Restricted Chemical Substances. Version

Transcription

1 Restricted Chemical Substances Version

2 Safe handling of chemical substances Environmental measures shall be taken throughout the chain. Chemical substances and preparations shall be carefully managed according to the requirements below. SUPPLIER REQUIREMENTS List of all chemicals used in the Suppliers shall establish and maintain a list of all chemical substances and preparations used in the process and maintenance of equipment. The list shall include the name of the chemical product, the purpose/area of use and a reference to a Material Safety Data Sheet (MSDS). Written policy Suppliers shall have a written procedure for the procurement, storage, handling and use of chemicals, including guidelines on safe handling and use of different chemicals, with specific emphasis on hazardous chemicals. Suppliers shall in addition appoint a responsible person in charge of implementing measures in accordance with these requirements. Competence and Training Suppliers must ensure that the risk associated with each chemical substance is assessed, understood and communicated to all employees. Employees that procure, store, handle and use chemicals must have the right competence and be sufficiently trained to take necessary measures for safe handling and use; records from training shall be kept. Storage Supplier shall prevent chemicals from leaking to air, ground and water. Chemical storage areas may require specific design and equipment regarding construction materials, lighting, ventilation and fire extinguishers. It shall include first aid and eyewash equipment. Additional requirements apply to chemicals that are classified as flammable or combustible liquids. Storage space for liquid chemicals shall be free of drainage holes and protected by sills. Hazardous Waste Disposal Supplier shall have a policy for disposing hazardous waste materials. Hazardous waste must not be allowed to accumulate, and hazardous waste collection must be arranged through certified firms. The frequency of collection is dependent upon the type and amount of waste generated. Supplier shall keep a record of all waste collections. Restricted Chemical Substances version

3 List of restricted substances The use of chemicals in the of goods is regulated according to the Restricted Chemical Substances List. The list is divided according to the following stages: pre-treatment; dyeing and printing; finishing treatment and sundry, and other factors of importance. Please note that some chemical substances may be used in several stages; however, they are only listed once. TABLE EXPLANATION Table categories description PRODUCTION STAGE CHEMICAL TYPE FAMILY OF CHEMICAL SUBSTANCES Name of the Restricted Substance (Synonym(s) and/or alternative name(s)) CAS No (*) Legal regulations Children < 3 yrs Recommended restrictions Max. concentration value allowed Adults & children > 3 yrs Recommended restrictions Max. concentration value allowed Test method Comments (*) The CAS No states the identification number for the substance or group of substances according to Chemical Abstract Service. The sign ++ means that there may be several substances and CAS numbers covered by the specification. Stated numbers are examples of substances covered. Symbol explanation Legal restrictions exist within Norway and/or the EU that regulate the use of the substance. The substance shall not be used in the. The substance shall not be used in the and is not allowed as additive. The list states a maximum acceptable concentration limit since there may be some unintended contamination of raw materials in the. Restricted Chemical Substances version

4 Comment to and : The restrictions does apply to intentionally addition of the actual substance. Low, trace concentrations of contaminants which are not intentionally added, will be accepted. However, the manufacturer shall work to avoid such contaminants. For some substances, no contamination is accepted above the analytical detection limit; for instance for chromium(vi). The substance can be used within the limits allowed. For babies and children s clothing, lower limits than those stated may be recommended. A fact sheet explaining the harmful health and environmental effects of the substance, its main use, legal regulations and standard test methods is available. The substance is listed on ECHA s candidate list of substances of very high concern for authorisation. Candidate for listing in Annex XIV to European REACH regulation on chemicals. The substance is listed in Annex XIV to European REACH regulation on chemicals, and cannot be used Europe without specific authorisation after a sunset period that ends in 2014 or Restricted Chemical Substances version

5 FAMILY OF CHEMICALS NAME OF SUBSTANCES CAS No. LEGAL REGULATIONS REQUIREMENTS CHILDREN < 3 YRS ADULTS & CHILDREN > 3 YRS TEST METHODS COMMENTS PRETREATMENT EMULGATORS / DISPERSING AGENTS ALKYLPHENOL ETHOXYLATES (APEO) Nonionic tensides. May be used in detergents and cleaning agents. Nonylphenol ethoxylates; 4-Nonylphenol, branched and linear, ethoxylated [substances with a linear and/or branched alkyl chain with a carbon number of 9 covalently bound in position 4 to phenol, ethoxylated covering UVCB- and well-defined substances, polymers and homologues, which include any of the individual isomers and/or combinations thereof] (NPEO; Nonylphenol polyethylene glycol ether; Nonylphenoxy polyethoxy ethanol) 2-[2-(Nonylphenoxy)ethoxy]-ethanol α-4-nonylphenyl-ω -hydroxy-poly(oxy-1,2- ethanediyl) α-nonylphenyl-ω-hydroxy-poly(oxy-1,2- ethanediyl) 2-[2-[2-[2-(4-Nonylphenoxy)ethoxy]ethoxy]- ethanol 2-[2-[2-[2-(4-Nonylphenoxy)ethoxy]ethoxy]- ethanol, branched 2-(Isononylphenoxy)-ethanol 4-Nonylphenol, branched and linear [substances with a linear and/or branched alkyl chain with a carbon number of 9 covalently bound in position 4 to phenol, covering also UVCB- and welldefined substances which include any of the individual isomers or a combination thereof] (Nonylphenol (decomposition product)) Isononylphenol EU REACH Annex XVII, 46 (a & b): Shall not be placed on the market, or used, as substances or in mixtures in concentrations equal to or greater than 0,1 % by weight for the following purposes: (3) textiles and leather processing except: processing with no release into waste water, systems with special treatment where the process water is pre-treated to remove the organic fraction completely prior to biological waste water treatment (degreasing of sheepskin); Max. acceptable concentration: 100 ppm (100 mg/kg) (Long term goal: Max. 30 ppm (30 mg/kg)) Shall not be used in the Solvent extraction (normally dichloromethane or methanol) followed by LC-MS, GC-MS, Reversed-phase HPLC-MS or LC-DAD (diode array detector) Sweden (July 2013), REACH restriction proposal: Textile clothing, fabric accessories and interior textile articles that can be washed in water shall not be placed on the market if they contain nonylphenol or nonylphenol ethoxylate alone or in combination in concentration equal or higher than 100 mg/kg textile. Restricted Chemical Substances version

6 Nonylphenol, branched 4-Nonyl-phenol, branched p-isononylphenol Octylphenol ethoxylates Octylphenol (decomposition product) ((1,1,3,3-Tetramethylbutyl)-phenol) α-sulfo-omega-(nonylphenoxy)-poly(oxy-1,2- ethanediyl) ammonium salt α-[4-(1,1,3,3-tetramethylbutyl)phenyl]-omegahydroxy-poly(oxy-1,2-ethanediyl) Other alkylphenol ethoxylates ++ QUARTERNARY AMMONIUM SALTS Used as detergents, fabric softeners, biocides Bis(hydrogenated tallow alkyl)dimethylchloride (Bis(hydrogenated tallow)dimethyl ammoniumchloride; DHTDMAC) Distearyl-dimethylammoniumchloride (DODMAC; DSDMAC) Bis(hydrogenated-tallow-alkyl)dimethylammoniumchloride (DTDMAC) ORGANIC SOLVENTS Used in several processes Shall not be used in the Declaration of non-use Carbon tetrachloride (Tetrachloromethane) 1,1,1-Trichloroethane (Methylchloroform) Benzene EU REACH Annex XVII (5): Max. 0,1 % weight Solvent extraction Shall not be used in toys or (1000 mg/kg) GC-MS parts of toys where the or concentration of benzene in LC-MS the free state is greater than 5 mg/kg (0,0005 %) of the weight of the toy or part of toy. 1,1,1,2-Tetrachloroethane EU REACH Annex XVII (36): Restricted Chemical Substances version

7 Shall not be placed on the market, or used 1,1,2,2-Tetrachloroethane EU REACH Annex XVII (35): Shall not be placed on the market, or used Pentachloroethane EU REACH Annex XVII (37): Shall not be placed on the market, or used Chloroform (Trichloromethane) EU REACH Annex XVII (32): Shall not be placed on the market, or used 1,1,2-Trichloroethane EU REACH Annex XVII (34): Shall not be placed on the market, or used 1,1-Dichloroethene (Vinylidene chloride) 2-Ethoxyethanol (Ethylene glycol monoethyl ether) Ethoxyethanol acetate (2-Ethoxyethyl acetate; Ethylglycol acetate) 2-Methoxyethanol; (Ethylene glycol monomethyl ether) 2-Methoxyethanol acetate (2-Methoxyethyl acetate; Methylglycol acetate) Trichloroethylene (TCE) N-Methylpyrrolidone (N-Methyl-2-pyrrolidone; 1-Methyl-2-pyrrolidone; NMP) N,N-Dimethylacetamide (Dimethylacetamide; DMAC) EU REACH Annex XVII (38): Shall not be placed on the market, or used Solvent for printing ink etc Solvent for printing ink etc Solvent carrier for textile desizing, leather preparation etc n-hexane Phenol Tetrachloroethene (Perchloroethylene; 1,1,2,2-Tetrachloroethylene) Toluene (Methylbenzene) EU REACH Annex XVII (48): Shall not be placed on the market, or used, as a substance or in mixtures in a concentration equal to or greater than 0,1 % by Restricted Chemical Substances version

8 N,N-Dimethylformamide (Dimethylformamide; DMF) Max. 30 mg/kg (30 ppm) 1,1'-Oxybis-2-propanol Chloro-3-methyl-phenol Max. 0,1 % weight (p-chloro-m-cresol) (1000 mg/kg) Hexachlorobutadiene (1,1,2,3,4,4-Hexachloro-1,3-butadiene) Bis(2-methoxyethyl)-ether Shall not be used in GC-MS (Diethylene glycol dimethyl ether; DEGME) Xylene GC-MS 2-(2-Butoxyethoxy)-ethanol (Diethylene glycol monobutyl ether; DEGBE) Max. 0.1 % weight (1000 mg/kg) GC-MS GC-MS 2-(2-Methoxyethoxy)-ethanol (Diethylene glycol monomethyl ether; DEGME) Cyclohexane GC-MS Cyclohexanone GC-MS weight where the substance or mixture is used in adhesives or spray paints intended for supply to the general public. AFIRMGroup: Not detected (< 1 ppm) textile and leather FAMILY OF CHEMICALS NAME OF SUBSTANCES CAS No. CARRIERS CHLORINATED BENZENES, TOLUENES, NAPHTHALENES AND XYLENES LEGAL REGULATIONS REQUIREMENTS CHILDREN < 3 YRS ADULTS & CHILDREN > 3 YRS TEST METHODS COMMENTS Monochlorobenzene Dichlorobenzenes ++ 1,2-Dichlorobenzene ,3-Dichlorobenzene ,4-Dichlorobenzene Dichloromethylbenzene Trichlorobenzenes 1,2,3-Trichlorobenzene 1,2,4-Trichlorobenzene 1,3,5-Trichlorobenzene Shall not be used in the Total concentration of all chlorinated benzenes, toluenes and naphthalenes shall not exceed 1 mg/kg (1 pppm) 1,2,4-Trichlorobenzene : EU REACH Annex XVII (49): Shall not be placed on the market, or used Restricted Chemical Substances version

9 Tetrachlorobenzenes 1,2,3,4-Tetrachlorobenzene 1,2,3,5-Tetrachlorobenzene 1,2,4,5-Tetrachlorobenzene Pentachlorobenzene Hexachlorobenzene Chlorotoluene (Chloromethylbenzenes) o-chlorotoluene p-chlorotoluene m-chlorotoluene Dichlorotoluene 2,6-Dichlorotoluene 2,4-Dichlorotoluene 3,4-Dichlorotoluene 2,3-Dichlorotoluene 2,5-Dichlorotoluene Trichlorotoluene (Trichloromethylbenzenes) 2,3,6-Trichlorotoluene 2,4,5-Trichlorotoluene Benzotrichloride 2,4-Dichlorobenzylchloride 1,3-Dichloro-2-(chloromethyl)-benzene 1,2-Dichloro-4-(chloromethyl)-benzene Tetrachlorotoluenes.alpha.,2,3,6-Tetrachlorotoluene 1,3-Dichloro-2-(dichloromethyl)- benzene 1-Chloro-2-(trichloromethyl)- benzene 1-Chloro-4-(trichloromethyl)- benzene Solvent extraction GC-MS Pentachlorotoluene Chlorinated naphthalenes ++ Chlorinated xylenes ++ VARIOUS CARRIERS Naphthalene Shall not be used in the 2-Chlorophenol Restricted Chemical Substances version

10 (o-chlorophenol) C 3 -Alkylbenzenes ++ 1,2,4-Trimethylbenzene C 4 -Alkylbenzenes ++ Butylbenzene Biphenyl Propylbenzene m-phenylphenol ([1,1'-Biphenyl]-ol; Hydroxybiphenyl) 1,2,3,4-Tetrahydro-naphthalene (Tetrahydronaphthalene; Benzocyclohexane) 1,1'-Oxybis-benzene (Diphenyl oxide) 2-Phenylphenol [(1,1 -Biphenyl)-2-ol; o-phenylphenol; 2-Biphenylol; 2-Hydroxybiphenyl; OPP] Total content of all should not exceed 1 mg/kg Max accepted value: 50 mg/kg GC-MS GC-MS FAMILY OF CHEMICALS NAME OF SUBSTANCES CAS No. LEGAL REGULATIONS REQUIREMENTS CHILDREN < 3 YRS ADULTS & CHILDREN > 3 YRS TEST METHODS COMMENTS DYEING & PRINTING DYES AZOCOLOURANTS EU REACH Annex XVII (43): 1. Azodyes which, by reductive cleavage of one or more azo groups, may release one or more of the aromatic amines listed in Appendix 8 (to REACH) (in the list below marked with an *), in detectable concentrations, i.e. above 30 mg/kg (0,003 % by weight) in the articles or in the dyed parts thereof, according to the testing methods listed in Appendix 10 (to REACH referred below), shall not be used, in textile and leather articles which may come into direct and prolonged contact with the human skin or oral cavity, such as: clothing, bedding, towels, hairpieces, wigs, hats, nappies and other sanitary items, sleeping bags, footwear, gloves, wristwatch straps, handbags, purses/wallets, briefcases, chair covers, purses worn round the neck, textile or leather toys and toys which include textile or leather garments, yarn and fabrics intended for use by the final consumer. 2. Furthermore, the textile and leather articles referred to in paragraph 1 shall not be placed on the market unless they conform to the requirements set out in that paragraph. Test Methods: 1. Leather Chemical tests Determination of certain azocolorants in dyed leathers: CEN ISO/TS 17234: Textiles Methods for the determination of certain aromatic amines derived from azocolorants Part 1: Detection of the use of certain azo colorants accessible without extraction: EN : Textiles Methods for determination of certain aromatic amines derived from azocolorants Part 2: Detection of the use of certain azo colorants accessible by extracting the fibres: EN : Aminobiphenyl * EU REACH Annex XVII (15): Restricted Chemical Substances version

11 Benzidine (4,4 -Diaminodiphenyl) Leather: ISO/TS 17234:2003 Shall not be placed on the market, or used, as substances or in mixtures in concentrations greater than 0,1 % by weight * EU REACH Annex XVII (9d): Shall not be used, in jokes and hoaxes or in mixtures or articles intended to be used as such, for instance as a constituent of sneezing powder and stink bombs. EU REACH Annex XVII (13): Shall not be placed on the Not detected (detection limit 20 mg/kg (20 ppm)) Natural fibres (cotton, viscose, wool, silk) and pigment prints: EN :2003 market, or used, as substances or in mixtures in concentrations greater than 0,1 % by weight. 4-Chloro-o-toluidine * 2-Naphthylamine (β-naphthylamine) * Synthetic fibres (polyester, polyacetate, polyamide etc.): EN :2003 EU REACH Annex XVII (12): o-aminoazotoluene (4-Amino-2,3-dimethylazobenzene; 2-Methyl-4-[(2-methylphenyl)azo]-benzenamine; AAT; 4-(o-Tolyazo)-o-toluidine; 2-Amino-azotoluene; C.I. Solvent Yellow 3; C.I ) 2-Amino-4-nitrotoluene (2-Methyl-5-nitro-benzenamine; 5-Nitro-o-toluidine; 6-Methyl-3-nitroaniline; C.I ) 4-Chloroaniline (p-chloroaniline) 2,4-Diaminoanisole (4-Methoxy-m-phenylenediamine) 4,4 -Diaminodiphenylmethane (4,4 -Methylenedianiline; MDA) * * * * REACH Annex XIV: Subject to authorisation from August * 3,3 -Dichlorobenzidine * 3,3 -Dimethoxybenzidine * Shall not be placed on the market, or used, as substances or in mixtures in concentrations greater than 0,1 % by weight. Restricted Chemical Substances version

12 (o-dianisidine) o-tolidine (3,3 -Dimethylbenzidine) 4,4 -Methylenebis-(2-methyl-benzenamine) (4,4 -Methylenedi-o-toluidine; 3,3 -Dimethyl-4,4 - diaminobiphenylmethane) p-cresidine (6-Methoxymethylaniline) 4,4 -Methylenebis(2-chloro-benzenamine) (4,4 -Methylenebis(2-chloroaniline); 2,2'-Dichloro-4,4'- methylenedianiline; MOCA) 4,4 -Oxybis-benzenamine (4,4 -Oxydianiline; 4-Aminophenyl ether) 4,4 -Thiobis-benzenamine (4,4 -Thiodianiline) o-toluidine (2-Methylbenzamine; 2-Aminotoluene; 2-Methylaniline) 4-Methyl-1,3-benzendiamine (2,4-Diaminotoluene; Toluene-2,4-diamine) 2,4,5-Trimethyl-benzenamine (2,4,5-Trimethylaniline) 2-Metoxybenzenamine (o-anisidine) 4-(Phenylazo)-benzenamine (4-Aminoazobenzene; p-aminoazobenzene; C.I. Solvent Yellow 1; C.I ) 2,4-Dimethyl-benzenamine (2,4-Xylidine) 2,6-Dimethyl-benzenamine (2,6-Xylidine) 2,6-Dichloro-4-nitroaniline Chloro-4-nitroaniline Diphenylamine Nitro-p-toluidine (4-Methyl-3-nitroaniline; 4-methyl-3-nitro-benzenamine) * * * * * * * * * * * AZOCOLOURANT (blue colorant mixture of the two substances) 2-Naphthalenesulfonic acid, 4-hydroxy-3-[(2- hydroxy-3,5-dinitrophenyl)azo]-7-[(4- methoxyphenyl)amino]-, chromium complex (Navy blue) EU REACH Annex XVII (43): Shall not be placed on the market, or used, as substances, or in mixtures in concentrations greater than 0.1 % by weight, Not detected (detection limit 20 mg/kg (20 ppm)) See testing methods under AZOCOLOURANTS above. Restricted Chemical Substances version

13 where the substance or the mixture is intended for colouring textile and leather articles. Trisodiumbis(6-(4-anisidino)-3-sulfonato-2-(3,5- Unknown dinitro-2-oxidophenylazo)-1-naphtolato)- chromate(1-) DISPERSE DYES Disperse dyes that are classified carcinogenic and/or sensitizing/allergenic C.I. Disperse Black 1; C.I (4-[(4-Aminophenyl)azo]-1-naphthalenamine) C.I. Disperse Black 2; C.I (4-[(4-Aminophenyl)azo]-2-methoxy-5-methyl-benzenamine) C.I. Disperse Blue 1; C.I (1,4,5,8-Tetraamino-9,10-anthracenedione) C.I. Disperse Blue 3; C.I (1-[(2-Hydroxyethyl)amino]-4-(methylamino)-9,10- anthracenedione) C.I. Disperse Blue 7; C.I (1,4-Dihydroxy-5,8-bis[(2-hydroxyethyl)amino]-9,10- anthracenedione) C.I. Disperse Blue 26; C.I (1,5-Dihydroxy-4,8-bis(methylamino)-9,10-anthracenedione) C.I. Disperse Blue 35 (1-Amino-4,5-dihydroxy-8-(methylamino)-9,10-anthracenedione) C.I. Disperse Blue C.I. Disperse Blue 106; C.I (2-[Ethyl[3-methyl-4-[(5-nitro-2-thiazolyl)azo]phenyl]amino] ethanol) C.I. Disperse Blue 124; C.I (2-[Ethyl[3-methyl-4-[(5-nitro-2-thiazolyl)azo]phenyl]- amino]-ethanol acetate (ester)) C.I. Disperse Brown 1; C.I. Disperse Orange 46; C.I (2,2'-[[3-Chloro-4-[(2,6-dichloro-4-nitrophenyl)azo]phenyl]- imino]bis- ethanol) C.I. Disperse Orange 1; C.I (4-[(4-Nitrophenyl)azo]-N-phenyl-benzenamine) C.I. Disperse Orange 3; C.I (4-[(4-Nitrophenyl)azo]-benzenamine) C.I. Disperse Orange 11; C.I (1-Amino-2-methyl-9,10-anthracenedione) Not detected (detection limit depending on dye) Shall not be used in the Extraction in acetonitrile. Determination according to DIN 54231:2005 (Detection limit said to be 5 mg/l of extract) Restricted Chemical Substances version

14 C.I. Disperse Orange 13; C.I (4-[[4-(Phenylazo)-1-naphthalenyl]azo]-phenol; C.I. Solvent Orange 52) C.I. Disperse Orange 37; C.I (C.I. Disperse Orange 76) C.I. Disperse Orange 37/59/ (3-[[4-[(2,6-Dichloro-4-nitrophenyl)azo]- phenyl]ethylamino]propanenitrile) C.I. Disperse Orange C.I. Disperse Orange C.I. Disperse Red 1; C.I (2-[Ethyl[4-[(4-nitrophenyl)azo]phenyl]amino]-ethanol) C.I. Disperse Red 7; C.I (2,2 - [3-Chloro-4-[(4-nitrophenyl)azo]phenyl]imino]bisethanol) C.I. Disperse Red 11; C.I (1,4-Diamino-2-methoxy-9,10-anthracenedione) C.I. Disperse Red 17; C.I (2,2 - [3-Methyl-4-[(4-nitrophenyl)azo]-phenyl]imino]bisethanol) C.I. Disperse Yellow 1; C.I (4-[(2,4-Dinitrophenyl)amino]-phenol) C.I. Disperse Yellow 3; C.I (N-[4-[(2-Hydroxy-5-methylphenyl)azo]phenyl]-acetamide) Disperse Yellow 7; C.I (2-Methyl-4-[[4-(phenylazo)phenyl]azo]- phenol) C.I. Disperse Yellow 9; C.I (N-(2,4-Dinitrophenyl)-1,4-benzenediamine) C.I. Disperse Yellow 23; C.I (4-[[4-(Phenylazo)phenyl]azo]-phenol) C.I. Disperse Yellow C.I. Disperse Yellow C.I. Disperse Yellow (2-(3-Hydroxy-2-quinolinyl)-1H-indene-1,3(2H)-dione) ACID DYES Acid dyes that are classified carcinogenic and/or sensitizing/allergenic. C.I. Acid Black 48; C.I (1,1 -Iminobis[4-amino-9,10-anthracenedione, sulfonated) C.I. Acid Black C.I. Acid Blue 113; C.I (8-(Phenylamino)-5-[[4-[(3-sulfophenyl)azo]-1- naphthalenyl]azo]-1-naphthalenesulfonic acid, disodium salt) Not detected (detection limit depending on dye) Extraction in Acetonitrile Restricted Chemical Substances version

15 C.I. Acid Orange 45; C.I (3-Amino-4-[[4 - [4-[[(4-methylphenyl)sulfonyl]-oxy]phenyl]- azo][1,1 -biphenyl]-4-yl]azo]-2,7-naphthalenedisulfonic acid, disodium salt) C.I. Acid Orange 156 C.I. Acid Red 4; C.I (4-Hydroxy-3-[(2-methoxyphenyl)azo]-1-naphthalenesulfonic acid, monosodium salt) C.I. Acid Red 5, disodium salt; C.I (4-Hydroxy-3-[(2-methoxyphenyl)azo]-2,7- naphthalenedisulfonic acid, disodium salt) C.I. Acid Red 24; C.I C.I. Acid Red 26; C.I (4-[(2,4-Dimethylphenyl)azo]-3-hydroxy-2,7-naphthalenedisulfonic acid, disodium salt) C.I. Acid Red 73; C.I (7-Hydroxy-8-[[4-(phenylazo)phenyl]azo]-1,3-naphthalenedisulfonic acid, disodium salt) C.I. Acid Red 85; C.I (7-Hydroxy-8-[[4 -[[4-[[(4-methylphenyl)-sulfonyl]oxy]- phenyl]azo][1,1 -biphenyl]-4-yl]-azo]-1,3- naphthalenedisulfonic acid, disodium salt) C.I. Acid Red 114; C.I (8-[[3,3 -Dimethyl-4 -[[4-[[(4-methylphenyl)-sulfonyl]oxy]- phenyl]azo][1,1 -biphenyl]-4-yl]azo]-7-hydroxy-1,3- naphthalenedisulfonic acid, disodium salt) CATONIC (BASIC) DYES Cationic (basic) dyes that are classified carcinogenic and/or sensitizing/allergenic. Shall not be used in the Determination according to DIN 54231:2005 (Detection limit said to be 5 mg/l of extract) C.I. Basic Black 1 C.I. Basic Blue 26; C.I (4-[[4-anilino-1-naphthyl][4- (dimethylamino)phenyl]methylene]cyclohexa-2,5-dien-1- ylidene] dimethylammonium chloride) C.I. Basic Green 1; C.I (Brilliant Green; [4-[4-(Diethylamino)-benzhydrylene]- cyclohexa-2,5-dien-1-ylidene]-diethylammonium hydrogen sulphate) C.I. Basic Green 4; C.I (Malachite green; N-[4-[[4-(Dimethylamino)-phenyl]phenyl methylene]-2,5-cyclohexadien-1-ylidene]-n-methyl- methanaminium chloride) C.I. Basic Red 9; C.I (4-[(4-Aminophenyl)(4-imino-2,5-cyclohexadien-1-ylidene) methyl]-benzenamine monohydrochloride) C.I. Basic Red 12; C.I Not detected (detection limit depending on dye) Shall not be used in the Extraction in Acetonitrile Determination according to DIN 54231:2005 (Detection limit said to be 5 mg/l of extract) Restricted Chemical Substances version

16 (2-[3-(1,3-Dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-1- propenyl]-1,3,3-trimethyl-3h-indolium chloride) C.I. Basic Red (Sulfuric acid, dimethyl ester, compound with N-methyl-N- [4-[(1-methyl-1H-1,2,4-triazol-5-yl)azo]phenyl]benzylamine (1:1)) C.I. Basic Red (Astrazon red FBL) C.I. Basic Violet 3; C.I ([4-[4,4 -bis(dimethylamino)benzhydrylidene]-cyclohexa- 2,5-dien-1-ylidene]-dimethylammonium chloride) C.I. Basic Violet 14; C.I (or C.I ?) (4-[(4-Aminophenyl)(4-imino-2,5-cyclohexadien-1-ylidene)- methyl]-2-methyl-benzenamine) monohydrochloride) DIRECT DYES (SUBSTANTIVE DYES) Direct dyes (substantive dyes) that are classified carcinogenic, teratogenic and/or sensitizing/allergenic C.I. Direct Black 38; C.I (4-Amino-3-[[4 - [(2,4-diaminophenyl)azo][1,1 -biphenyl]-4- yl]azo]-5-hydroxy-6-(phenylazo)-2,7-naphthalenedisulfonic acid, disodium salt) C.I. Direct Blue 1; C.I (6,6 -[(3,3 -Dimethoxy[1,1 -biphenyl]-4,4 -diyl)bis(azo)]bis[4- amino-5-hydroxy-1,3-naphthalenedisulfonic acid, tetrasodium salt) C.I. Direct Blue 6; C.I (3,3 -[[1,1 -Biphenyl]-4,4 -dylbis(azo)]bis[5-amino-4-hydroxy- 2,7-naphthalenedisulfonic acid, tetrasodium salt) C.I. Direct Blue 15; C.I (3,3 -[(3,3 -Dimethoxy[1,1 -biphenyl]-4,4 -diyl)bis(azo)]bis[5- amino-4-hydroxy-2,7-naphthalenedisulfonic acid, tetrasodium salt) C.I. Direct Blue 78; C.I (2-[[4-[[4-[[1-Hydroxy-6-(phenylamino)-3-sulfo-2- naphthalenyl]azo]-1-naphthalenyl]azo]-6-sulfo-1- naphthalenyl]azo]-1,4-benzenedisulfonic acid, tetrasodium salt) C.I. Direct Brown 95; C.I (Disodium-[5-[[4 -[[2,6-dihydroxy-3-[(2-hydroxy-5- sulfophenyl)azo]phenyl]azo][1,1 -biphenyl]-4-yl]azo]-2- hydroxybenzoato(4-)]-cuprate(2-)) C.I. Direct Red 28; C.I (3,3 -[[1,1 -Biphenyl]-4,4 -diylbis(azo)]bis[4-amino-1- naphthalenesulfonic acid, disodium salt) Not detected (detection limit depending on dye) Shall not be used in the Extraction in Acetonitrile Determination according to DIN 54231:2005 (Detection limit said to be 5 mg/l of extract) Restricted Chemical Substances version

17 OTHER DYES Dyes that are classified carcinogenic, teratogenic and/or sensitizing/allergenic H H N,N-Dimethyl-4-(phenylazo)-benzenamine (4-Dimetylaminoazobenzene; C.I. Solvent Yellow 2; C.I ) 1,4-Benzenediamine (p-phenylenediamine; Diaminobenzene; PPDA; C.I ) Not detected (detection limit depending on dye) Shall not be used in the Extraction in acetonitrile. Determination according to DIN 54231:2005 (Detection limit said to be 5 mg/l of extract) FAMILY OF CHEMICALS NAME OF SUBSTANCES CAS No. LEGAL REGULATIONS REQUIREMENTS CHILDREN < 3 YRS ADULTS & CHILDREN > 3 YRS TEST METHODS COMMENTS FINISHING TREATMENT & SUNDRY FORMALDEHYDE Formaldehyde free and partly hydrolysable METALS AND METAL COMPOUNDS Norway: a) For children < 2 yrs: 30 mg/kg textile b) Textiles that normally come in direct contact with skin: 100 mg/kg textile c) Textiles that normally do not come in direct contact with skin: 300 mg/kg textile Similar requirements in Finland, Poland, Russia, France, Germany, Austria Leather material: 20 mg/kg for materials with direct skin contact or else: 75 mg/kg (75 ppm) Leather material: 75 mg/kg material (75 ppm) For textile materials: EN ISO For leather materials: EN ISO or EN ISO For wooden materials: EN 120 Mercury and mercury compounds EU REACH Annex XVII (18): Shall not be placed on the market, or used, as substances or in mixtures where the substance or Extractable mercury: Maximum concentration 0.02 ppm (0.02 mg/kg) in any part of finished product. Extraction according to ISO 105-E04 (2008), acid solution. Test method: EN 1483:2007 (AAS) Restricted Chemical Substances version

18 Cadmium Cadmium oxide Cadmium compounds Nickel and nickel compounds mixture is intended for use: (c) in the impregnation of heavyduty industrial textiles and yarn intended for their manufacture; The Netherlads: Max. total concentration of cadmium 100 mg/kg (100 ppm) EU REACH Annex XVII (27): Shall not be used: (a) in any post assemblies which are inserted into pierced ears and other pierced parts of the human body unless the rate of nickel release from such post assemblies is less than 0,2 μg/cm 2 /week (migration limit); (b) in articles intended to come into direct and prolonged contact with the skin such as: earrings, necklaces, bracelets and chains, anklets, finger rings, wrist-watch cases, watch straps and Extractable cadmium: Maximum concentration 0.10 ppm (0.10 mg/kg) in any part of finished product. Total content of cadmium: Maximum concentration 40 ppm (40 mg/kg) Recommended maximum level in textile and leather 1 ppm (1 mg/kg) Trim parts 40 ppm Extractable nickel: Maximum concentrati 1 ppm (1 mg/kg) in any part of finished product. Extractable nickel: Maximum concentrati 4 ppm (4 mg/kg) in any part of finished product. or ICP-MS For leather: ISO :2011 ISO :2011 Extraction according to ISO 105-E04 (2008), acid solution. Testmethods: ISO 11885:2007 (ICP-OES) ISO 5961:1994 (AAS) Pre-treatment according to EN 1122:2002 (polymers) or microwave digestion Testmethods: ISO 11885:2007 (ICP-OES) ISO 5961:1994 (AAS) REACH Requirement: The standards adopted by the European Committee for Standardisation (CEN) shall be used as the test methods for demonstrating the conformity of articles. Pre-treatment according to EN 12472:2005+A1:2009 Test method EN 1811:2011 Test for extractable nickel: Extraction according to ISO 105-E04 (2008), acid solution. Testmethods: ISO 11885:2007 (ICP-OES) CR 13695:2000 EU REACH Annex XVII (23): Shall not be used in mixtures and articles produced from synthetic organic polymers (hereafter referred to as plastic material) such as: Community Eco-label for footwear: No Arsenic, Cadmium or Lead. Test methods according to EN 14602:2005 For leather products; sample preparation according to EN ISO 4044:2008. Restricted Chemical Substances version

19 Lead, lead alloys and lead compounds Antimony and antimony compounds tighteners, rivet buttons, rivets, zippers and metal marks, when these are used in garments, if the rate of nickel release from the parts of these articles coming into direct and prolonged contact with the skin is greater than 0,5 μg/cm 2 /week. (c) in articles referred to in point (b) where these have a non-nickel coating unless such coating is sufficient to ensure that the rate of nickel release from those parts of such articles coming into direct and prolonged contact with the skin will not exceed 0,5 μg/cm 2 /week for a period of at least two years Denmark: Max total concentration of lead 100 ppm (100 mg/kg) Extractable lead: Max. conc. 0.2 ppm (0.2 mg/kg) in any part of finished product. Total lead content: Max. conc. 45 ppm lead (45 mg/kg) Extractable antimony: Max. conc. 5 ppm (5 mg/kg) in Extractable lead: Max. conc. 1 ppm (1 mg/kg) in any part of finished product. Total lead content: Max. conc. 90 ppm lead (90 mg/kg) Extractable animony: Max. conc. 10 ppm (10 mg/kg) For leather: ISO :2011 ISO :2011 Screening tests for nickel release from alloys and coatings: CR 12471:2002 Extraction according to ISO 105-E04 (2008), acid solution. Testmethods: ISO 11885:2007 (ICP-OES) ICP-MS or AAS Pre-treatment according to EN 1122:2002 (polymers) or microwave digestion Testmethods: ISO 11885:2007 (ICP-OES) ISO 5961:1994 (AAS) Extraction according to ISO 105-E04 (2008), acid solution. Testmethods: ISO 11885:2007 (ICP-OES) Community Eco-label for footwear: No Arsenic, Cadmium or Lead. Test methods according to EN 14602:2005 For leather products; sample preparation according to EN ISO 4044:2008. Restricted Chemical Substances version

20 Arsenic and arsenic compounds Diarsenic pentaoxide Diarsenic trioxide Chromium(VI), hexavalent and its compounds Potassium dichromate Sodium dichromate Sodium dichromate (dehydrate) Sodium chromate Potassium chromate Ammonium dichromate Lead sulfochromate yellow (C.I. Pigment Yellow 34) Strontium chromate Zinc chromate(vi) hydroxide Lead chromate molybdate sulphate red (C.I. Pigment Red 104) Lead Chromate any part of finished product. in any part of finished product. Total concentration in polyester fibres shall not exceed 260 ppm (260 mg/kg). Extractable arsenic: Max. conc. 0.2 ppm (0.2 mg/kg) in any part of finished product. Extractable arsenic: Max. conc. 1.0 ppm (1.0 mg/kg) in any part of finished product. Total content: Max. conc. 10 ppm arsenic (10 mg/kg) Extractable chromium(vi) in leather: Under detection limit, less than 3 ppm (3 mg/kg) in any part of finished product. Extractable chromium(vi) in textiles: Not detected (detection limit 0,5 mg/kg) Total concentration of chromium(vi) in textiles, and leather: Not detected ICP-MS or AAS EN ISO Microwave digestion with H 2 O 2 /HNO 3 Measuring: EN ISO (2009) Extraction according to ISO 105-E04 (2008), acid solution. Analytical method - EN ISO 11885:2007 or EN ISO 11969:1996 Pre-treatment - EN 1122:2002 or microwave digestion with H 2 O 2 /HNO 3 Analytical method - EN ISO 11885:2007 or EN ISO 11969:1996 Extractable chromium in leather. Pre-treatment EN ISO 17075:2007. Aging of the sample is required (24 h, 80 C, 20 % rh). Analysis according to EN ISO 17075:2007. Not detected (detection limit 3 ppm (3 mg/kg). Pretreatment according to EN ISO BS EN420 ISO Leather - chemicals test - determination of chromium(vi) content. Community Eco-label for footwear: No Arsenic, Cadmium or Lead. Test methods according to EN 14602:2005 For leather products; sample preparation according to EN ISO 4044:2008. EU REACH Annex XVII (47): Cement and cementcontaining mixtures shall not be placed on the market, or used. Used in leather tanning and leather finishing; among other applications. Used in pigments. Restricted Chemical Substances version

21 Chromium metal and chromium(iii) with its compounds Extractable chromium in textile and artificial leather: Max. conc. 1 ppm (1 mg/kg). Extractable chromium in textile and artificial leather: Max. conc. 2 ppm (2 mg/kg). Leather: Max 100 ppm (100 mg/kg) Extraction according to ISO 105-E04 (2008), acid solution. Testmethods: ISO 11885:2007 or EN 1233:1996 Cobalt and cobalt compounds Cobalt dichloride Cobalt(II) sulphate Cobalt(II) dinitrate Cobalt(II) carbonate Cobalt(II) diacetate (Cobaltous acetate) Tin and inorganic tin compounds Barium and barium compounds (readily soluble) Zinc and zinc compounds Zinc oxide (C.I. Pigment White; C.I ) Copper and copper compounds Extractable cobalt: Max. conc. 1.0 ppm (1.0 mg/kg) in any part of finished product. Extractable cobalt: Max. conc. 4.0 ppm (4.0 mg/kg) in any part of finished product. Extractable inorganic tin: Max. conc.1.0 ppm (1.0 mg/kg) in any part of finished product. Extractable barium: 10 ppm (10 mg/kg) in any part of finished product. Extractable zinc: Max. conc. 50 ppm (50 mg/kg) in any part of finished product. Extractable copper: Max. conc. 25 ppm (25 mg/kg) Extractable zinc: Max. conc. 200 ppm (200 mg/kg) in any part of finished product. Extractable copper: Max. conc. 50 ppm (50 mg/kg) Extraction according to ISO 105-E04 (2008), acid solution. Testmethod: ICP-MS Extraction according to ISO 105-E04 (2008), acid solution. Testmethod: ICP-MS Extraction according to ISO 105-E04 (2008), acid solution. Testmethod: ICP-MS Extraction according to ISO 105-E04 (2008), acid solution. Testmethod: ICP-MS Extraction according to ISO 105-E04 (2008), acid solution. Testmethod: ICP-MS / ICP-OES Levi Strauss Levi Strauss: Max 25 mg/kg in textile and leather Puma: Max 60 mg/kg in all types of materials Restricted Chemical Substances version

22 SIlver applied as a substance with antibacterial effect (Silver ion Ag + ) (Metallic silver, C.I ) Silver chloride Silver sodium hydrogen zirconium phosphate Silver-zinc-aluminium-boronphosphate glass Silver zeolite complex Metalloids Boron and boron compounds Boric acid Disodium tetraborate, anhydrous Tetraboron disodium heptaoxide, hydrate ORGANOTIN COMPOUNDS in any part of finished product. in any part of finished product. Shall not be used in the Max. accepted concentration 0.1 mg/kg Shall not be used in of leather or leather containing articles AFIRMGroup: Max 25 ppm in textile and leather May be used in leather tanning. Flame retardants. Tribytyltin (TBT) and tributyltin compounds (Tributylstannane; Tributyltin hydride) Triphenyltin (TPhT) and triphenyltin EU REACH Annex XVII (20): Tri-substituted organostannic compounds: (a) Tri-substituted organostannic compounds such as tributyltin (TBT) compounds and triphenyltin (TPT) compounds shall not be used after 1 July 2010 in articles where the concentration in the article, or part thereof, is greater than the equivalent of 0,1 % by weight of tin. Max. 1 mg/kg (1 ppm) of each substance Max. 1 mg/kg (1 ppm) of each substance Extraction with ethanol or methanol. Test method ISO 17353:2004 (GC-MS) Restricted Chemical Substances version

23 compounds ++ Monobutyltin (MBT) compounds ++ Monooctyltin (MOT) compounds ++ Dibutyltin (DBT) and dibutyltin compounds Dioctyltin (DOT) and dioctyltin compounds EU REACH Annex XVII (20): Dibutyltin (DBT) compounds: (a) Dibutyltin (DBT) compounds shall not be used after 1 January 2012 in mixtures and articles for supply to the general public where the concentration in the mixture or the article, or part thereof, is greater than the equivalent of 0,1 % by weight of tin. (c) By way of derogation, points (a) and (b) shall not apply until 1 January 2015 to the following articles and mixtures for supply to the general public: paints and coatings containing DBT compounds as catalysts when applied on articles, soft polyvinyl chloride (PVC) profiles whether by themselves or coextruded with hard PVC, fabrics coated with PVC containing DBT compounds as stabilisers when intended for outdoor applications, EU REACH Annex XVII (20): Dioctyltin (DOT) compound: (a) Dioctyltin (DOT) compounds shall not be used after 1 January 2012 in the following articles for Restricted Chemical Substances version

24 Tetrabutyl tin compounds Tetrabutyltin (Tetrabutylstannane; Tetra-n-butyltin; TeBT) Tetraoctyltin Hexabutyldistannoxane (Tributyltinoxide; Bis(tributyltin)oxide; TBTO) Tricyclohexyltin (TCyhT) compounds ++ Tricyclohexyltin hydroxide Trioctylstannane (Trioctyltin; TOT) Tripropyltin (TPT) supply to, or use by, the general public, where the concentration in the article, or part thereof, is greater than the equivalent of 0,1 % by weight of tin: textile articles intended to come into contact with the skin, gloves, footwear or part of footwear intended to come into contact with the skin, wall and floor coverings, childcare articles, female hygiene products, nappies, two-component room temperature vulcanisation moulding kits (RTV-2 moulding kits). Restricted Chemical Substances version

25 FLAME RETARDANTS FAMILY OF CHEMICALS NAME OF SUBSTANCES CAS No. LEGAL REGULATIONS REQUIREMENTS CHILDREN < 3 YRS ADULTS & CHILDREN > 3 YRS TEST METHODS COMMENTS BROMINATED FLAME RETARDANTS Pentabromodiphenylether (PentaBDE) Pentabromodiphenylether, derivative BDE-99 BDE-100 Octabromodiphenylether (OctaBDE; 1,1'-Oxybis-benzene, octabromo derivatives) Norway: Banned in concentrations > 0.1% weight EU REACH Annex XVII (44): Articles shall not be placed on the market if they, or flame-retarded parts thereof, contain this substance in concentrations greater than 0,1 % by weight Norway: Banned in concentrations > 0.1% weight Octabromodiphenylether EU REACH Annex XVII (45): Articles shall not be placed on the market if they, or flame-retarded parts thereof, contain this substance in concentrations greater than 0,1 % by weight. Tris-(2,3-dibromopropyl)-phosphate (TRIS; TrisBP) EU REACH ANNEX xvii (4): 1. Shall not be used in textile articles, such as garments, undergarments and linen, intended to come into contact with the skin. 2. Articles not complying with paragraph 1 shall not be placed on the market. Polybrominated biphenyls EU REACH Annex XVII (8): Not detectable concentration Shall not be used in the Solvent extraction followed by GC-MS / LC-MS Restricted Chemical Substances version

26 (Polybromobiphenyls; PBB) 1,1'-Oxybis(2,3,4,5,6-pentabromo)-benzene (Bis(pentabromophenyl) ether; Decabromodiphenyl ether; DecaBDE) Hexabromocyclododecane and all diastereoisomers (HBCDD) 2,3-Dibromo-1-propanol-hydrogenphosphate (Bis(2,3-dibromopropyl)phosohate) 2,2-bis(Bromomethyl)-1,3-propanediol (Dibromoneopentyl glycol) Tetrabromobisphenol A (TBBP-A) 1,1'-(1-Methylethylidene)bis[3,5-dibromo-4- (2,3-dibromopropoxy)]benzene (1,1'-(Isopropylidene)bis[3,5-dibromo-4-(2,3-dibromopropoxy)benzene]; BDBPT) 1,2-bis(2,4,6-Tribromophenoxy)ethane (1,1'-[Ethane-1,2-diylbisoxy]bis[2,4,6-tribromobenzene]; BTBPE) Shall not be used in textile articles, such as garments, undergarments and linen, intended to come into contact with the skin Norway: Banned in concentrations > 0.1% weight REACH Annex XIV: Subject to authorisation from August Ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) 1,1'-(Ethane-1,2-diyl)bis[2,3,4,5,6-pentabromobenzene] (Decabromodiphenylethane; DBDPE) bis(2-ethylhexyl)-tetrabromophthalate (Tetrabromo-phthalic acid, di(2-ethylhexyl) ester; BEHTBP) 2,4,6-Tribromophenol (TBP) OTHER FLAME RETARDANTS Tris-(aziridinyl)-phosphinoxide (TEPA) EU REACH Annex XVII (7): Shall not be used in textile Restricted Chemical Substances version

27 H Short-chained chlorinated paraffins (SCCPs; Chloroalkanes, C10-13) Medium-chained chlorinated paraffins, C14-C17 (MCCPs) Paraffin waxes and hydrocarbon waxes, chlorinated Phosphoric acid tris(2-methylphenyl)-ester (Tri-o-tolyl-phosphate; Tri-o-cresyl-phosphate) 1,3-Dichloro-2-propanol-phosphate (3:1) (Tris(1,3-dichloro-2-propyl)-phosphate; TDCP) Tris(2-chloroethyl)-phosphate (2-Chloro-ethanol, phosphate (3:1); TCEP) articles, such as garments, undergarments and linen, intended to come into contact with the skin EU REACH Annex XVII (42): Shall not be placed on the market, or used as substances, or as constituents of other substances or in mixtures in concentrations greater than 1 % by weight, where the substance or mixture is intended for: metal working, fat liquoring of leather Triphenyl phosphate (TPhP; Phosphoric acid, triphenyl ester) Potassium hexafluorozirconate Potassium hexafluorotitanate Compounds of antimony Antimony trioxide Not detectable concentration Shall not be used in the Solvent extraction followed by GC-MS / LC-MS Can be found in articles made of plastics or rubber. Restricted Chemical Substances version

28 PLASTICIZERS FAMILY OF CHEMICALS NAME OF SUBSTANCES CAS No. LEGAL REGULATIONS REQUIREMENTS CHILDREN < 3 YRS ADULTS & CHILDREN > 3 YRS TEST METHODS COMMENTS PHTHALATES Mainly used as plasticisers in PVC prints but may also be used as carriers. Di(2-ethylhexyl)-phthalate (Bis(2-ethylhexyl)phthalate; DEHP) Dibutylphthalate (DBP) Butylbenzylphthalate (Benzyl butyl phthalate; BBP) Di-iso-nonylphthalate (DINP) Diisodecylphthalate (DIDP) REACH Annex XIV: Subject to authorisation from February REACH Annex XIV: Subject to authorisation from February REACH Annex XIV: Subject to authorisation from February Not detectable conc. (Detection limit 50 mg/kg for each phthalate) Shall not be used in the Max. 100 mg/kg (100 ppm) of each phthalate. Total conc. of all phthalates should not exceed 300 mg/kg (300 ppm). Shall not be used in the Solvent extraction followed by GC-MS Test methods in accordance with one of these standards: EN 71-11:2005 EN 14372:2004 EN ISO 18856:2004 Or EN 15777:2009 EU REACH Annex XVII (51a): 1. Shall not be used as substances or in mixtures, in concentrations greater than 0,1 % by weight of the plasticised material, in toys and childcare articles. EU REACH Annex XVII (51b): 1. Shall not be used as substances or in mixtures, in concentrations greater than 0,1 % by weight of the plasticised material, in toys and childcare articles. EU REACH Annex XVII (51c): 1. Shall not be used as substances or in mixtures, in concentrations greater than 0,1 % by weight of the plasticised material, in toys and childcare articles. EU REACH Annex XVII (52a): Shall not be used as substances or in mixtures, in concentrations greater than 0,1 % by weight of the plasticised material, in toys and childcare articles which can be placed in the mouth by children. EU REACH Annex XVII (52b): Shall not be used as Restricted Chemical Substances version

29 Di-n-octylphthalate (DNOP) Di-iso-butylphthalate (DIBP) Dimethylphthalate (DMP) Carrier Diethylphthalate (DEP) Carrier 1,2-Benzenedicarboxylic acid, di-c6-8-branched alkyl esters, C7-rich (Di(branched C6-C8)alkylphthalate; C6-8-(branched)-Alkyl benzene-1,2-dicarboxylate; Diisoheptyl phthalate; DIHP) 1,2-Benzenedicarboxylic acid, di-c7-11- branched and linear alkyl esters (Di-C7-11-(linear and branched)-alkyl phthalate; Di(heptyl, nonyl, undecyl) phthalate; 1,2-Benzenedicarboxylic acid, di- C7-11-branched and linear alkyl esters; DHNUP) Bis(2-methoxyethyl) phthalate (DMEP) Dipentyl phthalate (DPP; n-; iso-; or mixed) 1,2-Benzenedicarboxylic acid dipentylester, branched and linear (DPP) Di-n-hexylphthalate (DHP) substances or in mixtures, in concentrations greater than 0,1 % by weight of the plasticised material, in toys and childcare articles which can be placed in the mouth by children EU REACH Annex XVII (52c): Shall not be used as substances or in mixtures, in concentrations greater than 0,1 % by weight of the plasticised material, in toys and childcare articles which can be placed in the mouth by children OTHER PLASTICIZERS Hexahydromethylphthalic anhydride [1], Has been used as plasticizer Restricted Chemical Substances version

30 Hexahydro-4-methylphthalic anhydride [2], Hexahydro-1-methylphthalic anhydride [3], Hexahydro-3-methylphthalic anhydride [4] [The individual isomers [2], [3] and [4] (including their cis- and trans- stereo isomeric forms) and all possible combinations of the isomers [1] are covered by this entry] in polyester MICELLANEOUS FAMILY OF CHEMICALS NAME OF SUBSTANCES CAS No. LEGAL REGULATIONS REQUIREMENTS CHILDREN < 3 YRS ADULTS & CHILDREN > 3 YRS TEST METHODS COMMENTS POLYCYCLIC COMPOUNDS Polycyclic aromatic hydrocarbons (PAH) Anthracene Anthracene oil Anthracene oil, anthracene paste Anthracene oil, anthracene paste, anthracene fraction Anthracene oil, anthracene paste,distn. lights Anthracene oil, anthracene-low ISOCYANATES The content of PAH in any mineral oil applied shall not exceed 1.0 % by mass Anthracene, anthracene oils or anthracene pastes shall not be used in. ISO 18287:2006 (Method for PAH in soil) GC-MS EU REACH Annex XVII (50): Toluene-2,4-diisocyanate (TDI; 2,4-Diisocyanato-1-methyl-benzene) Diphenylmethane diisocyanate (MDI; 4,4'-Methylenediphenyl diisocyanate) Maximum accepted Analysis of free isocyanates: Solvent extraction / HPLC Methylenediphenyl diisocyanate (MDI) concentration in finished EU REACH Annex XVII (56): product: 1mg free isocyanate per kilo (1 ppm); Analysis of releasable (blocked) isocyanates: Shall not be placed on the market Hexamethylene diisocyanate (HDI) Isophorone diisocyanate (IPDI; 3-Isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate) mg releasable (blocked) isocyanates per kilo (50 ppm). Solvent extraction / GC-MS with injector block temperature at 300 C, confirmation at 180 C. Restricted Chemical Substances version

31 Tetramethylxylene diisocyanate (TMXDI; 1,3-bis(1-Isocyanato-1-methylethyl)benzene) MISCELLANEOUS Perfluorooctane-sulphonate (PFOS) and PFOS related compounds (Perfluorooctanyl-sulphonates with the formula C8F17SO2X where X = OH, metallic salt, halogenide, amide, and other derivates including polymers) Pentadecafluorooctanoic acid (Perfluorooctane-carboxylic acid; PFOA) EU REACH Annex XVII (53): 1. Shall not be placed on the market, or used, as substances or in mixtures in concentrations equal to or greater than 50 mg/kg (0,005 % by weight). 2. Shall not be placed on the market in semi-finished products or articles, or parts thereof, if the concentration of PFOS is equal to or greater than 0,1 % by weight calculated with reference to the mass of structurally or microstructurally distinct parts that contain PFOS or, for textiles or other coated materials, if the amount of PFOS is equal to or greater than 1 μg/m 2 of the coated material. Shall not be used in the Max.acceped: 1 µg/m Shall not be used in the Solvent extraction, LC-MS analysis Solvent extraction, LC-MS analysis Ammonium pentadecafluorooctanoate (APFO) Max.acceped: 1 µg/m Shall not be used in the Solvent extraction, LC-MS analysis PFOA (Pentadecafluorooctanoic acid) compounds Max.acceped: 1 µg/m 2 Shall not be used in the Max.acceped: Solvent extraction, LC-MS analysis Restricted Chemical Substances version

32 Linear alkydbenzene sulfonates (LAS) Ethylenediaminetetraacetic-acid (EDTA) Diethylenetriaminepentaacetic-acid sodium salt (DTPA) Nicotine Nitrobenzenamine (p-nitroaniline; C.I. Azoic Diazo Component 37; C.I ) µg/m Shall not be used in the Shall not be used in the Shall not be used in the Shall not be used in the Shall not be used in the Nitrobenzene Shall not be used in the N-Butylbenzenesulfonamide Shall not be used in the Octamethylcyclotetrasiloxane Shall not be used in the (Cyclomethicone; D4) Decamethylcyclopentasiloxane Shall not be used in the (Dimethylsiloxane pentamer; D5) Acrylamide Shall not be used in (2-Propenamide) Bisphenol A (BPA) Not detected. Detection limit Textile: 1 mg/kg Plastics: 5 mg/kg Acridine Shall not be used in Declaration of non-use Declaration of non-use Declaration of non-use Declaration of non-use Declaration of non-use Declaration of non-use Declaration of non-use Declaration of non-use Declaration of non-use Declaration of non-use EU REACH Annex XVII (60): Shall not be placed on the market or used as a substance or constituent ISO : 2009 Solvent (methanol) extraction, detection with GC-MS Declaration of non-use EU restriction on use in toys and water-bottles etc. ORGANOCHLORINES FAMILY OF CHEMICALS NAME OF SUBSTANCES CAS No. LEGAL REGULATIONS REQUIREMENTS CHILDREN < 3 YRS ADULTS & CHILDREN > 3 YRS TEST METHODS COMMENTS ORGANOCHLORINES Polychlorinated biphenyls Shall not be Shall not be Extraction followed by Restricted Chemical Substances version

33 (PCB) ++ used in the Polychlorinated terphenyls (PCT) ++ Dichloro[(dichlorophenyl)methyl]methylbenzene, mixture of isomers (Monomethyl-tetrachloro-diphenyl-methane; Ugilec 141) Monomethyl-dibromo-diphenyl methane Monomethyl-dichloro-diphenyl methane used in the GC-MS or LC-MS EU REACH Annex XVII (1): Shall not be placed o the Max. total 0.5 mg/kg Max. total 1 mg/kg market or used in EU REACH Annex XVII (24): Shall not be placed o the market or used in FAMILY OF CHEMICALS NAME OF SUBSTANCES CAS No. LEGAL REGULATIONS REQUIREMENTS CHILDREN < 3 YRS ADULTS & CHILDREN > 3 YRS TEST METHODS BIOCIDES / PESTICIDES Biocides/Pesticides are used in the of natural fibers like cotton, ramie, flax, wool etc. to protect against insects, fungus, plants etc. COMMENTS CHLORINATED PHENOLS Pentachlorophenol and its salts or esters Tetrachlorophenol and its salts and esters Including tetrachlorophenoxy compounds 5-Chloro-2-(2,4-dichlorophenoxy)-phenol (Triclosan) N-(4-Chlorophenyl)-N'-(3,4-dichlorophenyl)- urea (Triclocarban; 3,4,4 -Trichlorocarbanilide) Chlorinated phenols, and salts and esters of these Norway: Max concentration in clothing, textiles and leather: 5 ppm (5 mg/kg). Test according to USEPA 8270 or similar. Shall not be used in the, or during storage and transport. Max. conc.: 1.0 mg/kg textile (1.0 ppm) ref. Øko-Tex Test method leather: EN ISO 17070:2006 Wood: CEN/TR 14823:2003 EU REACH Annex XVII (22): Shall not be placed on the market, or used, as a substance, as a constituent in other substances, or in mixtures, in a concentration equal to or greater than 0,1 % by weight. Restricted Chemical Substances version

34 OTHER Dimethylfumarate (DMFU; DMFu) Methylbromide Isothiazolinones (sensitizing) 2-Octyl-2H-isothiazol-3-one (Octhilinone (ISO)) 5-Chloro-2-methyl-2H-isothiazol-3-one Methyl-2H-isothiazol-3-one DDT (Dichloro-diphenyl-trichloroethane; 1,1'-(2,2,2- Trichloroethylidene)bis[4-chlorobenzene]) DDE (1,1'-(Dichloroethenylidene)bis[4-chloro-benzene]; Dichloro-diphenyl-dichloroethylene) EU Commission Decision of 17 March 2009 Requiring Member States to ensure that products containing the biocide dimethylfumarate are not placed or made available on the market (2009/251/EC). Max. accepted concentration is 0.1 mg/kg Aldrine Carbaryl (1-Naphthalenol methylcarbamate) Chlordane Chlordecone (Kepone) Dieldrine Endrine Heptachlor Mirex Toxaphene (Camphechlor (ISO)) Shall not be used in the, or during storage and transport. Max. 1.0 mg/kg (1.0 ppm) Shall not be used in the, or during storage and transport. Max. total content of all should not exceed 0.5 mg/kg Max. 2.0 mg/kg (2.0 ppm) Shall not be used in the, or during storage and transport. Max. total content of all should not exceed 1 mg/kg EU REACH: Proposed to be included in Annex XVII to REACH. The use of DMFu for biocidal purpose in mixtures is prohibited, but treatment of articles is only temporary prohibited, and must be permanently banned in articles. Proposed maximum acceptable concentration in articles is 0.1 mg/kg. Hexachlorobenzene EU: Banned in Regulation (EU) No. 850/2004 (POPs) Hexabromo-1,1'-biphenyl (BP-6) Lindane Restricted Chemical Substances version

35 (γ-hch, including mixtures of isomers of HCH (BHC)) α-hexachlorocyclohexane β-hexachlorocyclohexane δ-hexachlorocyclohexane ,4,5-Trichlorophenoxyacetic acid, its salts and compounds (2,4,5-T) 2-(2,4,5-Trichlorophenoxy)propionic acid, its salts and compounds (Fenoprop (ISO); 2,4,5-TC) Captafol Chlordimeform (N'-(4-Chloro-2-methylphenyl)-N,N-dimethyl-methanimidamide) Dinozeb and its salts (6-sec-Butyl-2,4-dinitrophenol) Methamidophos Monocrotophos Parathion Methylparathion DDD (1,1-Dichloro-2,2-bis(p-chlorophenyl)ethane; Dichlorodiphenyl-dichloroethane; 1,1'-(2,2-dichloroethylidene)- bis[4-chlorobenzene)) Propetamphos ((E)-3-[[(Ethylamino)methoxyphosphinothioyl]-oxy]-2- butenoic acid 1-methylethyl ester) Chlorobenzilate Phosphamidon (Phosphoric acid, 2-chloro-3-(diethylamino)-1-methyl-3- oxo-1-propenyl dimethyl ester) 2,4-D (2,4-Dichlorophenoxyacetic acid, salts & compounds) Azinophosmethyl Azinophosethyl Bromophos-ethyl Chlorfenvinphos Coumaphos Cyfluthrin Cyhalothrin Cypermethrin S,S,S-Tributyl phosphorotrithioate (DEF) Restricted Chemical Substances version

36 Deltamethrin Diazinon Dichlorprop Dicrotophos Dimethoate Endosulfan α-endosulfan β-endosulfan Esfenvalerate Fenvalerate Heptachloroepoxide Isodrine Kelevane Pentachloronitrobenzene (Quintozene) Malathion (4-Chloro-2-methylphenoxy)- acetic acid (2-Methyl-4-chlorophenoxyacetic acid; MCPA) 4-(4-Chloro-2-methylphenoxy)- butanoic acid (MCPB) Mecoprop (2-(4-Chloro-2-methylphenoxy)- propanoic acid) Methoxychlor Perthane (1,1-Dichloro-2,2-bis(4-ethylphenyl)ethane) Mevinphos (3-[(Dimethoxyphosphinyl)oxy]- 2-butenoic acid, methyl ester; Phosdrin) Profenophos (O-(4-Bromo-2-chlorophenyl) O-ethyl S-propyl esterphosphorothioic acid) Quinalphos Strobane Telodrine Trifluralin (Thiocyanatomethylthio)-1,3-benzothiazole ((2-Benzothiazolylthio)methyl-thiocyanate; TCMTB) Additional Pesticides for Leather Chlorothalonil Dichlofluanid Pentachloroanisole Permethrine Max. total content of all should not exceed Max. total content of all should not exceed Restricted Chemical Substances version

37 Tolyfluanid mg/kg 1 mg/kg FAMILY OF CHEMICALS NAME OF SUBSTANCES CAS No. LEGAL REGULATIONS REQUIREMENTS CHILDREN < 3 YRS ADULTS & CHILDREN > 3 YRS TEST METHODS COMMENTS OTHER FACTORS OF IMPORTANCE ph VALUE Clothing and textiles for babies or that come in direct contact with skin Clothing and textiles that do not come into direct contact with skin ph 4,0-7,5 ph 4,0-9,0 EN ISO 3071:2005 AFIRMGroup: ph ph value, leather Extraction: ph EN ISO 4045:2008 AFIRMGroup: ph FAMILY OF CHEMICALS NAME OF SUBSTANCES CAS No. LEGAL REGULATIONS REQUIREMENTS CHILDREN < 3 YRS ADULTS & CHILDREN > 3 YRS TEST METHODS COMMENTS CHEMICALSUBSTANCES OF CONCERN THAT MAY BE USED IN THE PRODUCTION OF FOOTWEAR NITROSAMINES May be used in synthetic rubber and polyurethane N-Nitrosodimethylamine (N-Methyl-N-nitroso-methanamine; NDMA) N-Ethyl-N-nitroso-ethanamine (N-Nitrosodiethylamine; NDEA) N-Nitrosodipropylamine (NDPA) N-Butyl-N-nitroso-1-butanamine (N-Nitrosodibutylamine; NDBA) Should not be used in Should not be used in Should not be used in Should not be used in Restricted Chemical Substances version

38 N-Nitrosopiperidine (NPIP) 1-Nitrosopyrrolidine (N-Nitrosopyrrolidine; NPYR) N-Nitrosomorpholine (NMOR) N-Methyl-N-nitroso-benzenamine (N-Nitroso-N-methyl-N-phenylamine; N-Methyl-Nnitrosoaniline; NMPhA) N-Ethyl-N-nitroso-benzenamine (N-Nitroso-N-ethyl-N-phenylamine; N-Nitroso-etylfenylamin; N-Nitroso-N-ethylaniline; NEPhA) Monomers Acrylonitrile (2-Propenenitrile) Should not be used in Should not be used in Should not be used in Should not be used in Should not be used in (1 ppm (1 mg(kg) in leather or textile) Polychloroprene (Neoprene) p-tert-butylphenol-formaldehyde resin (Paratertiary butyl phenol formaldehyde; PTBF) Solvents Pitch, coal tar, high temperature Should not be used in Colophony Flame retardants 2,4,6-Tribromophenol Should not be used in Other 1,3,5-Tris[(2S and 2R)-2,3-epoxypropyl]-1,3,5- triazine-2,4,6-(1h,3h,5h)-trione (β-tgic) No standard test methods available for analysis in footwear / footwear components (GC/MS) No standard test method for analysis in footwear or footwear components May be found in rubber and adhesives ( May be used in rubber products Ingredient in adhesives, varnishes and printing inks May be used as plasticizer in plastics Restricted Chemical Substances version

39 Dioxobis(stearato)trilead May be used as a stabiliser in PVC Trilead dioxide phosphonate May be used as a stabiliser in plastics Pentalead tetraoxide sulphate May be used as a stabiliser in PVC Rubber chemicals Thiram (Tetramethylthioperoxydicarbonic diamide) Imidazolidine-2-thione (Ethylenethiourea) Diazenedicarboxamide (Azodicarbonamide) Mercaptobenzothiazole N-Ethyl-benzenamine (N-Ethylphenylamine; N-Ethylaminobenzene72-54) 4-(1,1,3,3,-Tetramethylbutyl)phenol (p-tert-octylphenol) Dibutyltin dichloride (DBTC) Should not be used in Should not be used in Should not be used in Should not be used in Listed in SIN list due to endocrine-disrupting effects Leather treatment chemicals 4-Nitrophenol (p-nitrophenol) Metham-sodium (Methylcarbamodithioic acid, monosodium salt) Should not be used in Should not be used in Listed in SIN list due to endocrine-disrupting effects Listed in SIN list due to endocrine-disrupting effects Restricted Chemical Substances version

40 METHODS OF ANALYSIS The chemical substances listed are quite different. However, for quality control to check that the supplied goods are within specified requirements, we think the number of standardised methods for chemical analysis can be limited to three. The sampling and preparation procedures should also be standardised to enable reproducible results. Organic substances Recommended method of analysis for organic substances is capillary column gas chromatography-massspectrometry (GC-MS). With standardised preparation procedures, the detection limit is in the range 0,1-20 mg per kilo textile. Detection of different organic substances may require use of different types of capillary columns. An alternative method of analysis may be high pressure liquid chromatography (HPLC). Dyes and colorants For dyes and colourants, the recommended test method is Öko-Tex method M4. Metals and metal compounds For metals, test samples may be analysed using atomic absorption spectrophotometry (AAS) or inductively coupled plasma mass spectrometry (ICP-MS). The preparing procedures for these analysis are tough only the metallic elements will be identified in the analysis, not the individual compounds. Tinorganic compounds must be analysed according to the procedure for organic compounds. Chemical analysis are carried out to verify that the products are according to specifications and do not contain banned substances. Samples for analysis should be taken from parts of the products where problematic substances are expected to be found not necessarily representing the average of the whole product. Restricted Chemical Substances version

41 Restricted Substances List NONYLPHENOL ETHOXYLATES (NPEO) Some examples of substances in this group: Nonylphenol ethoxylate (NPEO); (C 2 H 4 O) n C 15 H 24 O CAS No , Nonylphenol; C 6 H 4 (OH)C 9 H 19 CAS No , (branched) Nonylphenol ethoxylates have been used in several different applications. Their main use is as surfactants (nonionic tensides). Such chemicals have been used in autocare products, degreasers and cleaners, as disperging agents and as emulsifiers. Nonylphenol ethoxylates may be used as a surface active component in pre-washing detergents to remove sizing agents from woven fabrics, and as emulsifier and dispersant in coating pastes and printing inks. Legal regulations: REACH: Nonylphenol and nonylphenol ethoxylates shall not be placed on the market or used as a substance or constituent of preparations in concentrations equal or higher than 0,1 % by mass in textiles and leather processing, with two exceptions. Nonylphenol shall be labelled with hazard symbols for corrosive (C) and environmental (N) hazards, and with risk phrases to warn against possible effects on re and birth defects. Nonylphenol and nonylphenol ethoxylates are listed in Norwegian authorities list of priority. Nonylphenol and nonylphenol ethoxylates are included in the North Sea Declaration and OSPAR treaty. Recommended requirements: Nonylpneol ethoxylates and nonylphenol shall not be added intentionally to any process in the of textiles and clothing. Harmful health effects Nonylphenol ethoxylates are irritating to skin and respiratory organs, and are readily decomposed to nonylphenol, which is corrosive, harmful if ingested, and can possibly cause birth defects and affect re. Possible effects on the environment Nonylphenol ethoxylates are readily decomposed to nonylphenol, which is very toxic to fish and other aquatic organisms; persistent and slowly degradable; accumulates in organisms and sludge, and can cause long-term aquatic effects. Nonylphenol has shown hormone disrupting effects in fish. Methods of analyses Samples are extracted and analysed in reversed phase HPLC system coupled with mass spectrometer Alkylphenols Page 1

42 Restricted Substances List POSSIBLE SUBSTITUTES Fattyalcohol ethoxylates. PRODUCTION PROCESSES Washing processes throughout from fibre spinning to finished clothes. MAIN USE Tenside mix in detergents. COMMONLY APPLIED ON Alkylphenols Page 2

43 Recommended Restricted Substances QUATERNARY AMMONIUM COMPOUNDS Some examples of substances in this group Bis(hydrogenated tallow alkyl)dimethylchloride; (DHTDMAC) CAS No: Distearyl-dimethylammoniumchloride; (DODMAC; DSDMAC) CAS No: bis(hydrogenated-tallow-alkyl)-dimethylammoniumchloride; (DTDMAC) CAS No: N,N-Dimetyl-N-benzyl-N-dodecylammoniumklorid CAS No: These compounds are cationic tensids that may be used in detergents, as antistatic agents or biocides in various steps in the processes of textiles and clothing. In the dyeing process, quaternary ammonium compounds may be used as egalising agents to improve dyeing process and even dyeing result, and as retarders in dyeing of acrylic fibres. In the finishing process, quaternary ammonium compounds may be used as fabric softeners and as an agent to improve colour fastness. They are at present mainly used in auto care products. DTDMAC seems to be most frequently used of these substances. LEGAL REGULATIONS European Union: Regulation (EC) No 648/2004 of the European Parliament and of the Council of 31 March 2004 on detergents requires that tensids must fulfil certain degradability criteria to be used in products. European Union: Biocides are subject to authorization according to the Biocidal Products Directive (BPD (98/8/EC)). RECOMMENDED REGULATION Quaternary ammonium compounds shall not be used in. HARMFUL HEALTH EFFECTS A number of quaternary ammonium compounds can cause skin irritation and sensitization. POSSIBLE EFFECTS ON THE ENVIRONMENT Tensids are mainly spread through effluent water, and can be found bound to particles in sediments and sludge.the three quaternary ammonium compounds DHTDMAC, DSDMAC and DTDMAC are slowly degradable in the environment and toxic to water and sediment dwelling organisms. METHOD OF ANALYSES Gas chromatography coupled with mass spectroscopy (GC-MS) screening. Samples are extracted and analysed in reversed phase HPLC system coupled with mass spectrometer Quaternary ammonium compounds

44 Recommended Restricted Substances PRODUCTION PROCESSES These compounds may be used in detergents, as antistatic agents or biocides in various steps in the processes of textiles and clothing. Also used to improve dyeing process and even dyeing result. May be used in the finishing process as fabric softeners. MAIN USE / COMMONLY APPLIED ON Mainly used as tensids. Can be applied on all types of textiles. POSSIBLE SUBSTITUTES Other types of tensids Quaternary ammonium compounds

45 Recommended Restricted Substances ORGANIC SOLVENTS Some examples of substances in this group Benzene CAS No ,1,2-Trichloroethane CAS No ,1,1-Trichloroethane CAS No Toluene CAS No N,N-Dimethylformamide CAS No Solvents are liquids (solids or gases) that dissolve other liquids, solids or gaseous solutes resulting in a solution. Solvents normally have a low boiling point and evaporate easily. Solvents are widely used in industry as well as in consumer sector, and are important components in a number of products for instance glues and paints. Approximately every tenth employee is in contact with solvents daily in his work. Solvents may be used in a number of processes in the of textiles and clothing; for instance printing. LEGAL REGULATIONS EU: Council Directive 1999/13/EC on the limitation of emissions of volatile organic compounds due to the use of organic solvents in certain activities and installations. Most organic solvents are hazardous and must be classified and labelled accordingly. RECOMMENDED REGULATION Organic solvents shall not be used in the of textiles and clothing. HARMFUL HEALTH EFFECTS Solvents enter the body via inhalation and through the skin barrier. There are a large number of different solvents with different properties; some can cause serious health problems. The most serious health effects are permanent, not curable and develop over a long period. Brain and nervous system damages, cancer, impaired fertility and abortion, kidney and liver damages, tiredness, dizziness and skin problems are effects caused by organic solvents. POSSIBLE EFFECTS ON THE ENVIRONMENT Spill and discharges of solvents may contaminate soil and waterways and affect organisms living in these media. Some solvents react with other atmospheric gases and form more hazardous gases. METHOD OF ANALYSES Gas chromatography coupled with mass spectroscopy (GC-MS) screening. Samples are extracted and analysed in reversed phase HPLC system coupled with mass spectrometer Organic solvents

46 Recommended Restricted Substances PRODUCTION PROCESSES Organic solvents may be used in several processes, e.g. in stain removal and printing. POSSIBLE SUBSTITUTES Less hazardous solvents. Water thinned systems may be an option. MAIN USE / COMMONLY APPLIED ON Mainly used as solvents Commonly applied on all types of textiles and clothing Organic solvents

47 Recommended Restricted Substances CARRIERS Some examples of substances in this group Monochlorobenzene CAS No ,2,4-Trichlorobenzene CAS No o-chlorotoluene CAS No Chloroethene CAS No Naphthalene CAS No Biphenyl CAS No Dimethylphthalate CAS No Carriers are mainly used in the dyeing process of polyester and other synthetic fibres especially textiles made of blends of wool and synthetic fibres. They are applied to increase dyeing speed of disperse dyes. A number of different chemicals can be applied as carriers phenolic derivates, aromatic hydrocarbons, chlorinated hydrocarbons, esters of aromatic carboxylic acid, etc. Trade products are mixtures of different carriers, in preparations that also contain disperging or emulgating agents and possibly solvents. LEGAL REGULATIONS 1,2,4-Trichlorobenzene EU REACH: Shall not be placed on the market or used as a substance or constituent of preparations in a concentration equal to or higher than 0,1 % by mass for all uses except: as an intermediate of synthesis, or as a process solvent in closed chemical applications for chlorination reactions, or in the manufacture of 1,3,5-trinitro-2,4,6-triaminobenzene (TATB). RECOMMENDED REGULATION Carriers that are stated in the list shall not be used in the of textiles and clothing. HARMFUL HEALTH EFFECTS Carriers is a mixed group of chemicals with different properties. Some carriers are toxic and some have long term effects; for instance chloroetene is classified carcinogenic. There are lacking data on some substances that are used as carriers. POSSIBLE EFFECTS ON THE ENVIRONMENT Some carriers are persistent, some are also bioaccumulating; others are rapidly decomposed in the environment. Acute aquatic toxicity varies some are very toxic; some also show chronic toxicity in tests. METHOD OF ANALYSES Gas chromatography coupled with mass spectroscopy (GC-MS) screening. Samples are extracted and analysed in reversed phase HPLC system coupled with mass spectrometer Carriers

48 Recommended Restricted Substances PRODUCTION PROCESSES Dyeing of polyester and other synthetic fibres MAIN USE / COMMONLY APPLIED ON Mainly used as carriers. Commonly applied on synthetic fibres. POSSIBLE SUBSTITUTES Carriers can to a certain extent be substituted by other dyeing processes. High temperature dyeing do not require carriers, but cannot be applied in dyeing fabrics containing wool and other delicate fibres. Chlorinated carriers shall not be used Carriers

49 Restricted Substances List AZO COLOURANTS THAT CAN FORM CARCINOGENIC ARYLAMINES Azo colourants; azo dyestuffs and pigments, are used inn the dyeing and printing of textiles. It is the largest group of synthetic colourants, representing approximately 70 % of the organic dyestuffs on the market. Azo dyestuffs are found in several classes of dyes Acid, Basic, Direct, Disperse, Food, Mordant, Reactive or Solvent dyestuffs, and are applied in dyeing of cotton, silk, wool, viscose and synthetic fibres, as well as leather. Thousands of azo dyes exist there are approximately 2000 different azo colourants on the market. Only those that can degrade to form one or more of the arylamines listed are restricted. Colourants are in general persistent under aerobic conditions Legal regulations: Azo dyes which, by reductive (anaerobic) cleavage of one or more azo groups, may release one or more of aromatic amines listed in Appendix 8 to REACH regulation, in detectable concentrations, i.e. above 30 ppm in the finished article or in the dyed parts thereof, according to the testing methods listed below, shall not be used in textile and leather articles which may come into direct and prolonged contact with the human shin or oral cavity, such as: o Clothing, bedding, towels, hairpieces, wigs, nappies and other sanitary items, sleeping bags, o Footwear, gloves, wristwatch straps, handbags, purses/wallets, briefcases, chair covers, purses worn round the neck, o Textile or leather toys and toys which include textile or leather garments, o Yarn and fabrics intended for use by the final consumer. Recommended requirements: Azo colourants that can be broken down to carcinogenic arylamines shall not be used in or any other processes of any part of products purchased by Varner Group. Harmful health effects The colouring azo group of these dyes can be decomposed by reductive cleavage (anaerobic degradation) or through enzymatic action to aromatic amines (arylamines) that may cause cancer. Arylamines can be absorbed through the skin and accumulated in the body. Some arylamines are also allergenic. Most azo colourants are water soluble, and easily degradable. Possible effects on the environment Most azo colourants require anaerobic (reductive) conditions Some arylamines are toxic or very toxic to aquatic organisms and can cause long-term damage in the aquatic environment. Several arylamines are not readily degradable, but can stay in the environment for a long time. The arylamines ability to bioaccumulate differs considerably. The majority seems not to be potential bioaccumulative Azocolourants Page 1

50 Restricted Substances List Methods of analyses CEN ISO/TS 17234:2003 Leather Chemical tests Determination of certain azocolourants in dyed leathers. EN :2003 Textiles Methods for the determination of certain aromatic amines derived from azo colourants Part 1: Detection of the use of certain azo colourants accessible without extraction. EN :2003 Textiles Methods for the determination of certain aromatic amines derived from azo colourants Part 2: Detection of the use of certain azo colourants accessible by extracting the fibres. Alternative method: German method B Alternative method: French method XP G Gas chromatography coupled with mass spectroscopy (GC-MS) screening. POSSIBLE SUBSTITUTES Colourants that do not form carcinogenic or allergenic compounds. Sulphonated azo dyes may be alternative, since their degradation products do not seem to possess the same carcinogenic potential as the aromatic amines. PRODUCTION PROCESSES Dyeing MAIN USE Dyeing of cotton, but also other fibres. COMMONLY APPLIED ON Fabrics with strong, clear colours. The main risk factors are domestically produced dyes in Far Eastern countries qualities produced in Western countries are normally of no problem Azocolourants Page 2

51 Restricted Substances List DISPERSE COLOURANTS Disperse dyes are the main dyes for dyeing cellulose acetate fibres and synthetic fibres like polyester and polyamide. To achieve good results in dyeing synthetic fibres, the application of carriers are required; provided that dyeing temperature is not exceeding 110 C. Disperse colourants are quite little soluble in water, and are used as water dispersions with fine particles. Usually, an anionic dispersing agent is added. Disperse colourants are also applied in printing on synthetic textiles, often with transfer print technique. The number of disperse colourants is high, with varied properties. Approximately half of the disperse colourants are azo colourants; some of these can cleave off azo groups. Most of the disperse dyes that are listed have potential negative properties they can cause cancer or allergy. Legal regulations: According to our current knowledge, there are no legal regulation of disperse colourants applied in textiles. Recommended requirements: Disperse dyes that are classified carcinogenic and/or allergenic/sensitising shall not be used in the of raw materials or finished products. Harmful health effects Previously, dispersion dyes often caused skin allergies known as stocking allergy. Allergies caused by these dyes are seldom today, but a number of dispersion dyes can cause allergy, and should be avoided in use. Some disperse dyes can cause cancer. Some of these are azo colourants which may undergo reductive cleavage of one or more azo groups, and release one or more carcinogenic arylamines. Possible effects on the environment Colourants are generally persistent under aerobic conditions. Tests have indicated that some disperse dyes may bioaccumulate, and some shows high octanol/water partition coefficients (log K ow ). However, these dyes have low solubility in water, and will therefore probably not bioaccumulate due to their low bioavailability. Some disperse dyes are acute toxic to fish. Methods of analyses The determination of aromatic amines (arylamines) derived from azo colourants shall be carried out according to method EN :2003 or EN : Disperse colourants Page 1

52 Restricted Substances List Other organic compounds can be analysed using capillary gaschromatography combined with massspectrometry (GC-MS). Organic dyestuffs can be analysed using thin layer chromatography (TLC). POSSIBLE SUBSTITUTES Disperse colourants that do not cause allergy or cancer. PRODUCTION PROCESSES Printing and dyeing. MAIN USE Dyeing of synthetic fibres, mainly polyester and polyamide. COMMONLY APPLIED ON Synthetic fibres and cellulose acetate fibres Disperse colourants Page 2

53 Recommended Restricted Substances ACID DYES Some examples of substances in this group C.I. Acid Black 48; C.I CAS No C.I. Acid Red 85; C.I CAS No C.I. Acid Orange 45; C.I CAS No Nylon and protein fibres like wool and silk are dyed with acid dyes. Acid dyes are complex organic molecules with an anionic part being the colouring component that is attracted to cationic sites on the fiber. LEGAL REGULATIONS A number of acid dyes are classified carcinogenic and/or allergenic in accordance with European hazard classification and labelling rules. RECOMMENDED REGULATION Acid dyes that are classified carcinogenic and/or sensitising/allergenic shall not be used in the of textiles and clothing. HARMFUL HEALTH EFFECTS The complex molecular structure of organic dyes do that many of them have the potential to be metabolised in the body to hazardous compounds that can cause serious health effects; for instance allergy and cancer. The dye itself may not be harmful, but some intermediates used in the of the dyes are identified as toxic. POSSIBLE EFFECTS ON THE ENVIRONMENT Generally, dyes are quite persistent and not readily decomposed under aerobic conditions. However, most dye molecules are big and insoluble in water, which means that they are not or only limited bioavailable. Acid dyes are not bioaccumulative, but can be toxic to fish. METHOD OF ANALYSES Gas chromatography coupled with mass spectroscopy (GC-MS) screening. Samples are extracted and analysed in reversed phase HPLC system coupled with mass spectrometer Acid dyes

54 Recommended Restricted Substances PRODUCTION PROCESSES Dyeing POSSIBLE SUBSTITUTES Dyes with less hazardous properties. MAIN USE / COMMONLY APPLIED ON Mainly used as dyes Commonly applied on protein fibres (wool, silk) and polyamid (nylon) Acid dyes

55 Recommended Restricted Substances CATIONIC DYES Some examples of substances in this group C.I. Basic Violet 14; C.I CAS No C.I. Basic Red 12; C.I CAS No C.I. Basic Green 4; C.I CAS No / Cationic dyes are mainly used in dyeing of acrylic fibres silk may also be dyed with these dyes. Cationic dyes were previously called basic dyes, and have been applied on wool, silk and cotton; however, the colour fastness is not very good for these fibres dyed with cationic dyes. Dyeing polyacrylic fibres with these dyes give brilliant colours with good light fastness etc. LEGAL REGULATIONS A number of cationic dyes are classified carcinogenic and/or allergenic in accordance with European hazard classification and labelling rules. RECOMMENDED REGULATION Cationic dyes that are classified carcinogenic and/or sensitising/allergenic shall not be used in the of textiles and clothing. HARMFUL HEALTH EFFECTS The complex molecular structure of organic dyes do that many of them have the potential to be metabolised in the body to hazardous compounds that can cause serious health effects; for instance allergy and cancer. The dye itself may not be harmful, but some intermediates used in the of the dyes are identified as toxic. Serious manufacturers of dyes avoid the use of such intermediates, so the problem today is smaller than earlier. POSSIBLE EFFECTS ON THE ENVIRONMENT Generally, dyes are quite persistent and not readily decomposed under aerobic conditions. However, most dye molecules are big and insoluble in water, which means that they are not or only limited bioavailable. In general, cationic dyes are toxic for aquatic organisms. METHOD OF ANALYSES Gas chromatography coupled with mass spectroscopy (GC-MS) screening. Samples are extracted and analysed in reversed phase HPLC system coupled with mass spectrometer Cationic dyees

56 Recommended Restricted Substances PRODUCTION PROCESSES Dyeing POSSIBLE SUBSTITUTES Dyes with less hazardous properties. MAIN USE / COMMONLY APPLIED ON Mainly used as dyes Commonly applied on polyacrylic fibres Cationic dyees

57 Recommended Restricted Substances DIRECT (SUBSTANTIVE) DYES Some examples of substances in this group C.I. Direct Black 38; C.I CAS No C.I. Direct Blue 6; C.I CAS No C.I. Direct Brown 95; C.I CAS No C.I. Direct Red 28; C.I CAS No Direct dyes are applied in dyeing processes where dye molecules are attracted by physical forces at the molecular level to the fibres especially of cotton and regenerated cellulose. Sometimes these dyes are used in dyeing of wool, silk and polyamide. These are water soluble organic dyes a majority is azo colourants with one or more azo group(s). LEGAL REGULATIONS A number of direct dyes are carcinogenic, teratogenic and/or allergenic and shall be classified and labelled in accordance with European hazard classification and labelling rules. RECOMMENDED REGULATION Direct dyes that are classified carcinogenic, teratogenic and/or sensitising/allergenic shall not be used in the of textiles and clothing. HARMFUL HEALTH EFFECTS The complex molecular structure of organic dyes do that many of them have the potential to be metabolised in the body to hazardous compounds that can cause serious health effects; for instance allergy and cancer. The dye itself may not be harmful, but some intermediates used in the of the dyes are identified as toxic. POSSIBLE EFFECTS ON THE ENVIRONMENT Generally, dyes are quite persistent and not readily decomposed under aerobic conditions. However, most dye molecules are big and insoluble in water, which means that they have only limited or no bioavailability. METHOD OF ANALYSES Gas chromatography coupled with mass spectroscopy (GC-MS) screening. Samples are extracted and analysed in reversed phase HPLC system coupled with mass spectrometer Direct dyes

58 Recommended Restricted Substances PRODUCTION PROCESSES Dyeing POSSIBLE SUBSTITUTES Dyes with less hazardous properties. MAIN USE / COMMONLY APPLIED ON Mainly used as dyes Commonly applied on cotton and regenerated cellulose fibres Direct dyes

59 Restricted Substances List FORMALDEHYDE CAS No: Formaldehyde is widely used in different industries, and is formed by incomplete combustion. In apparel and textiles, formaldehyde and formaldehyde based polymer resins (e.g. phenol-formaldehyde and urea-formaldehyde) are used in different processes in the of fibre and textiles; in fibre reinforcement, dyeing, shrink proof treatment, water and dirt repellent treatment, etc. Formaldehyde can primarily be found in textiles made of cotton, viscose or mixtures with polyester. Legal regulations: NORWAY: It is prohibited to manufacture, import, export or sale textiles that contain free and partly hydrolysed formaldehyde exceeding following limits: o Textiles for children under age two years: 30 mg/kg textile o Textiles that normally do come into direct contact with skin: 100 mg/kg textile o Textiles that normally do not come into direct contact with skin: 300 mg/kg textile. Formaldehyde shall be labelled with hazard symbol Toxic (T) and corresponding risk phrases. Recommended requirements: Maximum accepted concentration limits of formaldehyde, free and partly hydrolysable, in finished textiles and clothing: o In textiles for children and textiles that normally come in direct contact with skin: 30 mg per kg textile (30 ppm) o In textiles that normally do not come in direct contact with skin: 100 mg per kg textile (100 ppm) Harmful health effects Formaldehyde is toxic, allergenic, corrosive and suspected human carcinogen. It is a strong irritant to the eyes, nose and throat; also irritating skin. Possible effects on the environment Formaldehyde is very toxic to aquatic organisms Formaldehyde is not persistent it degrades to formic acid. Methods of analyses EN ISO :1998 Textiles - Determination of formaldehyde - Part 1: Free and hydrolyzed formaldehyde (water extraction method). This Part of ISO specifies a method for determining the amount of free formaldehyde and formaldehyde extracted partly through hydrolysis by means of a water extraction method. The method can be applied to the testing of textile samples in any form. The procedure is intended for use in the range of free and hydrolysed formaldehyde on the fabric between 20 mg/kg and 3500 mg/kg when determined by this method. The lower limit is 20 mg/kg. Below this limit the result is reported as not detectable. Gas chromatography coupled with mass spectroscopy (GC-MS) screening Formaldehyde Page 1

60 Restricted Substances List. POSSIBLE SUBSTITUTES Resins based on cyclic urea derivate binds directly to the fibre, and gives less formaldehyde emission than the use of ureaformaldehyde or melaminformaldehyde resins. PRODUCTION PROCESSES Fibre reinforcement, dyeing, non-crease, water repellent, dirt repellent and unshrinkable treatment. MAIN USE. COMMONLY APPLIED ON Cotton Formaldehyde Page 2

61 Restricted Substances List NICKEL AND NICKEL COMPOUNDS Some examples of substances in this group: Metallic nickel CAS No: Nickel sulphate CAS No: Nickel acetate CAS No: Metallic nickel is widely used in nickel-plating, in various alloys to increase hardness and resistance to corrosion or to create attractive surfaces (e.g. new silver), in coins etc. and as a catalyst. Some nickel compounds may be used in dyeing and printing of fabrics with metal complex dyeing (of cellulose fibres). Nickel may also be a contamination in some colourants. In textiles, nickel is mainly associated with metal components, paints, inks, trims and plastic components. Legal regulations: Europe (EU + Norway, Iceland and Liechtenstein): Shall not be used in articles intended to come into direct and prolonged contact with the skin, among others; rivet buttons, tighteners, rivets, zippers and metal marks, when these are used in garments; if the rate of nickel released from the parts of these articles coming into direct and prolonged contact with the skin is greater than 0,5 µg/cm 2 /week. Nickel shall be labelled with hazard symbol Xn and risk phrases R Several nickel compounds shall be labelled with hazard symbol T and risk phrases R and others. Recommended requirements: Maximum accepted concentration of nickel in any part of a finished product is 4.0 ppm. Parts that may come in direct contact with skin shall comply with the European regulation. Harmful health effects Nickel and nickel compounds can cause nickel allergic contact dermatitis (nickel itch) in skin. It is estimated that % of women and 1 2 % of men are susceptible for this nuicance. Production of nickel can cause lung and nasal sinus cancer. Possible effects on the environment Several nickel compounds are toxic to aquatic organisms and can cause long lasting effects on the environment. Methods of analyses Standard test method to analyse the release of nickel from articles mentioned above, is EN Concentration of nickel in effluent water from dyeing can be analysed according to method ISO Nickel and nickel compounds Page 1

62 Restricted Substances List Elemental nickel in textiles can be analysed using flow injection inductively coupled plasma mass spectrometer (FI-ICP-MS) POSSIBLE SUBSTITUTES To avoid problems with nickel and its compounds, articles containing such substances should have a non-nickel coating that prevents release of nickel. PRODUCTION PROCESSES Nickel and nickel compounds are mainly used in the of buttons etc. Can be used in metal complex dyeing and some other textile dyeing processes. MAIN USE Used in the of buttons, rivets, zippers, metal marks etc. to give nice surface. COMMONLY APPLIED ON Jeans etc. Nickel and nickel compounds Page 2

63 Recommended Restricted Substances CHROMIUM COMPOUNDS Some examples of substances in this group Chromium CAS No Potassium dichromate CAS No Sodium chromate CAS No Sodium dichromate CAS No Chromium sulphate CAS No Chromium and chromium compounds have a wide variety of uses; in metal alloys (e.g. in stainless steel), in electroplating (chrome plating), wood preservatives, pigments, catalysts, and refractory materials. Chromium compounds are used in pigments, dyeing processes and not least in leather currying. Chromium is mainly present in two versions trivalent (Cr 3+ ) and hexavalent (Cr 6+ ). Hexavalent chromium is the most toxic for human health and the environment, and can cause a number of effects. Cr 6+ may be formed through oxidation of Cr 3+. LEGAL REGULATIONS Chromium compounds shall be classified and labelled in accordance with hazard classification and labelling regulations. Several chromium compounds are classified carcinogenic, mutagenic, allergenic, acute toxic to humans, oxidising, and acute toxic for aquatic organisms and potential bioaccumulating, and shall be labelled with hazard symbols and risk phrases according to this. Norway: Chromium is banned in wood impregnation (CCA copper, chromium and arsenic). RECOMMENDED REGULATION Hexavalent chromium (Cr 6+ ) and compounds and salts of this: Maximum concentration: 0.1 ppm (0.1 mg/kg) in any part of finished product. Chromium in skin and leather: Max. 3.0 ppm Trivalent chromium (Cr 3+ ) and compounds and salts of this: Maximum concentration: 2.0 ppm (2.0 mg/kg) in any part of finished product. HARMFUL HEALTH EFFECTS Chromium is an essential element in the human body. However, a number of chromium compounds are carcinogenic, mutagenic, toxic to re, acutely very toxic, allergenic if inhaled or in contact with skin, and chronic toxic. Chromium compounds are slowly degraded and can accumulate in the body. POSSIBLE EFFECTS ON THE ENVIRONMENT A number of chromium compounds are very toxic to aquatic organisms both acute and long term. Such compounds are slowly degradable, and show high potential for bioaccumulation METHOD OF ANALYSES Chromium is analysed using atomic absorption spectrophotometer (AAS) or ICP-MS (inductive plasma-mass coupled spectrometry) Chromium and chromium compounds

64 Recommended Restricted Substances PRODUCTION PROCESSES Dyeing and printing of textiles. Currying of leather and hides. MAIN USE / COMMONLY APPLIED ON Mainly used as a component in dyes, especially in metal complex dyes for dyeing wool (may be not common in Europe any longer). Also used in a number of pigments. Commonly applied on treatment of leather and hides. POSSIBLE SUBSTITUTES Avoid chromium-complex dyeing processes and chromium based pigments. Use pigments without chromium. There are chromium free currying processes available for leather Chromium and chromium compounds

65 Recommended Restricted Substances ORGANOTIN COMPOUNDS Some examples of substances in this group: Tributyltin (TBT) CAS No: Tributyltin oxide CAS No Triphenyltin CAS No Dibutyltin oxide CAS No Tetraoctyltin CAS No Organotin compounds have been widely used as biocides to control a broad spectrum of organisms; for instance as antifouling agents for boats and as antifungal agent in textiles and industrial water systems. LEGAL REGULATIONS EU: Biocides are subject to authorization according to The Biocidal Products Directive (BPD (98/8/EC)) EU - REACH: Organostannic compounds shall not be placed on the market or used as substances and constituents of preparations which act as biocides to prevent the fouling by micro-organisms, plants or animals of: (a) all craft irrespective of their length intended for use in marine, coastal, estuarine and inland waterways and lakes; (b) cages, floats, nets and any other appliances or equipment used for fish or shellfish farming; (c) any totally or partly submerged appliance or equipment. Norway: Manufacture, import, export, sell and use substances or preparations containing compounds of tributyltin or triphenyltin. RECOMMENDED REGULATION Organotin compounds should not be used in the. The maximum acceptable total concentration of organotin compounds should be set to 2.5 mg per kilo clothing (2.5 ppm). HARMFUL HEALTH EFFECTS A number of organotin compounds are toxic to humans. Some compounds can cause immunosuppression which may lead to secondary infections. POSSIBLE EFFECTS ON THE ENVIRONMENT A number of organotin compounds are very toxic to aquatic organisms and warm blooded animals. These substances are persistent and bioaccumulative, and can cause long term effects. Some of these substances are causing hormonal changes; dog whelks become infertile because females develop male sexual characteristics. METHOD OF ANALYSES Gas chromatography coupled with mass spectroscopy (GC-MS) screening. Samples may also be extracted and analysed in reversed phase HPLC system coupled with mass spectrometer Organotin compounds

66 Recommended Restricted Substances PRODUCTION PROCESSES Biocide to protect against moulds. MAIN USE / COMMONLY APPLIED ON Mainly used as biocides POSSIBLE SUBSTITUTES Less hazardous pesticides or better storage and transport that do not cause fungus attack Organotin compounds

67 Restricted Substances List BROMINATED FLAME RETARDANTS Some examples of substances in this group: Pentabromodiphenylether; (pentabde) CAS No Octabromodiphenylether; (octabde) CAS No Tris-(2,3-dibromopropyl)-phosphate ; (TRIS; TrisBP) CAS No Polybrominated biphenyles; (PBB) CAS No ,1'-Oxybis(2,3,4,5,6-pentabromo)-benzene; (deca-bromodiphenylether; dekabde) CAS No Hexabromocyclododecane; (HBCDD) CAS No , ,3-Dibromo-1-propanol-hydrogenphosphate CAS No ,2-bis(Bromomethyl)-1,3-propanediol; (Dibromoneopentyl glycol) CAS No Tetrabromobisphenol A; (TBBP-A) CAS No The use of flame retardants do not prevent fire, but delay the catch of a fire in a material. Some flame retardants are permanently fixed to the fibres others are easily washed off. Clothes for consumers should normally not be treated with chemical flame retardants, but rather be produced of fibres that do not readily catch fire. Legal regulations: REACH: Tris (2,3 dibromopropyl) phosphate, and polybrominatedbiphenyls shall not be used in textile articles intended to come into contact with the skin. REACH: Diphenylether, pentabromo derivative, C 12 H 5 Br 5 O, and diphenylether, octabromo derivative, C 12 H 2 Br 8 O: Articles may not be placed on the market if they, or flame-retarded parts thereof, contain one of these substances in concentrations higher than 0,1 % by mass. Norway: In addition to regulations reported above, dekabde shall not be used in textile articles intended to come into contact with the skin. PentaBDE shall be labelled with hazard symbols for harmful (Xn) and environmental (N) hazards with corresponding risk phrases. OctaBDE shall be labelled with hazard symbol toxic (T) with risk phrases warning against damage to re and the unborn child. Please observe that in Norway, highly flammable textiles are banned. Recommended requirements: Brominated flame retardants shall not be used in the of any goods for the group. Harmful health effects Brominated flame retardants are not acute toxic to man, but some can cause liver damage. Some brominated flame retardants are suspected to cause hormone disrupting effects and to cause damage of the nervous system Brominated flame retardants Page 1

68 Restricted Substances List Possible effects on the environment Several brominated flame retardants are persistent and can be accumulated in the food chain. Some of them are toxic to water dwelling organisms. Methods of analyses Brominated flame retardants can be analysed using inductively coupled plasma mass spectrometry (ICP-MS). POSSIBLE SUBSTITUTES Clothes for consumer market normally do not need to be treated with flame retardants. It is possible to reduce flammability of clothes and textiles in other ways than by applying chemical flame retardants. Use of chemical flame retardants may affect other characteristics of the textiles. Alternatives may be the use of fibres that do not readily catch fire or treatment with e.g. phosphorus or nitrogen based compounds. PRODUCTION PROCESSES Finishing treatment. MAIN USE Flame retardants. COMMONLY APPLIED ON Garments to be used under special conditions. According to literature, polybrominated biphenyles (PBB) and tris-(2,3-dibromopropyl)-phosphate (TrisBP) are no longer commercially available Brominated flame retardants Page 2

69 Recommended Restricted Substances NON-BROMINATED FLAME RETARDANTS Some examples of substances in this group: Tris-(aziridinyl)-phodphinoxide (TEPA) CAS No: Short-chained chlorinated paraffins (SCCPs; chloroalkanes, C10-13) CAS No: Medium-chained chlorinated paraffins, C14-C17 (MCCPs) CAS No: Paraffin waxes and hydrocarbon waxes, chlorinated CAS No: Phosphoric acid, tris(2-methylphenyl)-ester CAS No: ,3-Dichloro-2-propanol-phosphate (3:1) (Tris(1,3-dichloro-2-propyl)-phosphate; TDCP) CAS.No: Tris(2-chloroethyl)-phosphate (Ethanol, 2-chloro-, phosphate (3:1); TCEP) CAS No: Potassium hexafluorozirconate CAS No: Potassium hexafluorotitanate CAS No: Antimony trioxide CAS No: The use of flame retardants do not prevent fire, but delay the catch of a fire in a material. Some flame retardants are permanently fixed to the fibres others are easily washed off. Clothes for consumers should normally not be treated with chemical flame retardants, but rather be produced of fibres that do not readily catch fire. There are many different types of flame retardants that do not contain bromine. Short-chained chlorinated paraffins (SCCPs) and medium chained chlorinated paraffins (MCCPs) are complicated mixtures with varying chain length and chlorine content. LEGAL REGULATIONS REACH: Short-chain chlorinated paraffins (SCCPs) shall not be placed on the market for use as substances or as constituents of other substances or preparations in concentrations higher than 1 % for fat liquoring of leather. REACH: SCCPs are proposed to be subject to authorisation. Norway: SCCPs banned - preparations and articles containing more than 0,1 % (weight) cannot be sold. RECOMMENDED REGULATION Shall not be used in the of clothes or any other products. HARMFUL HEALTH EFFECTS SCCP are suspected human carcinogens Non-brominated flame retardants

70 Recommended Restricted Substances POSSIBLE EFFECTS ON THE ENVIRONMENT Short-chained chlorinated paraffins are very toxic to aquatic organisms. They have strong bioaccumulative potential, are persistent and can cause long term effects in the environment. Combustion of chlorinated paraffins can give products toxic to the environment. SCCP can be transported long distances in air. METHOD OF ANALYSES Capillary column gas chromatography-massspectrometry (GC-MS). PRODUCTION PROCESSES Finishing treatment. MAIN USE / COMMONLY APPLIED ON Mainly used as flame retardants. Commonly applied on garments to be used under special conditions. POSSIBLE SUBSTITUTES Clothes for consumer market normally do not need to be treated with flame retardants. It is possible to reduce flammability of clothes and textiles in other ways than by applying chemical flame retardants. Use of chemical flame retardants may affect other characteristics of the textiles. Alternatives may be the use of fibres that do not readily catch fire or treatment with e.g. phosphorus or nitrogen based compounds Non-brominated flame retardants

71 Restricted Substances List PHTHALATES Some examples of substances in this group: Bis (2-ethylhexyl) phthalate; (DEHP) CAS No: Dibutyl phthalate, (DBP) CAS No: Benzyl butyl phthalate; (BBP) CAS No: Di-isononyl phthalate; (DINP) CAS No: , Di-isodecyl phthalate; (DIDP) CAS No: , Di-n-octyl phthalate; (DNOP) CAS No: Di-iso-butyl phthalate; (DIBP) CAS No: Dimethyl phthalate; (DMP) CAS No: Phthalates are widely used as plasticisers in plastic, and are found in a wide range of products in our daily life. Phthalates may be used in a number of process steps in the of textiles mainly as carriers in dyeing, as plasticisers for plastisol prints, PVC coating and synthetic fibres, and as a fixing agent. Legal regulations: Europe (EU + Norway, Iceland and Liechtenstein): DEHP, DBP and BBP shall not be found in plasticised parts of toys and childcare articles in higher concentrations than 0,1 % by mass. Europe (EU + Norway, Iceland and Liechtenstein): DINP, DIDP and DNOP shall not be found in higher concentration than 0,1 % by mass of plasticised material in toys and childcare articles which can be placed in the mouth by children. Europe (EU + Norway, Iceland and Liechtenstein): DBP and BBP and chemical products containing these substances, shall be labelled with hazard symbols Toxic (T) and Harmful for the environment (N) with corresponding risk phrases; DEHP and chemical products containing DEHP, shall be labelled with hazard symbol Toxic (T) and corresponding risk phrases. Europe (EU + Norway, Iceland and Liechtenstein): DEHP, DBP and BBP are banned in cosmetics. Recommended requirements: Phthalates shall not be used in the of any product lines. Harmful health effects A number of phthalates are reproductive toxicants. Some show hormone mimicrying properties and have adverse effects on sexual function and fertility, and some cause birth defects in the offspring. Animal tests with phthalates have shown damages in liver, kidneys and central nervous system. Possible effects on the environment Some phthalates are toxic or very toxic to aquatic organisms, and can cause long term effects in aquatic environment Phthalates Page 1

72 Restricted Substances List Phthalates are decomposed in water, more slowly in sediments. They can be bioaccumulated in organisms less in fish than in crayfish. Methods of analyses: Gas chromatography coupled with mass spectroscopy (GC-MS) screening. (ISO : Phthalate esters for industrial use -- Methods of test -- Part 1: General) POSSIBLE SUBSTITUTES Change to other printing techniques will be effective since these substances are mainly used as plasticisers in plastisol printing. Avoid PVC especially soft PVC in clothes and textiles. Use less hazardous plasticisers. Avoid use of carriers prefer high temperature dyeing where applicable. PRODUCTION PROCESSES Phthalates are not used in ordinary textile processes. MAIN USE Phthalates are primarily used as plasticisers in plastisol printing on textiles, but can be used as carriers in dyeing, and as plasticisers in PVC coating. COMMONLY APPLIED ON Printing on sweaters Phthalates Page 2

73 Recommended Restricted Substances PFOS AND RELATED COMPOUNDS Some examples of substances in this group Perfluorooctanesulfonic acid CAS No Perfluorooctanesulfonic acid, potassium salt CAS No Perfluorooctanesulfonic acid and related compounds are part of a big group of chemical substances called perfluorinated compounds (PFCs), which are fluorocarbon derivatives. PFCs have unique properties to make materials stain, oil and water resistant, and are widely used. PFOS and related compounds are exceptional stable, and have been used in fabric protectors, impregnation agents, fire-fighting foams, metal plating, and in semiconductor industry. American has been phased out, but PFOS and related substances are currently produced in China. LEGAL REGULATIONS EU s expert groups on hazard classification have proposed classification of PFOA as carcinogenic and toxic to re. Norway: PFOS is banned in fire-fighting foams, textiles and impregnating agents. RECOMMENDED REGULATION PFOS and related compounds shall not be used in the of textiles and clothing. HARMFUL HEALTH EFFECTS PFOS is toxic after repeated exposures; toxic to re; bind to proteins in blood and can bioaccumulate in the body. Some studies also show carcinogenic effect. POSSIBLE EFFECTS ON THE ENVIRONMENT PFOS and related compounds are very persistent and hardly decomposed in nature. These substances can bioaccumulate in the food chain and may be distributed globally. They are toxic to aquatic organisms and may cause long term effects in the aquatic environment. METHOD OF ANALYSES Gas chromatography coupled with mass spectroscopy (GC-MS) screening. Samples are extracted and analysed in reversed phase HPLC system coupled with mass spectrometer PFOS

74 Recommended Restricted Substances PRODUCTION PROCESSES Raw material for of fluoropolymers used in breathing, waterproof membranes in clothing. POSSIBLE SUBSTITUTES Other membrane materials. MAIN USE / COMMONLY APPLIED ON Mainly used as raw material for membranes in all weather clothing Commonly applied on jackets, trousers and shoes PFOS

75 Recommended Restricted Substances PERFLUOROOCTANOIC ACID (PFOA) AND PFOA COMPOUNDS Some examples of substances in this group Perfluorooctanoic acid CAS No Pentadecafluorooctyl chloride CAS No Perfluorooctanoic acid and related compounds are part of a big group of chemical substances called perfluorinated compounds (PFCs), which are fluorocarbon derivatives. PFCs have unique properties to make materials stain, oil and water resistant, and are widely used to finish textiles especially for waterproof clothing. Fluorocarbons are applied in textiles in wind and water resistant, breathing membranes; in water, oil and/or dirt repellent coatings. PFOA is probably not used today in the telomerisation today, but there may be some residual content in fluoropolymers. LEGAL REGULATIONS EU s expert groups on hazard classification have proposed classification of PFOA as carcinogenic and toxic to re. Norway is assessing a ban of PFOA in consumer products. RECOMMENDED REGULATION PFOA and PFOA compounds shall not be used in the of textiles and clothing. HARMFUL HEALTH EFFECTS PFOA is carcinogenic, and is associated with infertility in humans. In highly exposed groups, some studies have indicated effects like birth defects, increased cancer rates and changes in the immune system. PFOA is toxic by repeated dosing. POSSIBLE EFFECTS ON THE ENVIRONMENT PFOA is very persistent in the environment, being resistant to degradation by natural processes. Concentration of PFOA in wildlife is much lower than in humans. METHOD OF ANALYSES Gas chromatography coupled with mass spectroscopy (GC-MS) screening. Samples are extracted and analysed in reversed phase HPLC system coupled with mass spectrometer PFOA

76 Recommended Restricted Substances PRODUCTION PROCESSES Raw material for of fluoropolymers used in breathing, waterproof membranes in clothing. POSSIBLE SUBSTITUTES Other membrane material. MAIN USE / COMMONLY APPLIED ON Mainly used as raw material for membranes in all weather clothing Commonly applied on jackets, trousers and shoes PFOA

77 Recommended Restricted Substances DIISOCYANATES Some examples of substances in this group Toluene-2,4-diisocyanate (TDI) CAS No Methylene diphenyl diisocyanate (MDI) CAS No Diisocyanates are mainly used in of polyurethanes. Polyurethanes are widely used, inter alia in flexible foam in upholstery, bedding and automotive seating; rigid foam for thermal insulation (refrigerators and freezers), carpet underlay, varnishes, adhesives and sealants, footwear, and in waterproof and windproof coating of textiles. Polyurethanes are also used as synthetic fibres (spandex, elastane). LEGAL REGULATIONS Diisocyanates are classified and shall be labelled because of their hazardous properties. These substances are classified carcinogenic category 3 (Carc Cat 3 suspected human carcinogen), allergenic if inhaled or in contact with skin, and very toxic or harmful after acute or chronic exposure. Some are classified as very toxic (T+) others are classified harmful (Xn). RECOMMENDED REGULATION Diisocyanates shall not be used in. HARMFUL HEALTH EFFECTS Diisocyanates cause allergic reactions in susceptible persons at very low concentration, and often several hours after exposure has taken place. A number of diisocyanates are suspected human carcinogens, are irritating to skin, eyes and respiratory organs, and show acute as well as chronic toxicity. Some are very toxic. POSSIBLE EFFECTS ON THE ENVIRONMENT Some diisocyanates are hazardous for water dwelling organisms, and may cause long term damages in aquatic environment. METHOD OF ANALYSES Gas chromatography coupled with mass spectroscopy (GC-MS) screening. PRODUCTION PROCESSES Fiber and waterproof coating MAIN USE / COMMONLY APPLIED ON Mainly used as component in coating and fiber Commonly applied on textiles for waterproofing and windproofing. POSSIBLE SUBSTITUTES Use of other fibres. Other coating material Isocyanate

78 Restricted Substances List PENTACHLOROPHENOL (PCP) and its salts or esters Some examples of substances in this group: Pentachlorophenol CAS No: Pentachlorophenol, sodium salt CAS No: Pentachlorophenol, potassium salt CAS No: Pentachlorophenol (PCP) is a polychlorinated compound mainly used as a preservative to wood, leather and textiles. It may be used in the of fibres and textiles in dyeing, fibre reinforcement and antimicrobial treatment. PCP is also used as a preserving agent to protect finished goods from insects and moulds during storage and long sea-transports. PCP can be sprayed directly into transport containers when the transport begins. Technical grade PCP can be contaminated with 1-5 % phenoxyphenols like chlorinated dioxins and furans, compounds that are highly toxic and persistent. Imperfect combustion of PCP causes formation of chlorinated dioxins. PCP is the main source for dioxins in textiles; probably there are some contamination of some dyestuffs too. Legal regulations: REACH (EU + Norway, Iceland and Liechtenstein): Pentachlorophenol and its salts and esters shall not be used in concentration equal to or greater than 0,1 % by mass in substances or preparations placed on the market. Pentachlorophenol used alone or as a component of preparations must have a total hexachlorodibenzoparadioxin (HCDD) content of not more than two part per million (ppm). PCP and its salt shall be labelled with hazard symbols Very toxic (T+) and Harmful for the environment (N), and corresponding risk phrases warning the user. Norway: Prohibited to manufacture, import, export or trade textiles and leather containing more than 5 parts per million (ppm) pentachlorophenol, or its salts or esters. Recommended requirements: Shall not be used in the or during storage and transportation of any product. Marterials can be contaminated maximum accepted level is 2 ppm (2 mg per kilo material). Harmful health effects PCP and its salts or esters are very toxic if inhaled, swallowed or after contact with skin. They can cause eye and skin damages (contact dermatitis). Cause lung, liver and kidney damage. Can cause cancer. Burning PCP containing products may give highly toxic sunstances. Possible effects on the environment PCP is persistent in the environment and toxic to aquatic organisms PCP Page 1

79 Restricted Substances List Methods of analyses US EPA 8270 or equivalent There is an official German test method. High pressure liquid chromatography (HPLC) with UV detection at 254 nm. Gas chromatography coupled with mass spectroscopy (GC-MS) screening. POSSIBLE SUBSTITUTES Must be substituted with less persistent and less toxic compounds. PRODUCTION PROCESSES. MAIN USE Preservative. COMMONLY APPLIED ON PCP Page 2

80 Recommended Restricted Substances PESTICIDES NOT COVERED BY OTHER FACT SHEETS Some examples of substances in this group Dimethylfumarate (DMF) CAS No: Methylbromide CAS No: DDT CAS No: Dieldrin CAS No: Hexachlorobenzene CAS No: Lindane (γ-hch, including mixtures of isomers of HCH (BHC)) CAS No: ,4,5-T ((2,4,5-Trichlorophenoxy)acetic acid) CAS No: Parathion CAS No: Pesticides are substances or mixtures of substances intended for preventing, destroying or controlling any pest, or substances which may be administered to animals for the control of insects, arachnids or other pests in or on their bodies. The term includes substances intended for use as a plant growth regulator, defoliant, and substances applied to crops either before or after harvest to protect the commodity from deterioration during storage and transport. Annual of pesticides is approximately 2.3 million tonnes world wide. In this context, most pesticides that may be found in textiles, leather and clothing will normally be residues from application during growing plant or animal fibres, or from pre-shipment treatment of ready made products. LEGAL REGULATIONS EU: Pesticides are strictly regulated. The Council Directive 91/414/EEC states an authorisation procedure for active substances and products containing these substances. Each active substance has to be proven safe in terms of human health, including residues in the food chain, animal health and the environment, in order to be allowed to be marketed. It is the responsibility of industry to provide the data. There is a specific regulation on pesticide residues in food Regulation (EC) No 396/2005. RECOMMENDED REGULATION Pesticides or biocides shall not be added intentionally to any process in the of textiles and clothing, or during storage and transport. Maximum acceptable concentration is 2.0 mg per kilo textile (2.0 ppm). HARMFUL HEALTH EFFECTS There are many different chemicals with different characteristics within the pesticide group, and can cause a number of health effects. They can be dangerous to workers and farmers during use, and to consumers exposed to pesticide residues in products. The World Health Organization and the UN Environment Programme estimate that as many as 3 million workers in the developing countries experience severe poisoning from pesticides every year causing about deaths Andre pesticider

81 Recommended Restricted Substances POSSIBLE EFFECTS ON THE ENVIRONMENT Pesticides reduce biodiversity and can threaten endangered species. A major part of the pesticides applied do reach other destinations than their target species, for instance contaminating water. Some pesticides are persistent and can bioaccumulate in the food chain. METHOD OF ANALYSES US EPA 8081 A US EPA 8151 A US EPA 8141 A US EPA 8270 C Organochlorine pesticides, with ultrasonic or Soxhlet extraction and apolar solvents (iso-octane or hexane) Chlorinated herbicides, using methanol Organophosphorous compounds Semi-volatile organic compounds Gas chromatography coupled with mass spectroscopy (GC-MS) screening Samples are extracted and analysed in reverse phase HPLC system coupled with mass spectrometer PRODUCTION PROCESSES Production of natural fibres. To protect against microorganisms and to prevent damage during transport. POSSIBLE SUBSTITUTES Less hazardous chemicals. MAIN USE / COMMONLY APPLIED ON Mainly used as pesticides and biocides. Commonly applied on natural fibres and textiles containing such fibres Andre pesticider