SVHC-59 甲醛与苯胺的低聚反应产物 Technical_mda_en(C 致癌)

SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE 1 9 December 2011 Substance Name(s): Formaldehyde, oligomeric reaction products with aniline EC Number: 500-036-1 CAS Number: 25214-70-4 SUPPORT DOCUMENT FOR IDENTIFICATION OF FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE AS A SUBSTANCE OF VERY HIGH CONCERN BECAUSE OF ITS CMR PROPERTIES SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE 2 SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE 3 NOTE During the public consultation, in accordance with Article 59 (4) of the REACH Regulation, on the proposed identification of “formaldehyde, oligomeric reaction products with aniline” as a Substance of Very High Concern (SVHC) on the basis of its classification as carcinogenic category 1B no comments were received objecting the conclusion that the substance meets criteria set out in Article 57(a). Therefore, in accordance with Article 59 (6), “formaldehyde, oligomeric reaction products with aniline” has been included in the Candidate List by ECHA. The present support document comprises Part I (Justification) of the Annex XV dossier for identification of “formaldehyde, oligomeric reaction products with aniline” as SVHC on the basis of Article 57(a) of REACH. SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE 4 CONTENTS JUSTIFICATION .........................................................................................................................................................6 1 IDENTITY OF THE SUBSTANCE AND PHYSICAL AND CHEMICAL PROPERTIES .................................6 1.1 Name and other identifiers of the substance ...................................................................................................6 1.2 Composition of the substance .........................................................................................................................7 1.3 Physico-chemical properties ...........................................................................................................................8 2 HARMONISED CLASSIFICATION AND LABELLING....................................................................................9 3 ENVIRONMENTAL FATE PROPERTIES...........................................................................................................10 4 HUMAN HEALTH HAZARD ASSESSMENT.....................................................................................................10 5 ENVIRONMENTAL HAZARD ASSESSMENT ..................................................................................................10 6 CONCLUSIONS ON THE SVHC PROPERTIES .................................................................................................10 6.1 PBT, vPvB assessment ...................................................................................................................................10 6.2 CMR assessment.............................................................................................................................................10 6.3 Substances of equivalent level of concern assessment ...................................................................................10 REFERENCES .............................................................................................................................................................11 ABBREVIATIONS ......................................................................................................................................................12 TABLES Table 1: Substance identity...........................................................................................................................................6 Table 2: Generic composition (based on registration dossiers received)......................................................................7 Table 3: Overview of physicochemical properties .......................................................................................................8 Table 4: Classification for MDA according to part 3 of Annex VI, Table 3.1 (List of harmonised classification and labelling of hazardous substances) of Regulation (EC) No 1272/2008 ........................................................................9 Table 5: Classification for MDA according to part 3 of Annex VI, Table 3.2 (list of harmonised classification and labelling of hazardous substances from Annex I of Council Directive 67/548/EEC) of Regulation (EC) No 1272/2008 9 FIGURES Figure 1: Structural formula with n = 1-5 (according to registration dossiers received) and eu = either unknown......7 SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE 5 Substance Name(s): Formaldehyde, oligomeric reaction products with aniline EC Number: 500-036-1 CAS number: 25214-70-4 • The substance is proposed to be identified as substance meeting the criteria of Article 57 (a) of Regulation (EC) 1907/2006 (REACH) owing to its classification as carcinogen 1 B1 which corresponds to classification as carcinogen category 22.. Summary of how the substance(s) meet(s) the CMR (Cat 1A or 1B) criteria The structurally related substance 4,4’-diaminodiphenylmethane is listed by index number 612-051- 00-1 of Regulation (EC) No 1272/2008 and classified in Annex VI, part 3, Table 3.1 (the list of harmonised classification and labelling of hazardous substances) as carcinogenic: Carc. 1B (H 350: “May cause cancer.”). The corresponding classification in Annex VI, part 3, Table 3.2 (the list of harmonised and classification and labelling of hazardous substances from Annex I to Directive 67/548/EEC) of Regulation (EC) No 1272/2008 is Carc. Cat. 2; R45 (“May cause cancer.”). 4,4’-diaminodiphenylmethane is a major constituent of the UVCB substance formaldehyde, oligomeric reaction products with aniline (CAS-No. 25214-70-4) and therefore the classification for 4,4’-diaminodiphenylmethane applies also for this UVCB substance. The classification of ,4’-diaminodiphenylmethane in Regulation (EC) No 1272/2008 shows that also the UVCB substance formaldehyde, oligomeric reaction products with aniline meets the criteria for classification as carcinogenic in accordance with Article 57 (a) of REACH. Registration dossiers submitted for the substance? Yes 1 Classification in accordance with Regulation (EC) No 1272/2008 Annex VI, part 3, Table 3.1 List of harmonised classification and labelling of hazardous substances. 2 Classification in accordance with Regulation (EC) No 1272/2008, Annex VI, part 3, Table 3.2 List of harmonised classification and labelling of hazardous substances (from Annex I to Council Directive 67/548/EEC). SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE 6 JUSTIFICATION 1 IDENTITY OF THE SUBSTANCE AND PHYSICAL AND CHEMICAL PROPERTIES 1.1 Name and other identifiers of the substance Table 1: Substance identity EC number: 500-036-1 EC name: Formaldehyde, oligomeric reaction products with aniline CAS number (in the EC inventory): 25214-70-4 CAS number: 25214-70-4 CAS name: Formaldehyde, polymer with benzenamine IUPAC name: Formaldehyde, oligomeric reaction products with aniline Index number in Annex VI of the CLP Regulation - Molecular formula: (C6H7N.CH2O)x Molecular weight range: > 168 g/mol Synonyms: polymeric MDA3 PMDA MDA, technical grade crude MDA 3 In Kirk-Othmer [1991] the substance is named polymeric MDA and this name is used in this dossier to refer to Formaldehyde, oligomeric reaction products with aniline. The name is abbreviated as PMDA. SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE 7 Structural formula: Figure 1: Structural formula with n = 1-5 (according to registration dossiers received) and eu = either unknown 1.2 Composition of the substance Name: Formaldehyde, oligomeric reaction products with aniline Description: Degree of purity: 100% Formaldehyde, oligomeric reaction product with aniline (Technical-grade MDA) is a UVCB substance with a varying content of tri- and polynuclear amines (so-called „polymers“). A typical standard product with a content of 4,4'-MDA between ca. 47 and < 65 %(w/w) is liquid at room temperature and comprises the following: Table 2: Generic composition (based on registration dossiers received) Impurity Content range4 % w/w CAS no. EC no. Molecular formular 4,4'-MDA ca. 47 to < 65 101-77-9 202-974-4 C13H14N2 2,4’-MDA < 1.4 to ca. 10 1208-52-2 214-900-8 C13H14N2 2,2’-MDA ca. 0.2 to 3 6582-52-1 229-512-4 C13H14N2 Higher Oligomers of MDA ca. 38.4 to < 65 - - (C6H7N)2 (CH2)(x + 1)(C6H6N)x or C(7x+13)H(6x+13)N(x+2) Water < 1 7732-18-5 231-791-2 H2O Aniline < 0.1 62-53-3 200-539-3 C6H7N The separate identities indicated in the registration dossiers received are confidential and were included in the technical dossier. 4 Based on registration dossiers received SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE 8 1.3 Physico-chemical properties Table 3: Overview of physicochemical properties5 Property Value Remarks Physical state at 20°C and 101.3 kPa olig. MDA is a yellow, clear, high viscous liquid/wax Melting/freezing point 30 — 70 °C Boiling point 410.6 °C at 1013.25 hPa Vapour pressure < 0.000001 hPa; 20 °C 0.000016 hPa; 50 °C Water solubility 0.36 g/L, Temp. 20 °C; pH 7.1 — 7.4; Remarks: 1 g test item per one liter of water 1.22 g/L, Temp. 20 °C; pH 7.5 — 7.6 Remarks: 10 g test item per one liter of water Partition coefficient n-octanol/water (log value) 1.3 - 2.5 at 23°C/pH = 6.2 1.2 -2.7 at 23°C/pH = 10 Key value for chemical safety assessment: Log Kow (Log Pow) 2.5, 23 °C Dissociation constant The test item consists of substances with a number of different amine groups. For each of these groups a discrete dissociation constant can be defined, but not determined by titration. The determination of the dissociation constant of an aqueous preparation of the test item is not possible. 5 The references of the values reported in Table 3 will be available in the technical dossier. In case references need to be included an additional column could be added manually in Table 3. SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE 9 2 HARMONISED CLASSIFICATION AND LABELLING The UVCB substance formaldehyde, oligomeric reaction products with aniline is covered by the entry of 4,4’-diaminodiphenylmethane under index number 612-051-00-1 in Annex VI, Part 3 of Regulation (EC) No 1272/2008. as provided in Table 4 and Table 5. Table 4: Classification for MDA according to part 3 of Annex VI, Table 3.1 (List of harmonised classification and labelling of hazardous substances) of Regulation (EC) No 1272/2008 Classification Labelling International Chemical Identification EC No CAS No Hazard Class and Category Code(s) Hazard Statement Code(s) Pictogram, Signal Word Code(s) Hazard statement Code(s) Suppl. Hazard statement Code(s) Specific Conc. Limits, M-factors Notes 4,4'-diamino- diphenylmethane; 4,4'-methylene- dianiline 202-974-4 101-77-9 Carc. 1B Muta. 2 STOT SE 1 STOT RE 2 * Skin Sens. 1 Aquatic Chronic 2 H350 H341 H370 ** H373 ** H317 H411 GHS08 GHS07 GHS09 Dgr H350 H341 H370 ** H373 ** H317 H411 Table 5: Classification for MDA according to part 3 of Annex VI, Table 3.2 (list of harmonised classification and labelling of hazardous substances from Annex I of Council Directive 67/548/EEC) of Regulation (EC) No 1272/2008 Index No Chemical name Notes related to substances EC No CAS No Classification Labelling Concen- tration Limits Notes related to preparations ANNEX 1 612-051-00-1 4,4'-diamino- diphenylmethane; 4,4'-methylene- dianiline 202-974-4 101-77-9 Carc. Cat. 2; R45 Muta. Cat. 3; R68 T; R39/23/24/25 Xn; R48/20/21/22 R43 N; R51-53 R: 45- 39/23/24/2 5-43- 48/20/21/2 2-68-51/53 S: 53-45- 61 SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE Page 10 of 12 3 ENVIRONMENTAL FATE PROPERTIES Not relevant for the identification of the substance as SVHC in accordance with Article 57(a). 4 HUMAN HEALTH HAZARD ASSESSMENT Not relevant for the identification of the substance as SVHC in accordance with Article 57(a). 5 ENVIRONMENTAL HAZARD ASSESSMENT Not relevant for the identification of the substance as SVHC in accordance with Article 57(a). 6 CONCLUSIONS ON THE SVHC PROPERTIES 6.1 PBT, vPvB assessment Not relevant 6.2 CMR assessment The structurally related substance 4,4’-diaminodiphenylmethane is listed by index number 612-051- 00-1 of Regulation (EC) No 1272/2008 and classified in Annex VI, part 3, Table 3.1 (the list of harmonised classification and labelling of hazardous substances) as carcinogenic: Carc. 1B (H 350: “May cause cancer.”). The corresponding classification in Annex VI, part 3, Table 3.2 (the list of harmonised and classification and labelling of hazardous substances from Annex I to Directive 67/548/EEC) of Regulation (EC) No 1272/2008 is Carc. Cat. 2; R45 (“May cause cancer.”). 4,4’-diaminodiphenylmethane is a major constituent of the UVCB substance formaldehyde, oligomeric reaction products with aniline (CAS-No. 25214-70-4) and therefore the classification for 4,4’-diaminodiphenylmethane applies also for this UVCB substance. The classification of ,4’-diaminodiphenylmethane in Regulation (EC) No 1272/2008 shows that also the UVCB substance formaldehyde, oligomeric reaction products with aniline meets the criteria for classification as carcinogenic in accordance with Article 57 (a) of REACH. 6.3 Substances of equivalent level of concern assessment Not relevant SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE Page 11 of 12 REFERENCES ECHA report (2008): Data on manufacture, import, export, uses and releases of 4,4’-diaminodiphenylmethane as well as information on potential alternatives to its use (specific contract ECHA/2008/02/SR5/ECA.227). ECHA website, 22.08.2011: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9d99d110-026b-3a79-e044- 00144f67d249/AGGR-5f11a3d8-0a0f-4285-9924-40641866f705_DISS-9d99d110-026b-3a79-e044- 00144f67d249.html#AGGR-5f11a3d8-0a0f-4285-9924-40641866f705 Kirk-Othmer (Edt.,1991): Encyclopedia of Chemical Technology, Vol. 2, 4th Ed., New York, John Wiley, pp. 461–473. SVHC SUPPORT DOCUMENT – FORMALDEHYDE, OLIGOMERIC REACTION PRODUCTS WITH ANILINE Page 12 of 12 ABBREVIATIONS ECB (Ex-)European Chemicals Bureau. ERB exposure-risk-relationship LOQ limit of quantification T25 tumourigenic dose at which 25 % additional incidence is expected tpa tons per anno UVCB substances substances of unknown or, variable, complex composition or biological origin