Compliance testing for food contact materials

Compliance testing for food contact materials

2

R. Veraart Keller and Heckman LLP, Brussels, Belgium

2.1

Introduction

Most types of food contact legislation have a sort of approval system to insert new substances and/or materials to the positive list. In many cases the food contact legislations include a kind of testing in order to chacracterize the material/substance that may used for contact with food. In this way the legislation wants to ensure that the materials/substances used are within the scope of the materials/substances that were evaluated. In addition also more generic requirements are applicable to all or a specified set of materials such as sensorial requirements. This chapters describes all kind of testing excluding the testing related to how much of a certain substance is migration to the food (simulant), the so-called specific migration testing.

2.2 2.2.1

Testing in the European Union Introduction

Food contact materials are regulated in the European Union in different ways. The European Union has issued legislation regarding generic requirements on all food contact materials in its Framework Regulation.1 In addition, the European Union requires that all food contact materials as well as intermediate products of food contact materials be made according to good manufacturing practices (GMP).2 Furthermore, EU legislation is issued on some food contact materials regarding the use of plastics,3 ceramics,4 and regenerated cellulose,5 and on some materials such as the use of 1

REGULATION (EC) No. 1935/2004 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of October 27, 2004 on materials and articles intended to come into contact with food and repealing Directives 80/590/EEC and 89/109/EEC.

2

COMMISSION REGULATION (EC) No. 2023/2006 of December 22, 2006, on GMP for materials and articles intended to come into contact with food. COMMISSION REGULATION (EU) No. 10/2011 of January 14, 2011, on plastic materials and articles intended to come into contact with food, as amended.

3

4

Council Directive 84/500/EEC on the approximation of the laws of the member states relating to ceramic articles intended to come into contact with food, as amended.

5

COMMISSION DIRECTIVE 2007/42/EC of June 29, 2007, relating to materials and articles made of regenerated cellulose film intended to come into contact with foodstuffs.

Global Legislation for Food Contact Materials. http://dx.doi.org/10.1016/B978-1-78242-014-9.00002-4 © 2015 Elsevier Ltd. All rights reserved.

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Global Legislation for Food Contact Materials

BADGE/BFDGE/NOGE.6 Some EU member states have issued legislation on one or more materials that are not regulated by the European Union. Both the European Union and the member state legislation testing of the food contact materials are described in this chapter. Also we have provided a description for some of the testing. This chapter focuses on the nonmigration end testing as we have covered the migration testing in a separate chapter of this book.

2.2.2

Overall migration testing

The overall migration is the total amount of the nonvolatile substances that is able to migrate to the food. In the past, the overall migration was intended for two purposes: (1) as an inertness test and (2) as a way to reduce the number of specific migrations. As of the publication of the plastics regulation in 2011, the overall migration is no longer intended to reduce the number of specific migrations. In addition, the time and temperature conditions have been changed and are no longer identical with the time and temperature conditions that need to be selected for the specific migration. The overall migration must be determined using one of the seven standardized conditions (OM1–OM7) as provided in Table 2.1 using food simulants, such as simulant

Overall migration conditions as included in the regulation of plastics

Table 2.1

6

Test number

Contact time in days or hours (h) at contact temperature (°C)

OM1

10 days at 20 °C

OM2

10 days at 40 °C

OM3

2 h at 70 °C

OM4

1 h at 100 °C

OM5 OM6

2 h at 100 °C or at reflux or alternatively 1 h at 121 °C 4 h at 100 °C or at reflux

OM7

2 h at 175 °C

Intended food contact conditions Any food contact at frozen and refrigerated conditions Any long-term storage at room temperature or below, including heating up to 70 °C for up to 2 h, or heating up to 100 °C for up to 15 min Any contact conditions that include heating up to 70 °C for up to 2 h, or up to 100 °C for up to 15 min, which are not followed by long-term room or refrigerated temperature storage High-temperature applications for all food simulants at temperature up to 100 °C High-temperature applications up to 121 °C Any food contact conditions with food simulants A, B, or C, at temperature exceeding 40 °C High-temperature applications with fatty foods exceeding the conditions of OM5

COMMISSION REGULATION (EC) No. 1895/2005 of November 18, 2005, on the restriction of use of certain epoxy derivatives in materials and articles intended to come into contact with food.

Compliance testing for food contact materials

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Table 2.2 Additional overall migration conditions as described in the plastics regulation

Test number OM 8

OM 9

Test conditions Food simulant E for 2 h at 175 °C and food simulant D2 for 2 h at 100 °C Food simulant E for 2 h at 175 °C and food simulant D2 for 10 days at 40 °C

Intended food contact conditions

Covers the intended food contact conditions described in

High-temperature applications only

OM1, OM3, OM4, OM5, and OM6

High-temperature applications including long-term storage at room temperature

OM1, OM2, OM3, OM4, OM5, and OM6

A (10% ethanol), simulant B (3% acetic acid), simulant C (20% ethanol), simulant D1 (50% ethanol), and simulant D2 (vegetable oil). It is described in the legislation that l

l

l

l

when testing with OM2, also the testing with OM1 and OM3 are covered; when testing with OM5, also the testing with OM1, OM2, OM3, and OM4 are covered; when testing with OM6, also the testing with OM1, OM2, OM3, OM4, and OM5 are covered; and when testing with OM7, also the testing with OM1, OM2, OM3, OM4, OM6, and OM7 are covered.

In some cases it is not possible to determine the overall migration into vegetable oil. Therefore, two additional tests (see Table 2.2) are described in the plastics regulation in cases in which OM7 cannot be performed. In the draft guidance document on testing,7 it is explained that in cases in which a vegetable oil cannot be used, a combination of 95% ethanol and isooctane and sometimes also MPPO (TENAX) might be used. A conversion table with testing conditions for the 95% ethanol, isooctane, and MPPO is provided. These testing conditions are different from those discussed in the earlier testing directive and are dependent not only on the original testing conditions of the vegetable oil but also on the plastic material. There is a set for polyolefin type of polymers and one for the more polar polymers such as PET. The overall migration limit for plastics is 60 mg/kg for products that are specifically intended for children or small children. In the other cases the limit is 10 mg/dm2. The overall migration may be applicable as well for materials not covered by the EU legislation. An example is in the Netherlands where the overall migration is applicable 7

Technical guidelines for migration testing, draft for consultation, version March 2014, Joint Research Center.

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Global Legislation for Food Contact Materials

for paper and board, cork, metals, glass, ceramics, textiles, wood, cork, and coatings. The testing must be done on the finished product. This means that when a coating is applied on a paper, the overall migration is not intended to be performed on the paper. Also in the Dutch legislation, the migration limits are identical to the EU legislation on plastics, with a few exceptions. For rubber in the Netherlands, for example, the following overall migration limits must be used: Category I rubber Category II rubber

2.2.3

3% acetic acid Other simulants

20 mg/kg 100 mg/kg 60 mg/kg

Specific migration testing

The specific migration testing mimics the amount of a specific substance or a group of related substances that can migrate to the food during contact. The migration testing is performed using simulants that mimic the different types of food. The simulants are brought into contact with food contact materials using specific time and temperature conditions that depend on the actual contact conditions as well as the material. The migration limits can be set in an EU regulation or be included in one of the member state’s legislation. More details can be found in the chapter dedicated to migration testing.

2.2.4

Determination of residual content

In some cases, substances can be very reactive and migration testing is not possible because the substances will react with the simulant(s). In those cases, the legislator may decide to set a limit on the residual amount that may be present of a substance or to a group of substances with a related toxicity. In other cases, the legislation may have set a residual amount limit because of political reasons as they consider that the presence of a substance is unwanted and should be limited as much as possible. Another reason for determining a residual limit is that an enforcement authority can verify that a substance is not used in an amount exceeding the maximum use level as stipulated in the applicable legislation. These kinds of maximum use levels can be found mostly in member state legislation or recommendations. The maximum residual amount can be described in different ways: l

l

l

expressed in mg/kg finished product; expressed in mg/6dm2 finished product; and expressed in mg/kg or % of another substance that is included in the positive list of a legislation or recommendation.

In most cases, no analytical method is proscribed in the legislation and any method can be used as long as it is able to detect the substance at the level required and the method can be considered as reliable. Validation testing might be needed to determine repeatability testing, recovery testing, and more.

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Table 2.3 List of CEN methods regarding residual amount testing in plastics CEN method

Substance

EN 13130-4:2004 EN 13130-6:2004 EN 13130-8:2004 CEN/TS 13130-17:2005 CEN/TS 13130-20:2005 CEN/TS 13130-22:2005

1,3-Butadiene Vinylidene chloride Isocyanates Carbonyl chloride Epichlorohydrine Ethylene oxide and propylene oxide

The European Normalization Organization (CEN) has published analytical methods for the determination of the residual content of some substances, as shown in Table 2.3.

2.2.5

Sensorial evaluation

One of the requirements of the Framework Regulation of Europe8 is that Article 3.1 Materials and articles, including active and intelligent materials and articles, shall be manufactured in compliance with good manufacturing practice so that, under normal or foreseeable conditions of use, they do not transfer their constituents to food in quantities which could: ... (c) bring about a deterioration in the organoleptic characteristics thereof.

This is not an easy test to do. Especially not for the packaging industry as they do not have the food, industrial processing, and filling applications available. Therefore, the organoleptic tests are often done by the food industry instead. No specific guidance is provided in the European Union. The best way is to use the actual food and not simulants. This is because not only do the migrating substances influence whether a change of the organoleptic characteristics is detected, the food is also important. The sensorial characteristics can be detected more easily when a substance migrates to a food with little or no taste or odor (such as flat water) compared with a food with a strong odor (such as mustard). In some cases the actual food is not used but food such as chocolate is used instead. This can be very useful if testing is done by a packaging company. One would, however, be sure that the food selected is a worst case compared with the food that will be in contact with the packaging later. The Dutch legislation provides some guidance on how this testing can be done. The testing is based on ISO 4120.9 Suppose that the question is whether the food that is packed in a packaging (situation A) takes on different organoleptic characteristics than 8

Regulation (EC) No 1935/2004 of the European Parliament and of the Council of October 27, 2004, on materials and articles intended to come into contact with food and repealing Directives 80/590/EEC and 89/109/EEC.

9

ISO 4120, Sensory analysis—Methodology—Triangle test.

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Global Legislation for Food Contact Materials

the food that is not packed in this packaging but is stored in an inert packaging (situation B). The principle is that a group of trained people (the panel) is given three coded samples. Half of the panel gets two samples of A and one sample B and the other half of the panel is given one sample A and two samples of B. As the samples are coded in an untraceable way, the member does not know what combination (twice sample A and one sample B or one sample A and twice sample B) he or she has to judge. The question that is asked is which of the three samples is the deviating one (a choice must be made). Using some statistics (based on the certainty needed and the number of members of the panel), it can be calculated whether or not a statistical deviation can be found. The German testing is based on EN 1230-1.10 This European Standard specifies a test procedure for the evaluation of the odor that is released from a paper or cardboard. It is applicable to all types of paper and board, including the coated and/or printed material. Samples of the material under investigation are to be kept in the dark in glass containers at (23
2) °C for 20–24 h. The smell of the air from the containers will be judged by a select group of auditors. The odor intensity is rated on a scale of 0–4.

2.2.6

Purity requirements

In some cases substances may be used only if they meet with certain purity requirements. These kinds of purity requirements are often set if it appears during the evaluation of the substance that some impurities can either be present due to the manufacturing process or be added as they are present in the raw materials to produce the substance. In other cases it is known that some group of substances might contain some toxic substances. Purity requirements can be set in multiple ways: l

l

As a residual amount, representing the total amount of a substance that might be present. As an extractable amount, representing the part that is not bound strongly enough (by either covalent or strong ionic bonding), and this fraction can be extracted using a specified extraction solvent, extraction time, and extraction temperature.

2.2.6.1

Colorants

The first colorants were salts of heavy metals. These salts could either contain impurities of substances with a toxicological concern or the heavy metal itself could leach during use. Hereafter colorants were made based on aromatic amines. Some substances with a concern for migration are aromatic amines, and more especially primary aromatic amines. Limits are provided in AP 89(1) (e.g., the extractable amount of heavy metals, unsulfated aromatic amines, and aromatic aminosulfonic acids) and the Dutch legislation (e.g., limits for extractable amount of heavy metals, primary aromatic amines). In most cases the extractable amount is determined using a strong acidic solution. There are, however, some differences in the ratio between the extractant and the sample, the contact time and temperature, and the limits as shown in Table 2.4. 10

Paper and board intended to come into contact with foodstuffs—Sensory analysis—Part 1: Odor.

Compliance testing for food contact materials

Table 2.4

49

Extraction conditions and limits for colorants Extraction conditions Extraction procedure

Method AP 89(1)

Dutch legislation Spanish legislation

10 g colorant + 100 ml 0.1 M HCl 10 g colorant + 150 ml 0.1 N HCl 0.1 N HCl (volumes and weight not provided)

T+t

Substances

10 min at 23 °C

Sb (0.05%), As (0.01%), Ba (0.01%), Cd (0.01%), Cr (0.1%), Pb (0.01%), Hg (0.005%), Se (0.01%) Sb (0.2%), As (0.01%), Ba (0.01%), Cd (0.1%), Cr (0.1%), Pb (0.01%), Hg (0.005%), Se (0.01%) Sb (0.05%), As (0.01%), Ba (0.01%), Cd (0.01%), Cr (0.1%), Pb (0.01%), Hg (0.005%), Se (0.01%)

15 min at 23 °C Extraction conditions not provided

2.2.6.2 Carbon black Carbon black can be used either as a filler or as a colorant. Carbon black can be made in different ways. One potential risk is the formation of polyaromatic hydrocarbons. These polyaromatic hydrocarbons are very toxic. Carbon black is used in many applications and therefore it is listed on many positive lists, and in almost all cases purity requirements are set. A few examples are provided in Table 2.5.

2.2.7

Color release

Much of the migration testing is related to the migration of substances with a toxicological concern. In most cases these substances are harmless. It is, however, possible that substances which have a color are migrating to such an extent that they can color the food packed but the amount migrated is not high enough to create a concern for toxicological effect. This is regarded as an effect that is not acceptable as described in the Framework article 3.1.b (although it is not mentioned specifically in this legislation). Testing is described in the Council of Europe Resolution on colorants,11 the Dutch legislation on food contact materials,12 as well as in the DIN 646.13 All three methods are based on the following principle. A filter paper is saturated with a simulant. The filter paper is brought into contact with the food contact material and, after some time, the filter paper that was in contact with the food contact material is compared visually 11

Council of Europe Resolution AP 89(1) on the use of colorants in plastic materials coming into contact with food.

12

Regeling on packagings and utensils coming into contact with food dated14 March 2012, Annex B, Chapter I, 5.3.6.

13

DIN 646 from 2006 Paper and Board intended to come into contact with foodstuffs—Determination of colour fastness of dyed paper and board.

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Global Legislation for Food Contact Materials

Table 2.5

Example of purity requirements for carbon black

Legislation

Purity requirements

Plastics Regulation 10/2011 of the EU

Primary particles of 10–300 nm which are aggregated to a size of 100–1200 nm which may form agglomerates within the size distribution of 300 nm – some mm Toluene extractables: maximum 0.1%, determined by ISO method 6209 UV absorption of cyclohexane extract at 386 nm: <0.02 AU for a 1-cm cell or <0.1 AU for a 5-cm cell, determined according to a generally recognized method of analysis Benzo(a)pyrene content: max 0.25 mg/kg carbon black Maximum use level of carbon black in the polymer: 2.5% (w/w) Toluene extractable fraction of carbon black, extractable fraction of polychlorinated PCBs Extraction of carbon black with toluene + spectrophotometric determination Toluene extractables: maximum 0.1%, determined according to ISO method 6209 UV absorption of cyclohexane extract at 386 nm: <0.02 AU for a 1-cm cell or <0.1 AU for a 5-cm cell, determined according to a generally recognized method of analysis Benzo(a)pyrene content: max 0.25 mg/kg carbon black Maximum use level of carbon black in the polymer: 2.5% (w/w)

AP 89(1) Dutch legislation Spanish legislation*

*

Real Decreto 847/2011 of June 17, 2011.

with the filter paper that was not in contact with the filter paper (only wetted with simulant). There should be no color difference between the two filter papers. It is obvious, as the conclusion is based on visual inspection, that it is possible that two people may come to different conclusions as this kind of inspection is subjective. Furthermore, it must be realized that two substances may be off spec at different concentrations, as the same concentration of two substances may result in different color intensions. No conclusion can be drawn on the safety of the colorants in question, even when the test gives a favorable result. Examples of testing conditions are provided in Table 2.6.

2.3 2.3.1

Testing in the United States Introduction

Food contact materials in the United States are regulated in different ways. One of the earliest forms (since 1958) is the legislation included in Code of Federal Regulations (CFR) 21, in which food additives are regulated. Substances migrating from food contact materials are regarded as indirect food additives. The following relevant chapters can be found in 21 CFR:

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Table 2.6 Details on CoE, DIN 646, and Dutch contact conditions for color release tests

Simulants to be used

Contact conditions Method standard

Dutch legislation

CoE Res. 89(1)

DIN 646

Distilled water 3% acetic acid 15% ethanol Decolorized edible oil 5 h at 50 °C

Distilled water 3% acetic acid saliva simulant olive oil

3% acetic acid Colorless oil*

10 min at 23 °C or 24 h at 23 °C DIN EN 646:2006

5 h at 40 °C

–

–

*

The following oils are mentioned in the legislation: groundnut oil, coconut oil, sunflower oil, olive oil, and HB307.

21 CFR 73, Subpart A: Color additives for direct food contact exempt from batch certification. 74, Subpart A: Color additives for direct food contact subject to batch certification. 21 CFR 170 Food additives. 21 CFR 171 Food additive petitions. 21 CFR 172 Food additives permitted for direct addition to food for human consumption. 21 CFR 173 Secondary direct food additives permitted in food for human consumption. 21 CFR 174 Indirect food additives: General. 21 CFR 175 Indirect food additives: Adhesives and components of coatings. 21 CFR 176 Indirect food additives: Paper and paperboard components. 21 CFR 177 Indirect food additives: Polymers. 21 CFR 178 Indirect food additives: Adjuvants, production aids, and sanitizers. 21 CFR 179 Irradiation in the production, processing, and handling of food. 21 CFR 180 Food additives permitted in food or in contact with food on an interim basis pending additional study. 21 CFR 181 Prior-sanctioned food ingredients. 21 CFR 182 Substances generally recognized as safe. 21 CFR 184 Direct food substances affirmed as generally recognized as safe. 21 CFR 186 Indirect food substances affirmed as generally recognized as safe. 21 CFR 189 Substances prohibited from use in human food. 21 CFR 190 Dietary supplements.

In many of these regulations end tests are described. The end tests are discussed in more detail in the next section. The end tests are not intended to mimic actual migration of substances during contact, but are intended to characterize the materials. They are characterization tests. The details that need to be taken into consideration for performing the end tests are included in the relevant CFR in full or a reference to the method is included in the relevant CFR. This is in contrast with the migration testing of substances, which are intended to describe how much of a certain substance is migrating to the food. The migration may or may not be converted to the exposure. The migration testing/exposure assessment is described in a few sections of the CFR (include examples), in using the no migration assumption, food contact notifications (FCNs), and generally recognized as safe (GRAS) determinations/notifications.

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2.3.2

Global Legislation for Food Contact Materials

End testing

As mentioned above the end tests are intended to describe the food contact materials to ensure that the material is falling within the class that is regulated. The end tests can only be used for compliance purposes for cleared substances only. In other words, migration testing or other testing is needed for other ways of demonstrating compliance. The difference between the conditions to be used for end tests and for migration testing is very large. Differences can be found in the extraction solvents to be used, the extraction conditions (time and temperature) to be used, the applicable limits, and the amount of material to be taken into account per amount of extractant. The conditions for the migration testing are discussed in detail in Section 2.3.3. The conditions to be used for the end tests can be found in 21 CFR. Here is a nonexhaustive overview of end testing as mentioned in 21 CFR: A few examples of end tests that are included are discussed here for paper, coating, and plastics.

2.3.2.1

Paper

Paper is regulated in 21 CFR 176.170 (intended to come into contact with all food types) and 21 CFR 176.180 (intended to come into contact with dry food only). Only in section 21 CFR 176.170 extraction tests are included. The extraction tests are often referred to as total nonvolatile extraction (TNV) tests. This is because the extraction test does not distinguish between the substances extracted (like the overall migration test as described above). It only determines the nonvolatiles as the extractants (water, heptane, 8% ethanol, or 50% ethanol) are evaporated and the residue is determined gravimetrically. The extractants to be selected as well as the time and temperature needed to be selected depends on two aspects: the food type (which is provided in Table 1 of 21 CFR 176.180) and the conditions of use (see Table 2.7). The time/temperature/ extractant selection is provided in Table 2 of 21 CFR 176.180 (for which an excerpt is provided in Table 2.8). The excerpt of Table 2 of 21 CFR 176.180 (as provided in Table 2.8) shows that not all the extractant needs to be included: when used for food type II that is hot filled or pasteurized above 150 °F, IV-B and VII-B only water should be used and the extraction should be done by filling the object with water at boiling and waiting until the temperature has dropped to 100 °F. When the table mentions “do” this means ditto and in that case the condition described above must be selected. Thus, for condition C for food types IV-A and VII-A, the same test must be conducted for water, with the addition of an extraction with heptane at 120 °F for 15 min. For the result obtained with heptane, the extractability results must be divided by a factor of five in arriving at the extractability for a food product having water-in-oil emulsion or free oil or fat. A heptane food-simulating solvent is not required in the case of wax-polymer blend coatings for corrugated paperboard containers intended for use in bulk packaging of iced meat, iced fish, and iced poultry.

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Table 2.7 21 CFR 176.180 Table 1—Types of raw and processed foods I II

IV

Nonacid, aqueous products; may contain salt or sugar or both (pH above 5.0) Acid, aqueous products; may contain salt or sugar or both, and including oil-inwater emulsions of low- or high-fat content Aqueous, acid, or nonacid products containing free oil or fat; may contain salt, and including water-in-oil emulsions of low- or high-fat content Dairy products and modifications:

V VI

A Water-in-oil emulsions, high- or low-fat B Oil-in-water emulsions, high- or low-fat Low-moisture fats and oil Beverages:

VII

A Containing up to 8% of alcohol B Nonalcoholic C Containing more than 8% alcohol Bakery products other than those included under types VIII or IX of this table:

XIII IX

A Moist bakery products with surface containing free fat or oil B Moist bakery products with surface containing no free fat or oil Dry solids with the surface containing no free fat or oil (no end test required) Dry solids with the surface containing free fat or oil

III

2.3.2.2 Coatings Coatings on metals are regulated in 21 CFR 175.300. Similar to the tests on paper, TNV tests need to be conducted using extractants, although in this case the extractants are water, heptane, and 8% ethanol. The time and temperature conditions to be selected depend on the food type (the food types are provided in Table 2.9) and the conditions of use. As will be described below, the food types are similar but different. Table 2.10 shows the extraction conditions that need to be used for 21 CFR 175.300. The testing conditions that need to be selected for coatings on metal substrates are similar, but sometimes different, compared with the testing conditions needed for paper. Those doing the testing need to ensure that the correct section of the 21 CFR is referred to when specifying extraction tests.

2.3.2.3 Plastics Most plastics listed in the 21 CFR can be found in 21 CFR 177. This section has two parts: part B (21 CFR 177.1010–21 CFR 177.2000), which describes plastics that can be used as basic components for single and repeated use food contact surfaces and part C (21 CFR 177.2210–177.2940), which describes plastics that can be used as basic components of articles intended for repeated use only. Table 2.11 provides an overview of the end test described in the 21 CFR (see the official publication for more details).

54

Table 2.8

An excerpt of Table 2 of 21 CFR 176.170

Food-simulating solvents

Condition of use

Types of food (see Table 1)

Water

Heptane1

8% alcohol

Time and temperature

Time and temperature

Time and temperature

Time and temperature

.......................

.......................

...........................

C. Hot filled or pasteurized above 150 °F .... II, IV-B, VII-B ..... Fill boiling,

50% alcohol

cool to 100 °F .......do ...........

120 °F, 15 min

.......................

...........................

V, IX ..................... VII-B ..................... III, IV-A, VII-A ...

....................... .......do ........... ....................... ....................... ....................... 150 °F, 2 h .......do ........... 100 °F, 30 min

....................... ....................... ....................... .......................

........................... ........................... ........................... ...........................

V, IX ..................... VI-A ...................... VI-C ......................

....................... ....................... .......................

.......do ........... ....................... .......................

....................... 150 °F, 2 h .......................

........................... ........................... 150 °F, 2 h

D. Hot filled or pasteurized below 150 °F .... II, IV-B, VI-B, ......

Global Legislation for Food Contact Materials

III, IV-A, VII-A ....

Compliance testing for food contact materials

Table 2.9 I

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Table 1 of 21 CFR 175.300

IV

Nonacid (pH above 5.0), aqueous products; may contain salt or sugar or both, and including oil-in-water emulsions of low- or high-fat content Acidic (pH 5.0 or below), aqueous products; may contain salt or sugar or both, and including oil-in-water emulsions of low- or high-fat content Aqueous, acid, or nonacid products containing free oil or fat; may contain salt, and including water-in-oil emulsions of low- or high-fat content Dairy products and modifications:

V VI

A Water-in-oil emulsion, high- or low-fat B Oil-in-water emulsion, high- or low-fat Low moisture fats and oils Beverages:

VII VIII

A Containing alcohol B Nonalcoholic Bakery products Dry solids (no end test required)

II III

2.3.3

Migration testing

Migration testing is needed in case the use of a substance is not cleared by an appropriate listing in the CFR, or is not covered by a FCN or a Threshold of Regulation. The migration testing can be used for uncleared substances in order to l

l

establish a status and prepare a FCN dossier.

The no migration assumption means that the migration of a substance is below the toxicological threshold. The threshold is in many cases 50 ppb (Ramsey Proposal), 10 ppb in case of high-consumption applications, or it may even be a lower limit when there are special toxicological concerns, for example, 1/10th of the virtual safe dose (VSD)14 in the case of carcinogenic substances. The no migration assumption is a selfdetermination method. This means that no blessing from the Food and Drug Administration (FDA) is required. Please note that for the no migration assumption only the migration is taken into account and not the dietary exposure. When one wants to apply for a FCN, he or she must first file a dossier. One of the topics that is covered in the FCN dossier is migration testing. The requirements for how this testing needs to be done are described in the chemistry guidance document issued by the FDA.15 The detection limit required depends on the amount of toxicity data that is available as well as the actual exposure. The exposure is calculated from

14

The virtual safe dose (VSD) is the dietary exposure that corresponds to a 1  106 risk of cancer.

15

http://www.fda.gov/Food/GuidanceRegulation/GuidanceDocumentsRegulatoryInformation/Ingredients AdditivesGRASPackaging/ucm081818.htm.

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Table 2.10

An excerpt of Table 2 of 21 CFR 175.300

Extractant Condition of use

Types of food (see Table 1)

Water (time and Heptane1,2 (time temperature) and temperature)

B. Boiling water sterilized ................

II ..........................

212 °F, 30 min ....

III, VII ................... .......do ...............

C. Hot filled or pasteurized above 150 °F

II, IV-B ................

D. Hot filled or pasteurized below 150 °F

E. Room temperature filled and stored (no thermal treatment in the container)

II, IV-B, VI-B ...... III, IV-A .............. V .......................... VI-A .....................

............................ 120 °F, 30 min

............................ 120 °F, 15 min

150 °F, 2 h ........ .......do ...............

.......do. 100 °F, 30 min .......do ...............

150 °F, 2 h

I, II, IV-B, VI-B ... 120 °F, 24 h ...... III, IV-A ............... .......do ............... V, VII ............... VI-A ......................

........................... 70 °F, 30 min .......do ...............

120 °F, 24 h

Global Legislation for Food Contact Materials

III, IV-A ............... V ..........................

Fill boiling, cool to 100 °F .......do ...............

8% alcohol (time and temperature)

Compliance testing for food contact materials

Table 2.11

57

An overview of end tests in 21 CFR

21 CFR

Polymer

End tests

177.1010

Acrylic and modified acrylic plastics, semi-rigid, and rigid

l

l

l

TNV Potassium permanganate oxidizable extractives UV absorbance of extractives

177.1020

Acrylonitrile/butadiene/styrene copolymer

l

TNV

177.1030

Acrylonitrile/butadiene/styrene/methyl methacrylate copolymer

l

Viscosity QM for specific substance(s) TNV

l

l

177.1040

Acrylonitrile/styrene copolymer

l

l

l

l

177.1050

Acrylonitrile/styrene copolymer modified with butadiene/styrene elastomer

l

l

l

l

QM for specific substance(s) TNV MW requirement Nitrogen amount Nitrogen amount Viscosity QM for specific substance(s) TNV

177.1060

n-Alkylglutarimide/acrylic copolymers

l

TNV

177.1200

Cellophane

l

None

177.1210

Closures with sealing gaskets for food containers Cross-linked polyacrylate copolymers

l

TNV

l

TNV

l

TNV

177.1310

1,4-Cyclohexylene dimethylene terephthalate and 1,4-cyclohexylene dimethylene isophthalate copolymer Ethylene-acrylic acid copolymers

l

TNV

177.1312

Ethylene-carbon monoxide copolymers

l

Melt index TNV

177.1211. 177.1240

l

177.1315 177.1320

Ethylene-1,4-cyclohexylene dimethylene terephthalate copolymers

l

Ethylene-ethyl acrylate copolymers

l

l

l

177.1330

Ionomeric resins

l

Viscosity TNV QM for specific substance(s) TNV TNV Continued

58

Table 2.11

Global Legislation for Food Contact Materials

Continued

21 CFR

Polymer

End tests

177.1340

Ethylene-methyl acrylate copolymer resins

l

TNV

177.1345

Ethylene/1,3-phenylene oxyethylene isophthalate/terephthalate copolymer

l

Softening point Density

Ethylene-vinyl acetate copolymers

l

177.1350

l

l

l

Melt flow* Viscosity* Fluorine content*

Ethylene-vinyl acetate-vinyl alcohol copolymers Fluorocarbon resins

l

TNV

l

TNV TNV

l

None

177.1400

Laminate structures for use at temperatures of 250 °F and above Laminate structures for use at temperatures between 120 °F and 250 °F Hydroxyethyl cellulose film, water-insoluble

l

l

None

177.1420

Isobutylene polymers

l

None

177.1430

Isobutylene-butene copolymers

l

MW requirements Viscosity Bromine value

177.1360 177.1380 177.1390 177.1395

l

l

177.1440 177.1460 177.1480

4,40 -Isopropylidenediphenol-epichlorohydrin resins minimum molecular weight 10,000 Melamine-formaldehyde resins in molded articles Nitrile rubber modified acrylonitrile-methyl acrylate copolymers

l

TNV

l

TNV

l

Nitrogen amount Viscosity QM for specific substance(s) TNV

l

l

l

177.1500

Nylon resins

l

l

l

l

177.1520

Olefin polymers

l

l

l

l

177.1550

Perfluorocarbon resins

l

l

l

Melting point Solubility in boiling HCl TNV Viscosity Density Melting point TNV Solubility in xylene Viscosity Thermal instability TNV

Compliance testing for food contact materials

Table 2.11

59

Continued

21 CFR

Polymer

End tests

177.1555

Polyarylate resins

l

TNV

177.1556

Polyaryletherketone resins

l

TNV

177.1560

Polyarylsulfone resins

l

TNV

177.1570

Poly-1-butene resins and butene/ethylene copolymers

l

Viscosity Density Melt index TNV

l

l

l

177.1580

Polycarbonate resins

l

l

177.1585

Polyestercarbonate resins

l

l

l

QM for specific substance(s) TNV TNV MW requirements QM for specific substance(s)

177.1590

Polyester elastomers

l

Abrasion test

177.1595

Polyetherimide resin

l

TNV

177.1600

Polyethylene resins, carboxyl modified

l

TNV

177.1610

Polyethylene, chlorinated

l

TNV

177.1615

Polyethylene, fluorinated

l

TNV

177.1620

Polyethylene, oxidized

l

TNV

177.1630

Polyethylene phthalate polymers

l

TNV

177.1632

Poly(phenyleneterephthalamide) resins

l

QM for specific substance(s) TNV

l

177.1635

Poly(p-methylstyrene) and rubber-modified poly(p-methylstyrene)

l

QM for specific substance(s)

177.1637

Poly(oxy-1,2-ethanediyloxycarbonyl-2,6naphthalenediylcarbonyl) resins

l

Viscosity TNV

177.1640

Polystyrene and rubber-modified polystyrene

l

QM for specific substance(s)

177.1650

Polysulfide polymer-polyepoxy resins

l

Abrasion test

177.1655

Polysulfone resins

l

MW requirement QM for specific substance(s) TNV

l

l

l

Continued

60

Table 2.11

Global Legislation for Food Contact Materials

Continued

21 CFR

Polymer

End tests

177.1660

Poly(tetramethylene terephthalate)

l

l

Viscosity TNV

177.1670

Polyvinyl alcohol film

l

Viscosity

177.1680

Polyurethane resins

l

Abrasion test

177.1810

Styrene block polymers

l

Mw requirement Solubility in toluene Glass transition point TNV

l

l

l

177.1820

Styrene-maleic anhydride copolymers

l

l

l

177.1830

Styrene-methyl methacrylate copolymers

l

l

l

Mw requirement QM for specific substance(s) TNV TNV Potassium permanganate oxidizable UV absorbance of extracts

177.1850

Textryls

l

TNV

177.1900

Urea-formaldehyde resins in molded articles

l

TNV

177.1950

Vinyl chloride-ethylene copolymers

l

Chlorine content Viscosity TNV

l

l

177.1960

Vinyl chloride-hexene-1 copolymers

l

l

177.1970

Vinyl chloride-lauryl vinyl ether copolymers

l

l

l

177.1980

Vinyl chloride-propylene copolymers

l

l

l

177.1990

Vinylidene

l

l

l

177.2000

Vinylidene chloride/methyl acrylate/methyl methacrylate polymers

l

l

l

Viscosity TNV Chlorine content Viscosity TNV Chlorine content Viscosity TNV QM for specific substance(s) MW requirement TNV QM for specific substance(s) MW requirement TNV

Compliance testing for food contact materials

Table 2.11

61

Continued

21 CFR

Polymer

End tests

177.2210

Ethylene polymer, chlorosulfonated

l

TNV

177.2250

Filters, microporous polymeric

l

QM for specific substance(s)

177.2260

Filters, resin-bonded

l

l

TNV QM for specific substance(s)

l

None

l

TNV

l

TGA TNV QM for specific substance(s)

177.2355

4,40 -Isopropyldenediphenolepichloro-hydrin thermosetting epoxy resins Mineral reinforced nylon resins

177.2400

Perfluorocarbon cured elastomers

177.2280

l

l

177.2410

Phenolic resins in molded articles

l

TNV

177.2415

Poly(aryletherketone) resins

l

TNV

177.2420

Polyester resins, crosslinked

l

TNV

177.2430

Polyether resins, chlorinated

l

None

177.2440

Polyethersulfone resins

l

TNV

177.2450

Polyamide-imide resins

l

QM for specific substance(s) TNV

l

177.2460

Poly(2,6-dimethyl-1,4-phenylene) oxide resins

l

l

l

177.2465

177.2470

Polymethylmethacrylate/poly (trimethoxysilylpropyl)methacrylate copolymers Polyoxymethylene copolymer

l

None

l

Density MW requirements Melting point QM for specific substance(s) TNV

l

l

l

l

177.2480

Polyoxymethylene homopolymer

Viscosity MW requirements TNV

l

l

l

l

MW requirements Density Melting point TNV Continued

62

Global Legislation for Food Contact Materials

Table 2.11

Continued

21 CFR

Polymer

End tests

177.2490

Polyphenylene sulfide resins

l

l

l

QM for specific substance(s) Viscosity TNV

177.2500

Polyphenylene sulfone resins

l

Glass transition temperature

177.2510

Polyvinylidene fluoride resins

l

TNV

177.2550

Reverse osmosis membranes

l

None

177.2600

Rubber articles intended for repeated use

l

TNV

177.2710

Styrene-divinylbenzene resins, cross-linked

l

TNV

177.2800

Textiles and textile fibers

l

None

177.2910

Ultrafiltration membranes

l

QM for specific substance(s)

*

Depending on comonomer used.

the migration and the consumption factor of the application. The toxicity data requirements as set by the FDA are (more details can be found in the guidance document on toxicology as issued by the FDA)16: 0.5 ppb 0.5–50 ppb 50–1 ppm >1 ppm

No toxicity testing needed 2 In vitro genotoxicity testing 90-Days studies and an in vivo genotoxicity testing Full 2-year study

Analytical migration testing may be replaced by 100% migration calculations or by calculations based on diffusion. The advantage of these nonanalytical methods is that they are administrative methods, which enables you to calculate the migration quickly and in a cost-efficient way. In the case of 100% migration it is assumed that all the substance that is present is migrating to the food during the contact. The calculation can be made only if the (residual) amount of the substance can be determined or estimated. Furthermore the generic assumption is a contact of 10 g of food with 1 in.2 The maximum migration can be calculated using the following equation:

16

http://www.fda.gov/Food/GuidanceRegulation/GuidanceDocumentsRegulatoryInformation/Ingredients AdditivesGRASPackaging/ucm081825.htm.

Compliance testing for food contact materials

63

thickness of layer ðin in:Þ  16:4 cm3 =in:3 ðconversion factor from in: to cmÞ density of the layer ðin g=cm3 Þ concentration of the substance ðin g substance=g layerÞ Migration ðin g substance=g foodÞ ¼ : 10g=in:2 In the case of using diffusion calculations, it is assumed that the molecules behave according to the second law of thermodynamics. The migration is a three-step process. In the first step, a substance in a material is migrating to the packaging food surface. The second step is the partitioning of the substance between the polymer layer and the food. The last step is considering the diffusion of the substance in the food. When performing modeling to estimate migration, the focus is on the first step. The other two steps are considered as rapid steps compared with the slow first step. The migration can be calculated with the following equation: rffiffiffiffiffi Dt ; Mt ¼ 2C0 p where Mt ¼ the migration at time t (s), D ¼ diffusion coefficient of migrant in polymer (cm2/s), C0 ¼ initial migrant concentration in food contact layer (g/cm3).

Both commercial and free modeling software is available for modeling calculations. Some of them can handle complicated cases such as multilayers, set-off, and influence of storage before use of the material. More details on the mathematic modeling can be found in the guidance document as issued by the JRC.17 Both the 100% migration assumption and the modeling calculations are worst-case estimations. This means that these methods can be used to demonstrate that a certain limit cannot be exceeded. In case the relevant limit is exceeded, analytical testing is needed. The FDA has defined simulants that can be used in place of actual food. As can be seen from Table 2.12, the simulants are different from the ones defined for in the European Union. These simulants must be brought into contact with the packaging for a certain period and time. The time and temperature must be selected depending on the actual use that is targeted. The FDA has defined the applications and test conditions that need to be chosen for these applications. A summary is provided in Table 2.13. The analytical testing can be done with any suitable method; validation is an important step. Recovery testing must be performed by adding a known amount to a 17

Simoneau, C. (Ed.) (2010) Applicability of generally recognized diffusion models for the estimation of specific migration in support of EU Directive 2002/72/EC, Publication Office of the European Union, Luxembourg, JRC Scientific and Technical Report, EUR 24514 EN. The main contributors to this document are R. Brandsch, B. Brands, R. Franz, M. Klatt, M.R. Milana, O. Piringer, A. Schaefer, C. Simoneau, X. Trier, and O. Vitrac. http://publications.jrc.ec.europa.eu/repository/handle/111111111/ 14935.

64

Global Legislation for Food Contact Materials

Table 2.12 Simulants to be chosen for different food types according to the FDA Food type

Simulant

Aqueous, acidic, and low-alcoholic foods High-alcoholic foods Fatty food

10% ethanol 50% ethanol Food oil or synthetic fat 95% ethanol (polyolefins) 50% ethanol (PET, PS, PVC, etc.) Isooctane (PET)

A summary of the application and test conditions for migration testing for FDA purposes

Table 2.13

Application

Test conditions

A B C

Heat sterilized over 100 °C Boiling water sterilized Hot filled/pasteurized above 66 °C

D

Hot filled/pasteurized below 66 °C

E F

I

Room temperature filled and stored Refrigerated storage (no heat treatment in package) Frozen storage (no heat treatment in package) Frozen or refrigerated storage-ready prepared food to be reheated in container Food irradiated in package

2 h at 121 °C + 10 days at 40 °C 2 h at 100 °C + 10 days at 40 °C 1/2 h at 100 °C or 2 h at 66 °C + 10 days at 40 °C 1/2 h at 66 °C + 10 days at 40 °C 10 days at 40 °C 10 days at 20 °C

J

Cooking (e.g., baking)

G H

l

l

l

5 days at 20 °C 2 h at 100 °C Consult with FDA for test guidance Consult with FDA for test guidance

microwaveable-only containers dual-ovenable trays microwave heat-susceptor packaging

simulant that has been in contact with the sample after it was in contact with the packaging for the time and temperature proscribed. In case the substance was detected, the simulant must be spiked at half of the concentration found, at the concentration found, and two times the concentration found. In case a substance is not detected, spiking needs to be done at the detection limit and twice the detection limit. More details can be found in the chemical guidance document of the FDA.