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Food Contact Rubbers - Products, Migration and Regulation
Silicone Products for Food Contact Applications
Coatings and Inks for Food Contact Materials
Food Contact Rubbers - Products, Migration and Regulation :
1. Introduction
2. Rubber Materials and Products used in Contact with Food
2.1 Polymers Used in Food Contact Rubbers
2.1.1 Natural Rubber (i.e., cis-1,4-polyisoprene)
2.1.2 Nitrile Rubber
2.1.3 Ethylene-propylene Rubber

Food Contact Rubbers - Products, Migration and Regulation
Silicone Products for Food Contact Applications
Coatings and Inks for Food Contact Materials
Food Contact Rubbers - Products, Migration and Regulation :
1. Introduction
2. Rubber Materials and Products used in Contact with Food
2.1 Polymers Used in Food Contact Rubbers
2.1.1 Natural Rubber (i.e., cis-1,4-polyisoprene)
2.1.2 Nitrile Rubber
2.1.3 Ethylene-propylene Rubber
2.1.4 Fluorocarbon Rubber
2.1.5 Silicone Rubber
2.1.6 Thermoplastic Elastomers
2.1.7 Other Types of Rubbers
2.2 Additives Used in Food Contact Rubbers
2.2.1 Plasticisers/Process Oils and Fillers
2.2.2 Curatives and Antidegradants
2.2.3 Miscellaneous Additives
2.3 Rubber Products Used in the Food Industry and the Contact Conditions
2.3.1 Types of Rubber Product
2.3.2 Contact Areas
2.3.3 Contact Times
2.3.4 Contact Temperatures
3. Regulations Covering the Use of Rubber as a Food Contact Material
3.1 European Union Legislation
3.2 Council of Europe (CoE) Resolution on Rubber Products
3.2.1 Technical Documents
3.2.2 Product Categories
3.2.3 R Factors
3.2.4 Silicone Rubbers
3.3 Food and Drug Administration (FDA) in the USA
3.4 Bundesinstitut für Risikobewertung (BfR) German Regulations
3.4.1 Categories of Use
3.4.2 Silicone Rubbers
3.5 Other European Legislation
3.5.1 Requirements in France
3.5.2 Requirements in the Netherlands
3.5.3 Requirements in Italy
3.5.4 Requirements in the United Kingdom
4. Assessing the Safety of Rubber as a Food Contact Material
4.1 Special Considerations When Using Rubber as a Food Contact Material
4.2 Migration Tests
4.2.1 Overall Migration Tests
4.2.1.1 FDA Regulations
4.2.1.2 BfR Regulations
4.2.1.3 CoE Resolution
4.2.2 Specific Migration Tests
4.3 Fingerprinting Potential Migrants from Rubber Compounds
4.3.1 Use of Gas Chromatography-Mass Spectrometry (GC-MS) to Fingerprint Food Contact Rubber Samples
4.3.1.1 Rubber Formulations
4.3.1.2 Experimental Conditions
4.3.2 Use of Liquid Chromatography-Mass Spectrometry (LC-MS) to Fingerprint Food Contact Rubber Samples
4.4 Determination of Specific Species in Rubbers and Migrants in Food Simulants and Food Products
4.4.1 Monomers
4.4.2 Plasticisers and Process Oils
4.4.3 Cure System Species, Accelerators and Their Reaction Products
4.4.4 Antidegradants and Their Reaction Products
4.4.5 Oligomers
4.5 Research Studies Carried out at Rapra for the FSA
4.5.1 FSA Project FS2219 - Migration Data on Food Contact Rubbers
4.5.1.1 Introduction
4.5.1.2 Standard Rubber Compounds
4.5.1.3 Migration Experiments Carried Out on the Standard Rubber Compounds
4.5.1.4 Results of the Migration Experiments
4.5.2 FSA Project FS2248 - Further Migration Data on Food Contact Rubbers
4.5.2.1 Introduction
4.5.2.2 Standard Rubber Compounds
4.5.2.3 Tests Carried Out on the Seven Rubber Compounds
4.5.2.4 Results Obtained During the Course of the Project
4.5.3 Project AO3038 - Rubber Breakdown Products
4.5.3.1 Introduction
4.5.3.2 Listing of the Breakdown Products for the CoE Curatives and Antidegradants
4.5.3.3 Factors Affecting the Formation of the Breakdown Products
4.5.3.4 Fingerprinting of the Breakdown Products
4.5.3.5 Migration Behaviour of the Breakdown Products
4.5.3.6 Overall Summary of the Migration Data
4.5.3.7 Overall Conclusions
4.5.4 Project AO3046 – Silicones
4.5.4.1 Introduction
4.5.4.2 Potential Migrants in Silicone Rubbers Stage 1 of the Project
4.5.4.3 Data Obtained on Commercial Silicone Rubber Products - Stage 2 of the Project
4.5.4.4 Overall Summary of the Project Findings
4.6 Published Migration Data
4.6.1 Food Contact Products
4.6.1.1 Teats and Soothers
4.6.1.2 Meat Netting
4.6.1.3 Rubber Gloves for Handling Food
4.6.2 Specific Chemical Migrants from Rubber Compounds
4.6.2.1 Alkylphenol and Bisphenol A
4.6.2.2 Peroxide Breakdown Products
4.6.2.3 Dimethyl Siloxanes and Other Components from Silicone Rubbers
4.6.2.4 Accelerators and Antidegradants
4.6.3 General Surveys
4.6.4 Analytical Techniques
5. Improving the Safety of Rubber as a Food Contact Material
5.1 Nitrosamines
5.2 Amines
5.3 Polyaromatic Hydrocarbons
5.4 Use of Alternative Compounds
6. Future Trends in the Use of Rubber with Food
6.1 Increased Use of Thermoplastic Rubbers and High Performance Rubbers
6.2 Developments in Additives
6.3 Surface Coatings and Modifications
6.4 Developments in Analytical Techniques
7. Conclusion
7.1 Sources of Further Information and Advice
7.1.1 Professional, Research, Trade and Governmental Organisations
7.1.2 Commercial Abstract Databases
7.1.3 Key Reference Books and Journals
7.1.4 Food Standards Agency Research Projects
Appendix 1
References
Coatings and Inks for Food Contact Materials :
1. Introduction
2. Coating and Ink Products for Food Contact Materials
2.1 Polymers for Coatings and Inks
2.1.1 Acrylic
2.1.2 Alkyd resins
2.1.3 Amino Resins (Urea-formaldehyde resins)
2.1.4 Epoxy Resins
2.1.5 Cellulosics
2.1.5.1 Nitrocellulose
2.1.5.2 Other Cellulose Esters
2.1.5.3 Cellulose Ethers
2.1.6 Polyesters - Saturated and Unsaturated
2.1.6.1 Saturated Polyesters
2.1.6.2 Unsaturated Polyesters
2.1.7 Polyurethanes
2.1.8 Rosin
2.1.9 Silicone Resins
2.1.10 Vinyl Polymers
2.1.11 Other Polymers (Hydrocarbons)
2.2.2 Constituents of Coatings
2.2.1 Crosslinking Agents
2.2.2 Other Additives
2.2.3 Solvents
2.3 Constituents of Inks
2.3.1 Solvents
2.3.2 Plasticisers
2.3.3 Driers
2.3.4 Photoinitiators
2.3.5 Colorants
2.3.5.1 Azo dyes and pigments
2.3.5.2 Phthalocyanines
2.3.6 Other Additives
3. Coatings and Inks used in the Food Chain
3.1 Food Packaging
3.1.1 Packaging Types
3.1.2 Coatings Used in Metal Packaging (Tables 5 to 9)
3.1.2.1 Beverage Body and End Stock Externals (Coatings Used in Conjunction With Inks)
3.1.3 Coatings and Adhesives for Flexible Packaging
3.1.4 Inks for Metal Packaging
3.1.4.1 Beverage Cans
3.1.4.2 Food Cans and Ends
3.1.4.3 Caps and Closures
3.1.4.4 General Line and Aerosols
3.1.5 Inks for Paper and Board Packaging
3.1.6 Inks for Flexible Packaging
3.2 Harvesting and Processing of Food
3.3 Storage and Transportation
3.4 Presentation, Dispensing and Cooking
4. Application Techniques for Inks
4.1 Lithogra phy
4.2 Flexography
4.3 Gravure
4.4 Inkjet
4.5 Influence of Substrate Type
4.5.1 Inks for Metal Packaging
4.5.2 Inks for Paper and Board
4.5.3 Inks for Flexible Plastic Packaging
4.5.4 Set Off
5. Regulations Covering the Use of Inks and Coatings with Food
5.1 Regulation in the European Union
5.2 Council of Europe (CoE) Regulations
5.2.1 Coatings
5.2.2 Inks
5.3 National Regulations within the EU
5.4 FDA Regulations
5.5 Other Considerations for Industrial Use
6. Assessing the Safety of Inks and Coatings for Food Applications
6.1 Global Migration Tests
6.2 Specific Migration Tests
6.3 Fingerprinting of Potential Migrants from Coatings and Inks
6.4 Determination of Specific Target Species in Coatings and Ink Products and in Food Simulants and Foods
6.4.1 Monomers, Solvents and Low Molecular Weight Additives and Breakdown Products
6.4.2 Oligomers
6.4.3 Plasticisers and Oil-type Additives
6.4.4 Polar Additives and Metal Containing Compounds
6.4.5 Cure System Species, Initiators, Catalysts and Their Reaction Products
6.4.6 Antidegradants, Stabilisers and Their Reaction Products
6.5 Sensory Testing
6.6 Toxicological Assessment of Migrants
7. Potential Migrants and Published Migration Data
7.1 Acrylates
7.2 Amines
7.3 Aromatics from Unsaturated Polyesters
7.4 Aromatics from Photo initiation Reactions and Photoinitiator Additives
7.5 BPA and BADGE and Derivatives
7.6 Epichlorohydrin
7.7 Bisphenol A
7.8 Solvents
7.9 Plasticisers
7.10 Extractables from UV-Cured Coating for Cardboard
7.11 Potential Migrants
8. Improving the Safety of Inks and Coatings for Food Use
8.1 New Food Approved Pigments
8.2 Water- Based Systems
8.3 UV/EB Curable Systems
8.4 New Initiators for UV Curable Inks
9. Future Trends
9.1 Improvements in Recycling Systems
9.2 Biodegradability
9.3 Use of Coatings to Improve Barrier Properties of Food Packaging
9.4 Antimicrobial Systems
9.5 Laser Marking to Replace Conventional Inks
9.6 Intelligent and Active Packaging
9.7 Applications of Nanotechnology
9.8 Developments in Analytical Techniques
10. Conclusion
Sources of Further Information and Advice
Reference Books
Reports
Professional, Research, Trade and Governmental Organisations
Commercial Abstract Data bases
Acknowledgements
References
Silicone Products for Food Contact Applications :
1. Introduction
2. Silicone Products for Food Contact Applications
2.1 Silicone Polymers - Chemistry, Structure and Properties
2.1.1 Definition of a Silicone Polymer
2.1.1.1 Summary of Principal Food Contact Silicone Products
2.1.2 Chemical Bonding in Silicones
2.1.3 Physical Characteristics
2.1.4 Chemical Properties
2.2 Food Contact Silicone Products - Manufacture and Composition
2.2.1 Introduction
2.2.2 Manufacture of Silicone Polymers and Their Precursors
2.2.3 Silicone Fluids and Silicone Gums
2.2.4 Silicone Rubbers - from High MW Gums
2.2.5 Silicone Rubbers - From Relatively Low MW Liquids
2.2.5.1 Two-o-pack Liquid Silicone Systems
2.2.5.2 One-pack Liquid Silicone Systems
2.2.6 Silicone Resins
2.2.7 Silicone Greases
2.2.8 Copolymers
2.2.8.1 Vinyl Silicones
2.2.8.2 Phenyl Silicones
2.2.8.3 Fluorosilicones
2.2.9 Silicone Surfactants
2.3 Food Contact and Food Related Applications
2.3.1 Release Agents
2.3.2 Silicone Rubbers
2.3.3 Silicones as Additives for Polymers
2.3.4 Silicones in Food Processing
3. Regulations Coverin the Use of Silicones With Food
3.1 Existing EU Legislation and Guideline Documents
3.2 Council of Europe Resolution on Silicones (Resolution AP (2004))
3.3 German Recommendation XV from the BfR
3.4 Other National Legislation in the EU
3.4.1 Belgium
3.4.2 Italy
3.4.3 Netherlands
3.4.4 United Kingdom
3.5 The US Food and Drug Administration (FDA)
4. Assessing the Safety of Silicone Materials and Articles for Food Applications
4.1 Fingerprinting of Potential Migrants from Silicone Products
4.1.1 Multi-element Semi-quantitative Inductively Coupled Plasma Scan
4.1.2 Targeting of Specific Species
4.1.2.1 Specific Elements
4.1.2.2 Residual Peroxides in Silicone Rubbers
4 .1.2.3 Silicone Additives
4.1.3 Identification of Low MW Potential Migrants
4.1.3.1 Dynamic Headspace GC-MS
4.1.3.2 Solvent Extraction GC- MS
4.1.3.3 Solvent Extraction LC-MS
4.2 Overall Migration Tests
4.2.1 FDA Regulations for Rubbers
4.2.2 Council of Europe Silicone Resolution
4.3 Determination of Specific Species in Food Simulants and Foods
4.3.1 Determination of Specific Elements
4.3.2 Determination of Formaldehyde
4.3.2.1 Silicone Rubbers
4.3.2.2 Silicone Resins
4.3.3 Determination of Low MW Species Using GC-MS and LC- MS
4.3.3.1 Two Dimensional Gas Chromatography Time-of-Flight Mass Spectroscopy (GCxGC- ToFMS)
4.3.3.2 Liquid Chromatography - Mass Spectrometry (LC- MS)
5. Foods Standards Agency Silicone Project - Con tract Number A03046
5.1 Silicone Products Studied in the Project
5.1.1 Silicone Rubbers
5.1.2 Silicone Fluids
5.1.3 Silicone Resins - Uncured Products
5.1.4 Silicon Resin Coated Bakeware from Supermarkets
5.1.5 Compositional Fingerprinting Work
5.2 Migration Experiments with Food Simulants
5.2.1 Overall Migration Work
5.2.1.1 Silicone Rubbers
5.2.1.2 Silicone Fluids
5 .2.1.3 Silicone Resins
5.2.2 Specific Migration Work
5.2.2.1 Determination of Specific Elements
5.2.2.2 Determination of Formaldehyde
5.2.2.3 Analysis of Food Simulants by GCxGC-ToFMS
5.3 Migration Experiments with Food Products
5.3.1 Contact Tests Performed on the Silicone Products
5.3.1.1 Silicone Rubbers
5.3.1.2 Silicone Fluids
5 .3.1.3 Silicone Resins
5.3.2 Determination of Specific Migrants in Food Products
5.3.2.1 Determination of Silicon
5.3.2.2 Determination of Specific Migrants by GCxGC-ToFMS
5.4 Summary of Project Results
5.4.1 Summary of the Data Obtained on the Silicone Rubber Samples
5.4.1.1 Determination of Potential Migrants Fingerprinting Data
5.4.1.2 Migration Work Using Food Simulants
5.4.2 Summary of the Data Obtained on the Silicone Fluids
5.4.2.1 Potential Migrants - from Fingerprint Data
5.4.2.2 Migration Work Using Food Simulants
5.4.2.3 Migration Work Using Food Products
5.4.3 Summary of the Data Obtained on the Silicone Resin Samples
5.4.3.1 Potential Migrants - from Fingerprinting Data
5.4.3.2 Migration Work Using Food Simulants
5.4.3.3 Migration Work Using Food Products
5.4.4 Overall Summary of the Project and the Results Obtained
5.4.4.1 Overview
5.4.4.2 Data Obtained for Silicone Rubbers
5.4.4.3 Data Obtained for Silicone Resins
5.4.4.4 Data Obtained for Silicone Fluids
6. Migration Mechanisms, Potential Migrants and Published Migration Data
6.1 Possible Migration Mechanisms for Chemical Species from Silicone Products
6.1.1 Migration to Air (Volatilisation)
6.1.1.1 Potential for Chemical Change Upon Thermal Volatilisation
6.1.1.2 Potential for Change on Ionisation
6.1.2 Migration into Fluids
6.1.3 Migration into Foodstuffs
6.2 Potential Migrants from Silicone Products
6.2.1 Summary of Potential Migrants
6.2.2 Specific Potential Migrants
6.2.2.1 Silicone Oligomers
6.2.2.2 Cure System Species in Silicone Rubbers
6.2.2.3 Low MW Products Formed Due to Oxidation Reactions
6.3 Published Migration Data
6.3.1 Silicone Rubber Study
6.3.2 Silicone Rubber Teats and Soothers
6.3.3 Peroxide Breakdown Products
6.3.4 Polydimethylsiloxane Oligomers
6.3.5 General Assessment of Silicone Rubbers
7 Improving the Safety of Silicones for Food Use and Future Trends
7.1 Silicone Foams
7.2 Antibacterial Additives and Coatings
7.3 Intelligent Packaging
7.4 Barrier Coatings
7.5 Non-stick Additives
7.6 Nanoparticulate Silicones
7.7 Inks and Varnishes
7.8 Radiation-cured Release Coatings
8. Conclusion
Acknowledgements
Structural Assignments for Silicone Polymers and Oligomers