602nd meeting – 30  September 1997

                                                                  - a37  -                              CM/Del/Dec(97)602

APPENDIX 12

(item 6.3)

                                                      RESOLUTION AP (97) 1

ON ION EXCHANGE AND ADSORBENT RESINS

USED IN THE PROCESSING OF FOODSTUFFS

                                                                          

(Adopted by the Committee of Ministers  on 30 September 1997

at the 602nd meeting of the Ministers' Deputies)

            The Representatives on the Committee of Ministers, of Austria, Belgium, Denmark, Finland, France, Germany, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom, member States of the Partial Agreement in the Social and Public Health field,

            Recalling Resolution (59) 23 of 16 November 1959, concerning the extension of the activities of the Council of Europe in the social and cultural fields;

            Having regard to Resolution (96) 35 of 2 October 1996, whereby they revised the structures of the Partial Agreement and resolved to continue, on the basis of revised rules replacing those set out in Resolution (59) 23, the activities hitherto carried out and developed by virtue of that Resolution; these being in particular aimed at:

            (a)        raising the level of health protection of consumers in its widest sense, including the making of a contribution to harmonising - in the field of products having a direct or indirect impact on the human food chain as well as in the field of pesticides, pharmaceuticals and cosmetics - legislation, regulations and practices governing, on the one hand, quality, efficiency and safety controls for products; and, on the other hand, the safe use of toxic or noxious products;

            (b)        integrating people with disabilities into the community; the definition - and contribution to implement it at European level - of a model coherent policy for people with disabilities, which takes account simultaneously of the principles of full citizenship and independent living; contribution to the elimination of barriers to integration, whatever their nature, whether psychological, educational, family-related, cultural, social, professional, financial or architectural;

            Having regard to the action carried out for several years for the purposes of harmonising their legislation in the public health field and, in particular, in the foodstuffs sector;

            Having regard to the fact that ion exchange and adsorbent resins are used in processing of foodstuffs, water for drinking water included;

CM/Del/Dec(97)602                                 - a38 -

Appendix 12

            Considering that this resolution does not affect the national regulations concerning the quality of drinking water, and that therefore the limits laid down in the national regulations for drinking water have to be met;

            Considering that ion exchange and adsorbent resins used in processing of foodstuffs may, by reason of migration of resin constituents to the foodstuffs, pose under certain conditions a risk to human health;

            Observing that the lists of Appendix 2 hereafter represent an inventory of substances used for the manufacture of ion exchange and adsorbent resins intended to come into contact with foodstuffs, but not a positive list;

            Observing that the date specified in Appendix 2 hereafter represents the state of the art of substances used for the manufacture of ion exchange and adsorbent resins intended to come into contact with foodstuffs at that date;

            Observing that the substances of List 1 of Appendix 2 hereafter have been evaluated by an international body and have been considered as toxicologically acceptable, taking into account their restrictions of use;

            Observing that the restrictions of use in Appendix 2 are those set by the Commission of the European Communities in its directives relating to plastic materials and articles intended to come into contact with foodstuffs;

            Observing that the substances of List 2 of Appendix 2 hereafter have not been fully evaluated, or evaluated at all, by an international body due to lack of data and that these substances should be subject to toxicological studies;

           

            Observing that the lists will be updated if new data on substances of Appendix 2 hereafter or on substances not included become available;

            Taking the view that each member State, faced with the need to introduce regulations governing this matter, would find it beneficial to harmonise such regulations at European level,

            Recommend to the governments of the member States of the Partial Agreement in the Social and Public Health Field to take into account in their national laws and regulations on ion exchange and adsorbent resins intended to come into contact with foodstuffs the principles and the inventory list set out in the appendices hereafter:

                                                                - a39 -                                CM/Del/Dec(97)602

                                                          Appendix 12

Appendix 1 to Resolution AP (97) 1

.

GENERAL PRINCIPLES

Definition

            Ion exchange and adsorbent resins, hereafter called resins, are synthetic organic macromolecular compounds which can be used in the processing of foodstuffs to bring about exchange of ions or adsorption of foodstuffs constituents. They do not include, however, cellulosic ion exchangers.

Specifications

            Resins used in processing of foodstuffs should meet the following requirements:

            They should be manufactured in accordance with a certified Quality Assurance System (e.g. ISO 9002 or CEN 29-004) and under the conditions specified in Appendix 2.

            The listing of a substance in a particular category (monomers, chemical modifiers or polymerisation aids) does not preclude its use at some other stage of the manufacturing process.

            The user should be instructed that mechanical attrition of the resin is possible, and steps should be taken to filter the treated liquor to ensure that any fine particles are removed.

            Resins should be made ready for use in accordance with the instructions of the manufacturer.

            Regeneration of resins should be performed in such a manner that they are not contaminated with substances detrimental to health.

            Resins should not release to or form in the foodstuffs any substance in a quantity that poses a risk to human health or that adversely affects the organoleptic properties of the food.

            Resins should be subjected to AFNOR test T 90-601[1]. All five bed-volumes prepared should be tested for total organic carbon (TOC) in order to demonstrate a decreasing release of organic carbon from the first through to the last bed-volume. Total organic carbon in the fifth bed-volume should not exceed 1 mg/l.

CM/Del/Dec(97)602                                 - a40 -

Appendix 12

            Where appropriate, migration of specific resin constituents should be determined as well, using water, 3% (w/v) acetic acid or 15% (v/v) ethanol as the food simulant, whichever is relevant. Migration of specific resin constituents to the fifth bed-volume, obtained as in the AFNOR test, should not exceed the limits set out in Appendix 2. Specific migration should be determined by a method of analysis validated at the specific migration limit level.

            Verification of compliance with specific migration limits is not compulsory if it can be demonstrated, for example by calculation, that by assuming complete migration of the residual quantity of a substance, the specific limit of migration of that substance will not be exceeded.

            Where appropriate, residual quantity of specific resin constituents should be determined in the resin. Residual quantity should meet the limits set out in Appendix 2.

                                                                  - a41 -                             CM/Del/Dec(97)602

                                                                                                                      Appendix 12

                                              Appendix 2 to Resolution AP (97) 1

Inventory list of substances used in the manufacture of

ion exchange and adsorbent resins for food processing

(State of the art: February 1997)

                                                                 Introduction

            Appendix 2 contains the inventory of monomers, chemical modifiers and polymerisation aids which are used in the manufacture of ion exchange and adsorbent resins used for food processing. The lists include:

            -           substances undergoing polymerisation, which includes polycondensation, polyaddition or any other similar process, to manufacture macromolecules;

            -           natural or synthetic macromolecular substances used in the manufacture of modified macromolecules, if the monomers or the other starting substances required to synthesise them are not included in the lists;

            -           substances used to provide a suitable medium in which polymerisation occurs;

            -           substances used to modify existing natural or synthetic macromolecular substances;

            -           substances which are incorporated into ion exchange and adsorbent resins in order to achieve a technical effect in the finished product.

            The lists do not include the salts (including double salts and acid salts) of aluminium, ammonium, calcium, iron, magnesium, potassium, sodium and zinc of the listed acids, phenols or alcohols. These salts can, however, be used as well. Chemical names containing ‘... acid(s), salts’ appear in the lists if the free acid(s) is (are) not listed separately. In such cases the meaning of the term ‘salts’ is ‘salts of aluminium, ammonium, calcium, iron, magnesium, potassium, sodium and zinc’.

            The lists neither include the following substances although they may be present:

            -           substances which could be present in the finished product as:

                        -           impurities of the substances used;

                        -           reaction intermediates;

                        -           decomposition products;

CM/Del/Dec(97)602                                 - a42 –

Appendix 12

            -           oligomers and natural or synthetic macromolecular substances as well as their mixtures, if the monomers or other starting substances required to synthesise them are included in the lists.

            Monomers, chemical modifiers and polymerisation aids shall be of good technical quality as regards the purity requirements.

            The lists contain the following information:

            -           column 1         Name: the chemical name of the substance;

            -           column 2         PM/REF: the EU food contact material reference number of the substance;

            -           column 3         CAS: the Chemical Abstracts Service registry number of the substance;

            -           column 4         Restrictions: restrictions may have been set to:

                                                - specific migration of the substance;

                                                - residual quantity of the substance in the resin;

                                                - any other parameter specifically mentioned.

            If a substance appearing in the list as an individual compound is also covered by a generic term, the restrictions applying to the substance should be those indicated for the individual compound.

           

The abbreviations of column 4 mean:

            -           DL                   detection limit of the method of analysis;

            -           FP                    finished product;

            -           ND                  not detectable. For the purpose of this resolution ‘ND’ means that the substance should not be detected, by a validated method of analysis, at the level of the detection limit specified;

           

            -           QM                  limit set to the residual quantity of a substance in the finished product. For the purpose of this resolution ‘QM’ also means that the residual quantity of the substance should be determined by a validated method of analysis at the level of the specified residual quantity limit;

                                                                  - a43 -                             CM/Del/Dec(97)602

                                                                                                                      Appendix 12

            -           SML                specific migration limit. Limit set to the migration of a specific substance to food or to food simulant(s). For the purpose of this resolution ‘SML’ also means that the specific migration of the substance should be determined by a validated method of analysis at the level of the specified migration limit.

            If any of the above methods of analysis does not currently exist, an analytical method with appropriate performance characteristics at the specified limit level may be used, pending development of a validated method.

CM/Del/Dec(97)602                                 - a44 –

Appendix 12                                                 

                                                                Inventory list

                                                                       List 1

                                    Substances evaluated by an international body

                                          (Substances classified in SCF-Lists 0 – 4)

NAME

 PM/REF

 CAS

 RESTRICTIONS (mg/kg)

Monomers and other starting substances

acrylic acid, n-butyl ester

 10780

 00141–32–2

  –

acrylic acid, ethyl ester

 11470

 00140–88–5

  –

acrylic acid, methyl ester

 11710

 00096–33–3

  –

acrylonitrile

 12100

 00107–13–1

 SML = ND (DL = 0.02)

formaldehyde

 17260

 00050–00–0

 SML = 15

methacrylic acid, methyl ester

 21130

 00080–62–6

  –

methanol

 21550

 00067–56–1

  –

styrene

 24610

 00100–42–5

  –

Chemical modifiers

acetic anhydride

 10150

 00108–24–7

  –

tert.butyl‑4‑hydroxyanisole ( = BHA )

 40720

 25013–16–5

 SML = 30

carbonic acid, salts

 42500

  –

  –

diethylenetriamine

 15790

 00111–40–0

 SML = 5

dimethylamine

 16145

 00124–40–3

 SML = 0.06

2-(dimethylamino)ethanol

 16150

 00108–01–0

 SML = 18

ethylene oxide

 17020

 00075–21–8

 QM = 1

formaldehyde

 17260

 00050–00–0

 SML = 15

hexamethylenediamine ( = 1,6-diaminohexane )

 15274

 00124–09–4

 SML = 2.4

hydrochloric acid

 59990

 07647–01–0

  –

nitrous acid, sodium salt

 86920

 07632–00–0

 SML = 0.6

phosphoric acid

 23170

 07664–38–2

  –

potassium hydroxide

 81600

 01310–58–3

  –

2-propanol

 23830

 00067–63–0

  –

silicic acid

 85680

 01343–98–2

  –

sodium hydroxide

 86720

 01310–73–2

  –

sulphuric acid

 91920

 07664–93–9

  –

Polymerisation aids

alkyl(C8-C22)sulphonic acids

 34230

  –

 SML = 6

alkyl(C8‑C22)sulphuric acids, linear, primary, even

 34281

  –

  –

ammonium hydroxide

 35600

 01336–21–6

  –

carboxymethylcellulose

 42640

 09000–11–7

  –

1,4-dihydroxybenzene

 15940

 00123–31–9

 SML = 0.6

formic acid

 17275

 00064–18–6

  –

gelatine

 55440

 09000–70–8

  –

CM/Del/Dec(97)602

- a45 –

-       

Appendix 12

hydroxyethylcellulose

 60560

 09004–62–0

  –

hydroxyethylmethylcellulose

 60880

 09

  –

magnesium hydroxide

 64640

 01309-42-8

  –

methanol

 21550

 000 67-56-1

  –

methylcarboxymethylcellulose

 66200

 37206-01-2

  –

methylene chloride

 66620

 00075-09-2

 SML = 0.05

methyl isobutyl ketone

 

 SML

tin(IV) chloride

 93420

07646-78-8

  –

toluene

 25205

00108-88-3


                                                                                             

     CM/Del/Dec(97)602                                 - a46 -

             Appendix 12

                                                                     List 2

                      1. Substances not fully evaluated by an international body

                                           (Substances classified in SCF-Lists 6 – 8)

NAME

 PM/REF

 CAS

 RESTRICTIONS (mg/kg)

Monomers and other starting substances

 16690

 01321–74–0

 SML = 0.05

methacrylic acid, diester with ethyleneglycol

 20440

 00097–90–5

  –

methacrylic acid, 2,3-epoxypropyl ester

 20590

 00106–91–2

 QM = 5 ( as epoxy )

methacrylic acid, triester with 1,1,1

 25840

 03290–92–4

  –

2-methyl-1,3-butadiene ( = isoprene )

 21640

 00078–79–5

 SML = 0.05

1,7‑octadiene

 22585

 03710–30–3

  –

1,1,1-trimethylolpropane, diallyl ether

 25645

 00682–09–7

 SML = 0.05

Chemical modifiers

N,N‑dimethyl‑1,3‑diaminopropane

 16225

 00109–55–7

  –

triethylamine

 94270

 00121–44–8

  –

triethylenetetramine

 25520

 00112–24–3

  –

Polymerisation aids

4‑tert.butylcatechol

 40640

 00098–29–3

  –

dibenzoyl peroxide

 46440

 00094–36–0

diisobutyl ketone

 49050

 00108–83–8

  –

hypochlorous acid, sodium salt

 62110

 07681–52–9

 SML = 0.05

4-methoxyphenol ( = hydroquinone, monomethyl ether)

 21615

 00150–76–5

  –

methylenebis(naphtalenesulphonic acid), disodium salt

 66600

 26545–58–4

  –

4-methyl-2-pentanol ( = methylisobutylcarbinol )

 22080

 00108–11–2

  –

2-methyl-1-propanol ( = isobutanol )

 18970

 00078–83–1

  –

polyvinyl acetate, partially hydrolysed

 81260

  –

  –

polyvinyl alcohols

 81280

 09002–89–5

  –

                                                                         - a47 -                    CM/Del/Dec(97)602

                                                                                                                    Appendix 12

                                                                           List 2

                                 2. Substances not evaluated by an international body

                                   (Substances classified in SCF-List 9 or not at all classified)

NAME

 PM/REF

 CAS

 RESTRICTIONS (mg/kg)

Monomers and other starting substances

diethyleneglycol, divinyl ether

  –

 00764–99–8

  –

dimethoxymethane ( = methylal )

 49100

 00109–87–5

  –

ethylvinylbenzene ( 1,2-, 1,3-, and 1,4-isomers )

  –

 28106–30–1

  –

1,2,4-trivinylcyclohexane

  –

 02855–27–8

  –

Chemical modifiers

bromine

  –

 07726–95–6

  –

2-chloroethanol ( = 1-hydroxy-2-chloroethane )

  –

 00107–07–3

  –

chloromethyl methyl ether

  –

 00107–30–2

  –

chlorosulphonic acid

  –

 07790–94–5

  –

1,2-dichloroethane

  –

 00107–06–2

  –

1,2-dichloropropane

  –

 00078–87–5

  –

3‑(dimethylamino)‑1-propanol

  –

 03179–63–3

  –

methyl chloride

  –

 00074–87–3

  –

monchloroacetic acid

  –

 00079–11–8

  –

nitrobenzene

  –

 00098–95–3

  –

nitrous acid, potassium salt

  –

 07758–09–0

  –

phosphorous acid

  –

 13598–36–2

  –

phthalimide

  –

 00085–41–6

  –

sulphur trioxide

  –

 07446–11–9

  –

trimethylamine

  –

 00075–50–3

  –

Polymerisation aids

tert.alkyl(C12-C14)amines, ethoxylated, propoxylated

  –

 68603–58–7

  –

alkyl(C10-C18)mono/di sulfonamides

  –

  –

  –

attapulgite

  –

 12174–11–7

  –

azobisisobutyronitrile

 36615

 00078–67–1

.–

dilauroyl peroxide

  –

 00105‑74‑8

 –

n-dodecyl mercaptan

  –

 00112–55–0

  –

CM/Del/Dec(97)602

    

- a48 -

                   

   Appendix 12

                  

tert.dodecyl mercaptan

  –

 25103–58–6

  –

tert.hexadecyl mercaptan

  –

 25360–09–2

  –

isododecane

 62405

 31807–55‑3

  –

isooctane ( = 2,2,4-trimethylpentane )

  –

 00540–84‑1

  –

lignosulphonic acid

 63940

 08062–15–5

  –

maleic anhydride-styrene copolymer, ammonium salt

  –

 26022–09–3

  –

nitric acid, silver salt

  –

 07761–88–8

  –

n-octane

  –

 00111–65–9

  –

peracetic acid

  –

 00079–21–0

  –

perbenzoic acid, tert.butyl ester

 71750

 00614–45–9

  –

percarbonic acid, bis(4‑tert.butylcyclohexyl) ester

 71796

 15520–11–3

  –

peroctanoic acid, tert.butyl ester

 72020

 13467–82–8

  –

  –

 09003–06–9

  –

 76460

 09003–01–4

  –

poly(diallyldimethylammonium chloride)

  –

 26062–79–3

  –

polyethyleneglycol, octylphenyl ether

78560

 09002–93–1

  –

poly(ethylene/propylene)glycol monobutyl ether

–

 09038-95-3

  –

poly(ethylene/propylene)glycol, 1,1,1,-trimethylolpropyl

–

 52624-57-4

  –

poly(styrenesulphonic acid), sodium salt

–

 09080-79-9

  –

polyvinylpyrrolidone

81500

 09003-37-8

  –


[1]               Association française de normalisation (AFNOR): T 90-601: Traitement des eaux - Résines échangeuses d’ions - Essai de relargage du carbone organique total, Décembre 1988