Bolognesi, Claudia

Castle, Laurence

Cravedi, Jean-Pierre

Croera, Cristina

EFSA Panel on Food Contact Materials Enzymes, Flavourings and Processing Aids (CEF)

Engel, Karl-Heinz

Fowler, Paul

Franz, Roland

Grob, Konrad

Gürtler, Rainer

Husøy, Trine

Kolf-Clauw , Martine

Kärenlampi, Sirpa

Lampi, Eugenia

Mennes, Wim

Milana, Maria Rosaria

Penninks, André

Silano, Vittorio

Smith, Andrew

Svensson, Kettil

Tavares Poças, Maria de Fátima

Tlustos, Christina

Wölfle, Detlef

Zorn, Holger

Zugravu, Corina-Aurelia

EFSA Journal

English

This scientific opinion of the EFSA Panelon Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF Panel) deals with the safety assessment of dimethyl carbonate used as monomer for making a polycarbonate prepolymer with 1,6-hexanediol and then reacted with 4,4-methylenediphenyldiisocyanate (MDI) and diols, such as polypropylene glycol and 1,4-butanediol, to form a thermoplastic polyurethane containing 29% of the polycarbonate prepolymer. This polymer is intended for repeated use articles with short-term contact (30min) at room temperature for types of food, simulated by 10% ethanol and 3% acetic acid. In the third migration test performed at 40 degrees C during 30min, overall migration was below 2mg/dm(2). Complete migration of the residual dimethyl carbonate would have amounted to less than 1.5g/kg food. The migration of two cyclic hexanediol carbonate oligomers was below 50g/kg food when determined by the third migration test; that of all others was below 1g/kg food. Three invitro genotoxicity studies performed in accordance with OECD Guidelines and covering the three endpoints gene mutation, structural and numerical aberrations were provided and were considered negative by the CEF Panel. The oligomers detected by the migration tests are formed from dimethyl carbonate and 1,6-hexanediol (FCM ref No1067) do not give rise to concern for genotoxicity. The CEF Panelconcluded that the use of dimethyl carbonate does not raise safety concern in the application described above. It is aware that dimethyl carbonate may be used for other polycarbonates and/or under other conditions. These are likely to result in different migrates which need to be evaluated by the business operators. In such cases, the migration of dimethyl carbonate and the total polycarbonate oligomers below 1,000Da is of no safety concern, if each of them does not exceed 0.05mg/kg food

Cravedi, Jean Pierre, J. P.

Engel, Karl‐heinz

Zugravu, Corina‐aurelia

Kolf-Clauw, Martine

HAL ENVT (Ecole Nationale Vétérinaire de Toulouse)

Safety assessment of the substance dimethyl carbonate for use in food contact materials

null null

Vittorio Silano

Claudia Bolognesi

Jean‐Pierre Cravedi

Karl‐Heinz Engel

Paul Fowler

Roland Franz

Konrad Grob

Rainer Gürtler

Trine Husøy

Sirpa Kärenlampi

Wim Mennes

Maria Rosaria Milana

André Penninks

Andrew Smith

Maria de Fátima Tavares Poças

Christina Tlustos

Detlef Wölfle

Holger Zorn

Corina‐Aurelia Zugravu

Martine Kolf‐Clauw

Eugenia Lampi

Kettil Svensson

Cristina Croera

Laurence Castle

Crossref

European Food Safety Authority

Engel, Karl‐Heinz

Zugravu, Corina‐Aurelia

Kolf‐Clauw, Martine

ProdInra

HAL Université de Toulouse, et Toulouse INP

The Open University

SCIENTIFIC OPINIONADOPTED: 15 June 2017doi: 10.2903/j.efsa.2017.4901Safety assessment of the substance dimethyl carbonate foruse in food contact materialsEFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF),Vittorio Silano, Claudia Bolognesi, Jean-Pierre Cravedi, Karl-Heinz Engel, Paul Fowler,Roland Franz, Konrad Grob, Rainer G€urtler, Trine Husøy, Sirpa K€arenlampi, Wim Mennes,Maria Rosaria Milana, Andre Penninks, Andrew Smith, Maria de Fatima Tavares Pocas,Christina Tlustos, Detlef W€olﬂe, Holger Zorn, Corina-Aurelia Zugravu, Martine Kolf-Clauw,Eugenia Lampi, Kettil Svensson, Cristina Croera and Laurence CastleAbstractThis scientiﬁc opinion of the EFSA Panel on Food Contact Materials, Enzymes, Flavourings and ProcessingAids (CEF Panel) deals with the safety assessment of dimethyl carbonate used as monomer for making apolycarbonate prepolymer with 1,6-hexanediol and then reacted with 4,40-methylenediphenyldiisocyanate(MDI) and diols, such as polypropylene glycol and 1,4-butanediol, to form a thermoplasticpolyurethane containing 29% of the polycarbonate prepolymer. This polymer is intended for repeateduse articles with short-term contact (≤ 30 min) at room temperature for types of food, simulated by10% ethanol and 3% acetic acid. In the third migration test performed at 40°C during 30 min, overallmigration was below 2 mg/dm2. Complete migration of the residual dimethyl carbonate would haveamounted to less than 1.5 lg/kg food. The migration of two cyclic hexanediol carbonate oligomerswas below 50 lg/kg food when determined by the third migration test; that of all others was below1 lg/kg food. Three in vitro genotoxicity studies performed in accordance with OECD Guidelines andcovering the three endpoints gene mutation, structural and numerical aberrations were provided andwere considered negative by the CEF Panel. The oligomers detected by the migration tests are formedfrom dimethyl carbonate and 1,6-hexanediol (FCM ref No 1067) do not give rise to concern forgenotoxicity. The CEF Panel concluded that the use of dimethyl carbonate does not raise safetyconcern in the application described above. It is aware that dimethyl carbonate may be used for otherpolycarbonates and/or under other conditions. These are likely to result in different migrates whichneed to be evaluated by the business operators. In such cases, the migration of dimethyl carbonateand the total polycarbonate oligomers below 1,000 Da is of no safety concern, if each of them doesnot exceed 0.05 mg/kg food.© 2017 European Food Safety Authority. EFSA Journal published by John Wiley and Sons Ltd on behalfof European Food Safety Authority.Keywords: dimethyl carbonate, CAS number 616-38-6, FCM materials No 1067, Food contactmaterials, Safety assessmentRequestor: Bundesamt f€ur Verbraucherschutz und Lebensmittelsicherheit, GermanyQuestion number: EFSA-Q-2015-00832Correspondence: ﬁp@efsa.europa.euEFSA Journal 2017;15(7):4901www.efsa.europa.eu/efsajournalPanel members: Claudia Bolognesi, Laurence Castle, Jean-Pierre Cravedi, Karl-Heinz Engel, PaulFowler, Roland Franz, Konrad Grob, Rainer G€urtler, Trine Husøy, Sirpa K€arenlampi, Wim Mennes, MariaRosaria Milana, Andre Penninks, Vittorio Silano, Andrew Smith, Maria de Fatima Tavares Pocas,Christina Tlustos, Detlef W€olﬂe, Holger Zorn and Corina-Aurelia Zugravu.Suggested citation: EFSA CEF Panel (EFSA Panel on Food Contact Materials, Enzymes, Flavouringsand Processing Aids, Silano V, Bolognesi C, Cravedi J-P, Engel K-H, Fowler P, Franz R, Grob K, G€urtlerR, Husøy T, K€arenlampi S, Mennes W, Milana MR, Penninks A, Smith A, Tavares Pocas MF, Tlustos C,W€olﬂe D, Zorn H, Zugravu C-A, Kolf-Clauw M, Lampi E, Svensson K, Croera C and Castle L, 2017.Scientiﬁc Opinion on the safety assessment of the substance dimethyl carbonate, for use in foodcontact materials. EFSA Journal 201715(7):4901, 7 pp. https://doi.org/10.2903/j.efsa.2017.4901ISSN: 1831-4732© 2017 European Food Safety Authority. EFSA Journal published by John Wiley and Sons Ltd on behalfof European Food Safety Authority.This is an open access article under the terms of the Creative Commons Attribution-NoDerivs License,which permits use and distribution in any medium, provided the original work is properly cited and nomodiﬁcations or adaptations are made.The EFSA Journal is a publication of the European FoodSafety Authority, an agency of the European Union.Safety assessment of dimethyl carbonatewww.efsa.europa.eu/efsajournal 2 EFSA Journal 2017;15(7):4901Table of contentsAbstract.................................................................................................................................................... 11. Introduction...................................................................................................................................... 41.1. Background and Terms of Reference as provided by the requestor........................................................ 42. Data and methodologies .................................................................................................................... 42.1. Data................................................................................................................................................. 42.2. Methodologies................................................................................................................................... 43. Assessment....................................................................................................................................... 53.1. Non-toxicological data ....................................................................................................................... 53.2. Toxicological data .............................................................................................................................. 64. Conclusions....................................................................................................................................... 6Documentation provided to EFSA ............................................................................................................... 6References................................................................................................................................................ 7Abbreviations ............................................................................................................................................ 7Safety assessment of dimethyl carbonatewww.efsa.europa.eu/efsajournal 3 EFSA Journal 2017;15(7):49011. Introduction1.1. Background and Terms of Reference as provided by the requestorBefore a substance is authorised to be used in food contact materials (FCM) and is included in apositive list, EFSA’s opinion on its safety is required. This procedure has been established in Articles 8,9 and 10 of the Regulation (EC) No 1935/20041 of the European Parliament and of the Council of 27October 2004 on materials and articles intended to come into contact with food.According to this procedure, the industry submits applications to the Member States’ competentauthorities which transmit the applications to the European Food Safety Authority (EFSA) for evaluation.In this case, EFSA received an application from the Bundesamt f€ur Verbraucherschutz undLebensmittelsicherheit, Germany, requesting the evaluation of the substance dimethyl carbonate foruse as monomer in FCMs, with the CAS number 616-38-6 and the FCM substance No 1067.According to Regulation (EC) No 1935/2004, of the European Parliament and of the Council onmaterials and articles intended to come into contact with food EFSA is asked to carry out anassessment of the risks related to the intended use of the substance and to deliver a scientiﬁc opinion.2. Data and methodologies2.1. DataThe applicant has submitted a dossier in support of their application for the authorisation ofdimethyl carbonate as monomer to be used in FCM.Data submitted and used for the evaluation are:Non-toxicological data and information• Chemical identity• Description of manufacturing process of the substance• Physical and chemical properties• Intended use• Existing authorisation(s)• Migration of the substance• Residual content of the substance• Oligomers• Identiﬁcation, quantiﬁcation and migration of reaction products and impuritiesToxicological data• Bacterial gene mutation test• In vitro mammalian cell gene mutation test• In vitro mammalian chromosome aberration test2.2. MethodologiesThe assessment was conducted in line with the principles laid down in Regulation (EC) No 1935/2004on materials and articles intended to come into contact with food. This Regulation underlines thatapplicants may consult the Guidelines of the Scientiﬁc Committee on Food (SCF) for thepresentation of an application for safety assessment of a substance to be used in FCM prior to itsauthorisation (European Commission, 2001), including the corresponding data requirements. Thedossier that the applicant submitted for evaluation was in line with the SCF guidelines (EuropeanCommission, 2001).The methodology is based on the characterisation of the substance that is the subject of therequest for safety assessment prior to authorisation, its impurities and reaction and degradationproducts, the evaluation of the exposure to those substances through migration, and the deﬁnition ofminimum sets of toxicity data required for safety assessment.To establish the safety from ingestion of migrated substances, the toxicological data indicating thepotential hazard and the likely human exposure data need to be combined. Exposure is estimated from1 Regulation (EC) No 1935/2004 of the European parliament and of the council of 27 October 2004 on materials and articlesintended to come into contact with food and repealing Directives 80/590/EEC and 89/109/EEC. OJ L 338, 13.11.2004, p. 4–17.Safety assessment of dimethyl carbonatewww.efsa.europa.eu/efsajournal 4 EFSA Journal 2017;15(7):4901studies on migration into food or food simulants, and considering that a person may consume daily upto 1 kg of food in contact with the relevant FCM.As a general rule, the greater the exposure through migration, the more toxicological data isrequired for the safety assessment of a substance. Currently, there are three tiers with differentthresholds triggering the need for toxicological information as following:a) In case of high migration (i.e. 5–60 mg/kg food), an extensive data set is needed;b) In case of migration between 0.05 and 5 mg/kg food, a reduced data set may sufﬁce;c) In case of low migration (i.e. < 0.05 mg/kg food), only a limited data set is needed.More detailed information on the required data is available in the SCF guidelines (EuropeanCommission, 2001).The assessment was conducted in line with the principles described in the EFSA Guidance ontransparency in the scientiﬁc aspects of risk assessment (EFSA, 2009) and considering the relevantguidance from the EFSA Scientiﬁc Committee.3. AssessmentAccording to the applicant, dimethyl carbonate was reacted with 1,6-hexanediol to 1,6-hexanediol-polycarbonate. This prepolymer was then reacted with 4,40-methylenediphenyldiisocyanate (MDI) anddiols, such as polypropylene glycol and 1,4-butanediol, to form a thermoplastic polyurethane (TPU).The TPU is intended for repeated use articles used at ambient temperature for short times (≤ 30 min)and in contact with foods for which 3% acetic acid and 10% ethanol are speciﬁed as simulants (EUReg. No 10/2011).2The applicant limited the scope of use of the substance to this formulation. No data are available toindicate if this formulation can be considered to be a representative example or a ‘worse case’compared to other potential uses.The use of dimethyl carbonate has not been evaluated by EFSA or the SCF for food contactmaterials in the past.3.1. Non-toxicological dataChemical formula: C3H6O3Chemical structure:Molecular weight = 90 DaDimethyl carbonate is a liquid with a boiling point of 90°C. The substance used by the applicanthad a purity of 99%, with methanol and water being the principal impurities. It was made frompropylene oxide and CO2; the resulting propylene carbonate was reacted with methanol in combinationwith sodium methoxide as a catalyst to produce dimethyl carbonate and propylene glycol. There are,however, also other methods of synthesis. Solubility in water at 20°C exceeds 100 g/L; the log Po/wwas calculated as 0.23.The substance was used to make a prepolymer with 1,6-hexanediol in a molar ratio close to 1:1,which was then reacted with MDI, polypropylene glycol and 1,4-butanediol to the corresponding TPU.The prepolymer made up about 30% of the TPU.Overall, migration from this TPU sample (sheets of 1 cm thickness) into 3% acetic acid and 10%ethanol under repeated use conditions, during 30 min at 40°C, was below 2 mg/dm2 in the thirdmigration test.The speciﬁc migration of dimethyl carbonate was not measured. The residual content in thepolycarbonate prepolymer was below the detection limit of 0.2 mg/kg prepolymer. Assuming aproportion of 50% prepolymer in the polyurethane, 6 dm2/kg food contact surface and a thickness ofthe article of 0.25 mm from which all residual dimethyl carbonate migrates into food, the calculatedmigration was less than 1.5 lg/kg food.2 Commission Regulation (EU) No 10/2011 of 14 January 2011 on plastic materials and articles intended to come into contactwith food. Available online: http://eur-lex.europa.eu/legal-content/EN/TXT/HTML/?uri=CELEX:32011R0010&from=ENSafety assessment of dimethyl carbonatewww.efsa.europa.eu/efsajournal 5 EFSA Journal 2017;15(7):4901In the third migration test, the concentrations of cyclic oligomeric hexanediol carbonates with n = 2(MW = 288 Da) and n = 3 (MW = 432 Da) from the TPU in 3% acetic acid amounted to 33 and 6 lg/kg,respectively, that in 10% ethanol to 42 and 15 lg/kg, respectively. The migration of the oligomer n = 4(MW = 576 Da) was below the limit of quantiﬁcation of 0.7 lg/kg. The migration of other oligomericreaction products incorporating the substance that had been identiﬁed in a 95% ethanol extract wasbelow the detection limit. Other substances were found to migrate, but did not originate from thepolycarbonate prepolymer and, therefore, were not considered.3.2. Toxicological dataDimethyl carbonate was tested for genotoxicity in three adequately performed in vitro tests,according to OECD guidelines, in the presence and absence of metabolic activation up to therecommended maximum test concentrations.The substance (purity 99.9%) dissolved in dimethyl sulfoxide (DMSO), was tested for mutagenicityusing the pre-incubation assay in Salmonella Typhimurium strains TA98, TA100, TA1535, TA1537 andEscherichia coli WP2uvrA, at concentrations up to 5,000 lg/plate. No signiﬁcant increases in thefrequency of revertant colonies were recorded for any of the bacterial strains, with any concentrationof the test compound.In an in vitro gene mutation assay carried out in mammalian cells (Chinese hamster V79 HPRTlocus), the substance (purity not reported), dissolved in water up to a concentration of 10 mM, did notreveal any mutagenic response.The substance (purity not reported) tested for chromosomal aberrations in human lymphocytes upto the concentration of 10 mM (in water) did not show any induction of chromosomal damage.Based on the results of these three tests, the substance does not give rise to concern for genotoxicity.The oligomers detected by the migration tests are formed from dimethyl carbonate and 1,6-hexanediol (FCM ref No. 18700) and based on the knowledge of their structures, they do not give riseto concern for genotoxicity.4. ConclusionsBased on the above-mentioned data, the EFSA Panel on Food Contact Materials, Enzymes,Flavourings and Processing Aids (CEF Panel) concluded that there is no safety concern for the use ofdimethyl carbonate described by the applicant, when:• used with 1,6-hexanediol in the manufacture of polycarbonate prepolymers• this prepolymer is used at up to 30% to make a thermoplastic polyurethane with MDI anddiols, such as polypropylene glycol and 1,4-butanediol• applied in repeated use articles intended for contact with foods for which 3% acetic acid and10% ethanol are speciﬁed as simulants and under contact conditions covered by simulationduring 30 min at 40°CThe CEF Panel is aware that dimethyl carbonate may be used for other polycarbonates and/orunder other conditions. These are likely to result in different migrates which need to be evaluated bythe business operators. In such cases, the migration of dimethyl carbonate and total polycarbonateoligomers below 1,000 Da is of no safety concern, if each of them does not exceed 0.05 mg/kg food.Documentation provided to EFSA1) Dossier “Dimethyl carbonate” for use as monomer in plastics. December 2015. Submitted byWTConsulting GmbH on behalf of Covestro Deutschland AG.2) Additional data for dossier “Dimethyl carbonate”. April 2016. Submitted by WTConsultingGmbH on behalf of Covestro Deutschland AG.3) Additional data for dossier “Dimethyl carbonate”. July 2016. Submitted by WTConsultingGmbH on behalf of Covestro Deutschland AG.4) Additional data for dossier “Dimethyl carbonate”. April 2017. Submitted by WTConsultingGmbH on behalf of Covestro Deutschland AG.Safety assessment of dimethyl carbonatewww.efsa.europa.eu/efsajournal 6 EFSA Journal 2017;15(7):4901ReferencesEFSA (European Food Safety Authority) Scientiﬁc Committee, 2009. Guidance of the Scientiﬁc Committee ontransparency in the scientiﬁc aspects of risk assessments carried out by EFSA. Part 2: general principles. EFSAJournal 2009;7(5):1051, 22 pp. https://doi.org/10.2903/j.efsa.2009.1051European Commission, 2001. Guidelines of the Scientiﬁc Committee on Food for the presentation of an applicationfor safety assessment of a substance to be used in food contact materials prior to its authorisation. Availableonline: https://ec.europa.eu/food/sites/food/ﬁles/safety/docs/sci-com_scf_out82_en.pdfAbbreviationsCAS Chemical Abstracts ServiceCEF Panel EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing AidsDa DaltonDMSO dimethyl sulfoxideFCM food contact materialsMDI 4,40-methylenediphenyldiisocyanatePo/w octanol/water partition coefﬁcientSCF Scientiﬁc Committee on FoodTPU thermoplastic polyurethaneSafety assessment of dimethyl carbonatewww.efsa.europa.eu/efsajournal 7 EFSA Journal 2017;15(7):4901

HAL: Hyper Article en Ligne

Abstract This scientific opinion of the EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF Panel) deals with the safety assessment of dimethyl carbonate used as monomer for making a polycarbonate prepolymer with 1,6‐hexanediol and then reacted with 4,4′‐methylenediphenyldiisocyanate (MDI) and diols, such as polypropylene glycol and 1,4‐butanediol, to form a thermoplastic polyurethane containing 29% of the polycarbonate prepolymer. This polymer is intended for repeated use articles with short‐term contact (≤ 30 min) at room temperature for types of food, simulated by 10% ethanol and 3% acetic acid. In the third migration test performed at 40°C during 30 min, overall migration was below 2 mg/dm2. Complete migration of the residual dimethyl carbonate would have amounted to less than 1.5 μg/kg food. The migration of two cyclic hexanediol carbonate oligomers was below 50 μg/kg food when determined by the third migration test; that of all others was below 1 μg/kg food. Three in vitro genotoxicity studies performed in accordance with OECD Guidelines and covering the three endpoints gene mutation, structural and numerical aberrations were provided and were considered negative by the CEF Panel. The oligomers detected by the migration tests are formed from dimethyl carbonate and 1,6‐hexanediol (FCM ref No 1067) do not give rise to concern for genotoxicity. The CEF Panel concluded that the use of dimethyl carbonate does not raise safety concern in the application described above. It is aware that dimethyl carbonate may be used for other polycarbonates and/or under other conditions. These are likely to result in different migrates which need to be evaluated by the business operators. In such cases, the migration of dimethyl carbonate and the total polycarbonate oligomers below 1,000 Da is of no safety concern, if each of them does not exceed 0.05 mg/kg food

EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF)

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Safety assessment of the substance dimethyl carbonate for use in food contact materials

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