics
1) mg/ 100 ml
Unit: mg/100 ml
Sample No. 1 week 2 weeks 4 weeks 8 weeks 12 week 24 week
1 2.10 2.08 2.06 1.99 1.90 1.80
03 2 2.06 2.04 2.01 1.94 1.87 1.78
3 2.13 2.11 2.09 2.02 1.94 1.85
Ave 2.10 2.07 2.05 1.98 1.90 1.81
Std 0.03 0.04 0.04 0.04 0.03 0.04
I 2.04 1.97 1.91 1.89 1.69 1.48
Comm] 2 2.09 2.01 1.95 1.93 1.74 1.52
3 2.11 2.04 1.98 1.97 1.73 1.53
Ave 2.08 2.00 1.95 1.93 1.72 1.51
Std 0.04 0.03 0.04 0.04 0.03 0.03

 

 

 

 

 

 

 

 

 

 

 

 

 

181

 

 

From the standard curve,
Y =11284X + 819.79
X = Y — 819.79

1 1284
where, X: Retinol concentration (mg/ 100 ml)

Y: Area Response of retinol in HPLC

 

 

 

 

 

 

 

 

 

 

 

2) IU/g
Unit: lU/g
Sample No. 1 week 2 weeks 4 weeks 8 weeks 12 week 24 week
1 3,498 3,462 3,428 3,312 3,164 3,001
OS 2 3,440 3,392 3,356 3,240 3,122 2,971
3 3,556 3,519 3,476 3,365 3,233 3,085
Ave 3,498 3,458 3,420 3,306 3,173 3,019
Std 58 64 60 63 56 59
1 3,399 3,281 3,182 3,146 2,814 2,462
Control 2 3,478 3,350 3,255 3,215 2,902 2,528
3 3,516 3,392 3,298 3,278 2.881 2,543
Ave 3,464 3,341 3,245 3,213 2,866 2,51 1
Std 60 56 59 66 46 43

 

 

 

 

 

 

 

 

 

Ifa retinol concentration is X (mg/100 ml),
X __ 2 x C(IU / g)

C:

 

7 3333(IU/mg)
Xx 3333(IU/mg)

 

2

where, C: Retinol concentration (IU/g)
1 mg retinol = 3333 IU, 1 1U = 0.300 ug

182

 

 

APPENDIX C: Migration data into various food simulants

Table 39. Standard calibration curve data of Na for 95 % ethanol in AA

 

PPm

Abs

Ave Abs

 

0.0051

 

0.0033

 

0.0018

0.00340

 

0.1278

 

0.1178

 

0.1134

0.11967

 

0.3465

 

0.3473

 

0.3492

0.34767

 

0.5577

 

0.5554

 

0.5531

0.55540

 

0.9418

 

0.9372

 

0.9385

0.93917

 

10

1.1002

 

1.1014

 

 

1.0089

 

1.07017

 

183

 

Table 40. Standard calibration curve data of Na for water and 3 % acetic acid in AA

 

ppm Abs Ave Abs
0 0.0044

 

 

0.01 13 0.00830

 

0.0092

 

1 0.8524
0.8457 0.85787
0.8755

 

 

 

3 1.7301

 

1.7211 1.73140

 

1.7430
5 2.6479
2.6044 2.62223
2.6144

 

 

 

 

10 4.2305

 

4.1864 4.19513
4.1685
15 6.4023
6.4025 6.41267

 

 

 

 

6.4332

 

20 8.4421
8.3321 8.33853
8.2414

 

 

 

 

 

 

 

184

Table 41. Standard calibration curve data of Na for olive oil in AA

 

ppm Abs Ave Abs

 

0 0.0816

 

0.0578 0.05880

 

0.0370

 

1 0.4272

 

0.4275 0.42623

 

0.4240

 

3 0.6252

 

0.6926 0.67263

 

0.7001

 

5 1.2936

 

1.3866 1.33093

 

1.3126

 

 

 

 

 

185

Table 42. Standard calibration curve data of Ca for 95 % ethanol in AA

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

ppm Abs Ave Abs
0 0.0028
0 0.0010 0.00287
0 0.0048
1 0.451 1
1 0.4456 0.44610
1 0.4416
3 0.9301
3 0.9217 0.92230
3 0.9151
5 1.5265
5 1.5098 1.51003
5 1.4938
8 2.2413
8 2.2119 2.22087
8 2.2094
10 2.7070
10 2.6802 2.68173
10 2.6580

 

186

 

Table 43. Standard calibration curve data of Ca for water and 3 % acetic acid in AA

 

ppm Abs Ave Abs

 

0 0.0057

 

0.0034 0.00333

 

0.0009

 

1 0. 1269

 

0.1306 0.12827

 

0.1273

 

3 0.3448

 

0.3473 0.34650

 

0.3474

 

5 0.5577

 

0.5558 0.55533

 

0.5525

 

8 0.9434

 

0.9441 0.94200

 

0.9385

 

10 1.1052

 

1.1007 1.10160

 

1.0989

 

 

 

 

 

187

 

Table 44. Standard calibration curve data of Ca for olive oil in AA

 

ppm

Abs

Ave Abs

 

0.0021

 

0.0051

 

0.0022

0.00313

 

0.0541

 

0.0612

 

0.0555

0.05693

 

0.0955

 

0.0899

 

0.0943

0.09323

 

0.1241

 

0.1342

 

 

0.1289

 

0.129067

 

188

 

Table 45. Standard calibration curve data of Fe for 95 % ethanol in AA

 

PPm

Abs

Ave Abs

 

0.0001

 

0.0007

 

0.0014

0.00073

 

0.1367

 

0.1407

 

0.1412

0.13953

 

0.3140

 

0.3111

 

0.3127

0.31260

 

0.3650

 

0.3657

 

0.3770

0.36923

 

0.7964

 

0.7991

 

0.7990

0.79817

 

1.5557

 

1.5552

 

1.5653

1.55873

 

20

3.1302

 

3.1021

 

 

 

3.1209

 

3.11773

 

189

 

Table 46. Standard calibration curve data of Fe for water and 3 % acetic acid in AA

 

ppm Abs Ave Abs

 

0 0.0029

 

0.0064 0.00480

 

0.0051

 

 

 

1 0.0885

 

0.0898 0.09010

 

0.0920

 

2 0.1941

 

0.1934 0.19330

 

0.1924

 

3 0.2935

 

0.2954 0.29513

 

0.2965

 

5 0.4855

 

0.4872 0.48750

 

0.4898

 

10 0.9391

 

0.9401 0.94200

 

0.9468

 

20 1.8915

 

1.9113 1.89677

 

 

1.8875

 

 

 

 

190

Table 47. Standard calibration curve data of Fe for olive oil in AA

 

ppm Abs Ave Abs

 

0 0.0099
0.0087 0.00877
0.0077

 

 

 

1 0.0170
0.0184 0.01713
0.0160

 

 

 

3 0.0712
0.0685 0.07127
0.0741

 

 

 

5 0.1098
0.1222 0.11453
0.1116

 

 

 

 

 

 

 

191

 

Table 48. Migration of NaCl into 95 % ethanol as calculated from observed migration of

sodium (Na), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Na NaCl NaCl
samp'e # ug/30m1 ug/30m1 m g/L Ave Std
1 3.54 9.01 0.30
1 3.54 8.99 0.30 0.300 0.000
1 3.54 9.00 0.30
2 3.42 8.70 0.29
2 3.41 8.66 0.29 8.663 0.001
2 3.40 8.63 0.29
05' 3 3.27 8.31 0.28
3 3.28 8.34 0.28 8.344 0.001
3 3.30 8.38 0.28
4 3.74 9.50 0.32
4 3.73 9.47 0.32 9.457 0.002
4 3.70 9.41 0.31
1 1.24 3.14 0.10
1 1.22 3.11 0.10 3.111 0.001
1 1.21 3.09 0.10
2 1.15 2.92 0.10
2 1.15 2.93 0.10 2.920 0.000
2 1.14 2.91 0.10
032 3 1.35 3.42 0.11
3 1.34 3.40 0.1 1 3.405 0.001
3 1.33 3.39 0.1 1
4 1.08 2.75 0.09
4 1.09 2.78 0.09 2.750 0.001
4 1.07 2.72 0.09
1 0.60 1.52 0.05
1 0.62 1.56 0.05 1.553 0.001
1 0.62 1.58 0.05
2 0.58 1.48 0.05
2 0.55 1.41 0.05 1.430 0.001
2 0.55 1.40 0.05
LLDPE 3 0.49 1.25 0.04
3 0.47 1.19 0.04 1.223 0.001
3 0.48 1.22 0.04
4 0.42 1.06 0.04
4 0.44 1.13 0.04 1.091 0.001
4 0.43 1.09 0.04

 

 

 

 

 

 

 

192

 

Table 49. Migration of NaCl into water as calculated from observed migration of sodium

(Na), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Na NaCI NaCl
Sample # ttg/30m1 ug/30ml mg/L Ave Std
1 17.95 45.60 1.52
1 18.01 45.77 1.53 1.526 0.005
1 18.07 45.92 1.53
2 17.85 45.35 1.51
2 17.79 45.20 1.51 1.510 0.003
OSI 2 17.86 45.39 1.51
3 17.96 45.64 1.52
3 17.82 45.27 1.51 1.518 0.008
3 17.99 45.70 1.52
4 17.47 44.38 1.48
4 17.44 44.31 1.48 1.478 0.001
4 17.45 44.33 1.48
1 3.40 8.63 0.29
1 3.44 8.74 0.29 0.290 0.002
1 3.42 8.70 0.29
2 3.97 10.09 0.34
2 3.90 9.90 0.33 0.333 0.003
2 3.93 9.97 0.33
082 3 3.35 8.52 0.28
3 3.34 8.48 0.28 0.282 0.002
3 3.31 8.42 0.28
4 3.70 9.41 0.31
4 3.76 9.55 0.32 0.317 0.003
4 3.77 9.58 0.32
1 2.12 5.39 0.18
1 2.15 5.47 0.18 0.183 0.003
1 2.20 5.59 0.19
2 2.52 6.39 0.21
2 2.36 6.00 0.20 0.204 0.008
LLDPE 2 2.35 5.97 0.20
3 2.07 5.25 0.18
3 2.09 5.31 0.18 0.176 0.001
3 2.07 5.25 0.17
4 1.95 4.94 0.16
4 1.93 4.91 0.16 0.164 0.001
4 1.93 4.90 0.16

 

 

 

 

 

 

 

193

 

Table 50. Migration of NaCl into 3 % acetic acid as calculated from observed migration
of sodium (Na), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Na NaCl NaCl
Sample # ag/30ml 1tg/30m1 mg/L Ave Std
1 16.84 42.79 1.43
1 16.87 42.86 1.43 1.430 0.005
1 16.96 43.09 1.44
2 17.38 44.15 1.47
2 17.32 44.02 1.47 1.473 0.006
OS 1 2 17.47 44.40 1.48
3 17.92 45.53 1.52
3 17.93 45.56 1.52 1.518 0.001
3 17.92 45.52 1.52
4 17.46 44.35 1.48
4 17.44 44.32 1.48 1.476 0.003
4 17.39 44.18 1.47
1 4.25 10.79 0.36
_ 1 4.31 10.95 0.36 0.366 0.007
1 4.41 1 1.21 0.37
2 4.32 10.97 0.37
2 4.65 11.82 0.39 0.373 0.018
2 4.26 10.82 0.36
082 3 4.57 1 1.62 0.39
3 4.33 1 1.00 0.37 0.374 0.01 l
3 4.35 1 1.06 0.37
4 3.84 9.76 0.33
4 3.91 9.93 0.33 0.334 0.010
4 4.07 10.35 0.35
1 2.83 7.20 0.24
1 2.87 7.29 0.24 0.243 0.003
1 2.89 7.35 0.24
2 2.68 6.80 0.23
2 2.71 6.90 0.23 0.230 0.004
LLDPE 2 2.77 7.03 0.23
3 3.23 8.20 0.27
3 3.15 7.99 0.27 0.270 0.003
3 3.18 8.08 0.27
4 2.45 6.22 0.21
4 2.62 6.67 0.22 0.216 0.008
4 2.59 6.58 0.22

 

 

 

 

 

 

 

194

 

Table 51. Migration of NaCl into olive oil as calculated from observed migration of

sodium (Na), respectively

 

Na

NaCl

NaCl

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sample # ug/30ml /tg/30m| mg/L Ave Std
1 0.57 1.45 0.05
1 0.57 1.44 0.05 1.317 0.219
1 0.42 1.06 0.04
2 0.39 1.00 0.03
2 0.56 1.42 0.05 1.355 0.331
2 0.65 1.65 0.05
OS] 3 0.01 0.04 0.00
3 0.59 1.50 0.05 1.046 0.878
3 0.63 1.61 0.05
4 0.59 1.51 0.05
4 0.07 0.17 0.01 1.332 1.085
4 0.91 2.32 0.08
1 0.38 0.98 0.03
1 0.40 1.02 0.03 1.055 0.099
1 0.46 1.17 0.04
2 0.46 1.17 0.04
2 0.59 1.50 0.05 1.301 0.178
2 0.49 1.23 0.04
082 3 0.40 1.01 0.03
3 0.40 1.02 0.03 1.026 0.017
3 0.41 1.05 0.03
4 0.40 1.01 0.03
4 0.38 0.97 0.03 0.961 0.059
4 0.35 0.90 0.03
1 0.50 1.28 0.04
1 0.50 1.26 0.04 1.207 0.109
1 0.43 1.08 0.04
2 0.34 0.86 0.03
2 0.35 0.90 0.03 0.923 0.076
2 0.40 1.01 0.03
LLDPE 3 0.36 0.91 0.03
3 0.39 0.98 0.03 1.167 0.386
3 0.63 1.61 0.05
4 0.69 1.75 0.06
4 1.08 2.74 0.09 1.921 0.750
4 0.50 1.27 0.04

 

195

 

Table 52. Migration of CaClz into 95 % ethanol as calculated from observed migration of

calcium (Ca), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ca CaClz CaCl
Sample # [1g /3 Oml [1g /3 0m1 m g/Lz Ave Std
I -0.38 -1.07 -0.04
1 -0.39 -1.09 -0.04 -0.036 0.000
1 -0.39 -1.07 -0.04
2 -0.39 -1.09 -0.04
2 -0.40 -1.10 -0.04 -0.036 0.001
2 -0.38 -1.05 -0.03
OSI 3 -0.38 -1.05 -0.04
3 -0.38 -1.06 -0.04 -0.035 0.001
3 -0.36 -1.01 -0.03
4 -0.37 -1.03 -0.03
4 -0.36 -1.01 -0.03 -0.035 0.001
4 -0.39 -1.09 -0.04
1 -0.37 -1.01 -0.03
1 -0.38 -1.06 -0.04 -0.035 0.001
1 -0.39 -1.07 -0.04
2 -0.37 -1.02 -0.03
2 -0.38 -1.06 -0.04 -0.035 0.001
2 -0.37 -1.04 -0.03
082 3 -0.36 -1.01 -0.03
3 -0.38 -1.05 -0.03 -0.034 0.001
3 -0.36 -1.00 -0.03
4 -0.37 -1.02 -0.03
4 -0.36 -1.00 -0.03 -0.034 0.000
4 -0.36 -1.00 -0.03
1 -0.34 -0.95 -0.03
1 -0.36 -0.99 -0.03 -0.032 0.001
1 -0.34 -0.94 -0.03
2 -0.33 -0.93 -0.03
2 -0.35 -0.97 -0.03 -0.032 0.001
2 -0.35 -0.96 -0.03
LLDPE 3 -0.34 -0.96 -0.03
3 -0.36 -0.99 -0.03 -0.032 0.001
3 -0.34 -0.95 -0.03
4 -0.34 -0.95 -0.03
4 -0.32 -0.89 -0.03 -0.031 0.001
4 -0.34 -0.93 -0.03

 

 

 

 

 

 

 

196

 

Table 53. Migration of CaClz into water as calculated from observed migration of

calcium (Ca), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

, Ca CaClz CaCl
Sample # ttg/30m1 ug/30m1 mg/L2 Ave Std
1 0.04 0.12 0.00
1 0.00 0.00 0.00 000! 0.002
1 0.00 0.00 0.00
2 0.06 0.18 0.01
2 0.00 0.00 0.00 0.002 0.003
OS 1 2 0.00 0.00 0.00
3 0.05 0.13 0.00
3 0.00 0.00 0.00 0.001 0.003
3 0.00 0.00 0.00
4 0.04 0.1 1 0.00
4 0.00 0.00 0.00 0.001 0.002
4 0.00 0.00 0.00
1 0.40 1.1 1 0.04
1 0.00 0.00 0.00 0.012 0.021
1 0.00 0.00 0.00
2 0.58 1.62 0.05
2 0.00 0.00 0.00 0.018 0.031
2 0.00 0.00 0.00
082 3 0.40 1.1 1 0.04
3 0.00 0.00 0.00 0.012 0.021
3 0.00 0.00 0.00
4 1.14 3.16 0.1 1
4 0.00 0.00 0.00 0.035 0.061
4 0.00 0.00 0.00
1 0.21 0.59 0.02
1 0.00 0.00 0.00 0.007 0.01 1
1 0.00 0.00 0.00
2 0.27 0.76 0.03
2 0.00 0.00 0.00 0.008 0.015
2 0.00 0.00 0.00
LLDPE 3 0.23 0.63 0.02
3 0.00 0.00 0.00 0.007 0.012
3 0.00 0.00 0.00
4 0.48 1.33 0.04
4 0.00 0.00 0.00 0.015 0.026
4 0.00 0.00 0.00

 

 

 

 

 

 

 

 

197

 

Table 54. Migration of C3C12 into 3 % acetic acid as calculated from observed migration

of calcium (Ca), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ca C3C12 CaCl
sample # ug/30m1 jig/30ml mg/Lz Ave Std
1 0.27 0.75 0.02
1 0.27 0.76 0.03 0.025 0.000
1 0.28 0.76 0.03
2 0.32 0.89 0.03
2 0.35 0.97 0.03 0.031 0.001
2 0.32 0.90 0.03
OS] 3 0.35 0.98 0.03
3 0.34 0.94 0.03 0.031 0.001
3 0.32 0.90 0.03
4 0.27 0.76 0.03
4 0.24 0.67 0.02 0.024 0.002
4 0.27 0.76 0.03
1 4.95 13.74 0.46
1 4.93 13.69 0.46 0.457 0.001
1 4.95 13.72 0.46
2 4.47 12.39 0.41
2 4.28 1 1.87 0.40 0.405 0.009
2 4.39 12.17 0.41
052 3 4.27 11.84 0.39
3 5.13 14.23 0.47 0.420 0.047
3 4.24 1 1.77 0.39
4 4.17 1 1.57 0.39
4 4.09 1 1.34 0.38 0.156 0.001
4 4.24 1 1.76 0.39
1 0.37 1.03 0.03
1 0.39 1.08 0.04 0.035 0.001
1 0.37 1.03 0.03
2 0.42 1.17 0.04
2 0.50 1.38 0.05 0.042 0.004
2 0.43 1.18 0.04
LLDPE 3 0.33 0.92 0.03
3 0.30 0.85 0.03 0.031 0.002
3 0.36 0.99 0.03
4 0.15 0.43 0.01
4 0.14 0.38 0.01 0.014 0.001
4 0.15 0.42 0.01

 

 

 

 

 

 

198

 

 

Table 55. Migration of CaClz into olive oil as calculated from observed migration of

calcium (Ca), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ca C8C12 CaCI
Sample # ttg/30ml [tg/30m1 mg/L2 Ave Std
1 -0.41 -1.13 -0.04
1 0.43 1.19 0.04 0.022 0.053
1 0.70 1.93 0.06
2 1.49 4.15 0.14
2 0.32 0.88 0.03 0.070 0.059
2 0.47 1.31 0.04
OS] 3 0.81 2.26 0.08
3 -0.06 -0.18 -0.01 0.036 0.041
3 0.43 1.19 0.04
4 0.85 2.36 0.08
4 0.40 1.12 0.04 0.053 0.022
4 0.47 1.31 0.04
1 1.29 3.57 0.12
1 1.25 3.47 0.12 0.1 17 0.002
1 1.27 3.51 0.12
2 -0.06 -0.18 -0.01
2 1.27 3.53 0.12 0.086 0.081
2 1.59 4.41 0.15
052 3 2.01 5.57 0.19
3 1.66 4.60 0.15 0.176 0.019
3 2.03 5.62 0.19
4 1.70 4.73 0.16
4 0.87 2.41 0.08 0.109 0.042
4 0.98 2.71 0.09
1 1.08 3.00 0.10
| 0.41 1.13 0.04 0.060 0.035
1 0.45 1.24 0.04
2 0.61 1.70 0.06
2 0.50 1.38 0.05 0.037 0.025
. 2 0.09 0.25 0.01
LLDPE 3 0.60 1.66 0.06
3 0.27 0.75 0.02 0.037 0.016
3 0.32 0.90 0.03
4 0.39 1.07 0.04
4 0.39 1.07 0.04 0.046 0.017
4 0.71 1.96 0.07

 

 

 

 

 

 

 

 

199

 

Table 56. Migration of F6303 into 95 % ethanol as calculated from observed migration of

iron (Fe), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Fe F6203 F630
samp'e # ,ttg/30m1 [lg/30ml m g/L3 Ave 31“
1 0.15 0.21 0.01
1 0.13 0.19 0.01 0.007 0.000
1 0.14 0.19 0.01
2 0.15 0.21 0.01
2 0.13 0.18 0.01 0.006 0.000
2 0.13 0.19 0.01
05' 3 0.13 0.19 0.01
3 0.15 0.21 0.01 0.007 0.000
3 0.14 0.20 0.01
4 0.13 0.19 0.01
4 0.13 0.18 0.01 0.006 0.000
4 0.13 0.18 0.01
1 0.14 0.19 0.01
1 0.16 0.23 0.01 0.007 0.001
1 0.13 0.19 0.01
2 0.15 0.22 0.01
2 0.13 0.19 0.01 0.007 0.000
2 0.14 0.20 0.01
052 3 0.13 0.19 0.01
3 0.13 0.18 0.01 0.006 0.000
3 0.13 0.19 0.01
4 0.14 0.20 0.01
4 0.14 0.20 0.01 0.007 0.000
4 0.13 0.19 0.01
1 0.14 0.19 0.01
1 0.15 0.22 0.01 0.007 0.000
1 0.14 0.19 0.01
2 0.14 0.20 0.01
2 0.15 0.21 0.01 0.007 0.000
2 0.15 0.21 0.01
LLDPE 3 0.14 0.21 0.01
3 0.14 0.20 0.01 0.007 0.000
3 0.16 0.23 0.01
4 0.14 0.20 0.01
4 0.14 0.20 0.01 0.007 0.000
4 0.13 0.19 0.01

 

200

 

Table 57. Migration of F6203 into water as calculated from observed migration of iron
(Fe), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Fe Fe203 F630
Sample # ttg/30m1 /tg/30m1 mg/L3 Ave Std
1 2.18 3.12 0.10
1 0.00 0.00 0.00 0.035 0.060
1 0.00 0.00 0.00
2 1.54 2.20 0.07
2 0.00 0.00 0.00 0.024 0.042
2 0.00 0.00 0.00
OSI 3 1.87 2.68 0.09
3 0.00 0.00 0.00 0.030 0.052
3 0.00 0.00 0.00
4 1.65 2.36 0.08
4 0.00 0.00 0.00 0.026 0.045
4 0.00 0.00 0.00
1 0.00 0.00 0.00
1 0.00 0.00 0.00 0.000 0.000
1 0.00 0.00 0.00
2 -0.03 -0.04 0.00
2 0.00 0.00 0.00 0.000 0.001
2 0.00 0.00 0.00
082 3 0.00 0.00 0.00
3 0.00 0.00 0.00 0.000 0.000
3 0.00 0.00 0.00
4 0.01 0.01 0.00
4 0.00 0.00 0.00 0.000 0.000
4 0.00 0.00 0.00
1 -0.01 -0.01 0.00
1 0.00 0.00 0.00 0.000 0.000
1 0.00 0.00 0.00
2 -0.02 -0.02 0.00
2 0.00 0.00 0.00 0.000 0.000
2 0.00 0.00 0.00
LLDPE 3 -0.02 -0.02 0.00
3 0.00 0.00 0.00 0.000 0.000
__ 3 0.00 0.00 0.00
4 -0.03 -0.05 0.00
4 0.00 0.00 0.00 -0.001 0.001
4 0.00 0.00 0.00

 

201

 

Table 58. Migration of F6203 into 3 % acetic acid as calculated from observed migration
of iron (Fe), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Fe F6203 F620
Sample # rig/30ml /tg/30m| mg/L3 Ave Std
1 19.79 28.29 0.94
1 19.86 28.40 0.95 0.945 0.002
1 19.84 28.37 0.95
2 15.47 22.11 0.74
2 15.41 22.04 0.73 0.736 0.001
OSI 2 15.43 22.06 0.74
3 16.17 23.12 0.77
3 16.19 23.14 0.77 0.772 0.001
3 16.22 23.19 0.77
4 17.28 24.70 0.82
4 17.25 24.66 0.82 0.822 0.002
4 17.20 24.59 0.82
1 2.93 4.19 0.14
1 2.93 4.19 0.14 0.140 0.001
1 2.98 4.26 0.14
2 3.09 4.42 0.15
2 3.06 4.37 0.15 0.146 0.001
2 3.06 4.38 0.15
082 3 2.92 4.18 0.14
3 2.93 4.19 0.14 0.140 0.001
3 2.96 4.23 0.14
4 3.33 4.76 0.16
4 3.35 4.79 0.16 0.159 0.001
4 3.33 4.76 0.16
1 0.34 0.49 0.02
1 0.29 0.42 0.01 0.015 0.001
1 0.32 0.45 0.02
2 0.31 0.44 0.01
2 0.29 0.41 0.01 0.014 0.001
2 0.28 0.40 0.01
LLDPE 3 0.31 0.44 0.01
3 0.30 0.42 0.01 0.014 0.001
3 0.27 0.38 0.01
4 0.28 0.40 0.01
4 0.29 0.41 0.01 0.013 0.001
4 0.27 0.38 0.01

 

202

 

Table 59. Migration of F6203 into olive oil as calculated from observed migration ofiron

(Fe), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Fe F6203 F 620
Sample # ,ug/30m1 rig/30ml mg/L3 Ave Std
1 0.32 0.46 0.02
1 -0.21 -0.29 -0.01 0.006 0.014
1 0.25 0.36 0.01
2 0.18 0.26 0.01
2 -0.10 -0.15 0.00 0.005 0.009
, 2 0.23 0.33 0.01
05] 3 0.27 0.38 0.01
3 0.14 0.19 0.01 0.009 0.003
3 0.17 0.24 0.01
4 0.75 1.07 0.04
4 0.66 0.94 0.03 0.037 0.007
4 0.93 1.34 0.04
1 -0.25 -0.36 -0.01
1 0.35 0.51 0.02 0.007 0.016
1 0.32 0.46 0.02
2 0.09 0.13 0.00
2 0.10 0.15 0.00 0.007 0.004
2 0.26 0.37 0.01
082 3 0.24 0.34 0.01
3 0.34 0.48 0.02 0.012 0.003
3 0.21 0.31 0.01
4 0.23 0.32 0.01
4 0.18 0.26 0.01 0.009 0.002
4 0.14 0.21 0.01
1 0.35 0.51 0.02
1 0.26 0.37 0.01 0.014 0.002
1 0.27 0.39 0.01
2 0.18 0.26 0.01
2 0.24 0.35 0.01 0.010 0.002
2 0.19 0.27 0.01
LLDPE 3 0.15 0.22 0.01
3 0.25 0.36 0.01 0.010 0.002
3 0.20 0.29 0.01
4 0.18 0.26 0.01
4 0.17 0.24 0.01 0.010 0.002
4 0.25 0.36 0.01

 

 

 

 

 

 

 

 

203

 

Table 60. Migration of NaCl into 3 % acetic acid as calculated from observed migration
of sodium (Na), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sample # Abs ugggml #2231ng :23 Ave Std

1 0.8070 1.1 145 2.83 0.09

1 1.1121 1.8757 4.77 0.16 0.129 0.032

1 0.9874 1.5646 3.98 0.13

2 1.0253 1.6592 4.22 0.14

2 0.9943 1.5818 4.02 0.13 0.139 0.004
Tube(OS2) 2 1.0324 1.6769 4.26 0.14

3 0.8804 1.2977 3.30 0.1 1

3 0.8616 1.2507 3.18 0.1 1 0.107 0.003

3 0.8554 1.2353 3.14 0.10

4 1.0221 1.6512 4.20 0.14

4 1.3499 2.4691 6.27 0.21 0.186 0.040

4 1.3552 2.4823 6.31 0.21

 

 

 

 

 

 

Table 61. Migration of CaClz into 3 % acetic acid as calculated from observed migration
of calcium (Ca), respectively

 

Ca

C3C12

C3C12

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sample # Abs ttg/30m1 ug/30m1 mg/L Ave Std
1 0.2049 1.7410 4.83 0.16
1 0.2026 1.7204 4.77 0.16 0.160 0.001
1 0.2025 1.7195 4.77 0.16
2 0.2794 2.4087 6.68 0.22
2 0.2841 2.4507 6.80 0.23 0.226 0.003
Tube(OS2) 2 0.2852 2.4606 6.83 0.23
3 0.2834 2.4445 6.78 0.23
3 0.2861 2.4686 6.85 0.23 0.199 0.049
3 0.1825 1.5404 4.27 0.14
4 0.2364 2.0233 5.61 0.19
4 0.2394 2.0502 5.69 0.19 0.188 0.001
4 0.2365 2.0242 5.62 0.19

 

204

 

 

Table 62. Migration of F6303 into 3 % acetic acid as calculated from observed migration

of iron (Fe), respectively

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sample # Abs ”g /F3I)m1 ”2:38;” :1:/(:3 Ave Std
1 0.1482 1.3361 1.91 0.06
1 0.1497 1.3500 1.93 0.06 0.064 0.000
1 0.1493 1.3463 1.92 0.06
2 0.1293 1.1606 1.66 0.06
2 0.1313 1.1792 1.69 0.06 0.056 0.000
2 0.1302 1.1690 1.67 0.06
Tube(OS2)
3 0.1924 1.7465 2.50 0.08
3 0.1933 1.7549 2.51 0.08 0.084 0.001
3 0.1952 1.7725 2.53 0.08
4 0.1438 1.2953 1.85 0.06
4 0.1424 1.2823 1.83 0.06 0.061 0.001
4 0.141 1 1.2702 1.82 0.06

 

 

 

 

 

 

l

 

 

205