ECOLOGICAL CONSIDERATIONS, PARAMETERS AND TESTING

Transcription

1 ECOLOGICAL CONSIDERATIONS, PARAMETERS AND TESTING FOR THE TEXTILE INDUSTRY A TREATISE BY Ver : June

2 PREFACE This is essentially a compilation of information from various sources, both personal and published. A very large number of books, magazines, articles and the Internet were consulted for the preparation of this booklet and it is not possible for us to acknowledge all of these individually here. The main source of information however remains our own research and work over the past several years on Ecological Testing for the European market. It includes our own experimental findings and experiences of over 125,000 samples tested so far at our laboratory in India. Information has also been gathered from some of the retailers and brands whom we test for and we thank them for their support. This information would be useful to all engaged in the export of textile merchandise to the EU and the US. Information given in this booklet is given in good faith and for information of the reader. We cannot accept any liability arising from the same. In the interest of the scientific community and knowledge sharing in the textile field, we would wholeheartedly welcome suggestions, comments and information regarding errors and omissions that may be noticed. Please contact us at: thane@texanlab.com with your comments. Rahul Bhajekar Managing Director 2

3 TABLE OF CONTENTS TABLE OF CONTENTS INTRODUCTION TYPICAL ECO REQUIREMENTS IN EUROPE BACKGROUND BUYERS REQUIREMENTS / RSLS EU REGULATIONS GERMAN REGULATIONS RESTRICTED SUBSTANCES LISTS PARAMETERS IN DETAIL BANNED AMINES IN AZO DYES ALLERGENIC DISPERSE DYES CARCINOGENIC DYES NAVY BLUE (BLUE COLOURANT) PENTACHLOROPHENOL (PCP) & TETRACHLOROPHENOL (TECP) ORTHOPHENYLPHENOL (OPP) HEAVY METAL RESIDUES / TOTAL HEAVY METAL CONTENT HEAVY METALS, EXTRACTABLE TOTAL HEAVY METALS NICKEL RELEASE IN EXTENDED WEAR ORGANOTIN COMPOUNDS CHLORINATED ORGANIC CARRIERS FORMALDEHYDE GLYOXAL ALKYL PHENOL ETHOXYLATES FLUOROCARBONS PFOS AND PFOA PHTHALATES POLYVINYL CHLORIDE (PVC) PH OF AQUEOUS EXTRACT RESIDUAL PESTICIDES FLAME RETARDANTS POLYCHLORINATED BIPHENYLS (PCBS) AND POLYCHLORINATED TERPHENYLS (PCTS) POLYAROMATIC HYDROCARBONS DIOXINS & FURANS CHLORINATED PARAFFINS DIMETHYL FORMAMIDE (DMF) DIMETHYL FUMARATE (DMFU) ACRYLAMIDE OTHERS CPSIA LEAD AND PHTHALATE COMPLIANCE LEGISLATION ON LEAD (SEC. 101):

4 LEGISLATION ON PHTHALATES (SEC. 108): REACH & SVHCS REACH SVHC CANDIDATE LIST AS ON 16 JUNE GREENPEACE: DIRTY LAUNDRY REPORTS AND JOINT ROAD MAP ECO LABELS GLOBAL ORGANIC TEXTILE STANDARD (GOTS) ADSORBABLE ORGANIC HALOGENS (AOX) BIODEGRADABILITY & BIOACCUMULATION TOXICITY AQUATIC TOXICITY ACUTE TOXICITY: ORAL (LD 50) THE EU ECO LABEL: THE FLOWER CRITERIA INTRODUCTION FOR WHICH PRODUCTS CAN AN APPLICATION BE MADE? WHO CAN APPLY FOR ECOLABEL? APPLYING FOR THE FLOWER PROCEDURE FOR ASSESSING THE APPLICATION

5 INTRODUCTION The history of fabrics is as old as the history of civilization itself. The use of Wool, Silk, Cotton and Linen has been known to exist since time immemorial. These natural fibres have been produced, processed and traded in all ancient civilizations. Many other natural fibres were also used by past generations. Most modern fibres have a history that is only about 60 years old. For example, the first synthetic fibre produced was polyamide (Nylon) in Initially used for stockings, its applications expanded to parachute cloth, shirting, bed linen, underclothing, carpets, tyres and belts. Acrylic was produced in 1948 and is popularly used in knitwear, carpets and pile fabrics. Polyester was commercially produced in 1953 and today has become the largest synthetic fibre being produced. By itself and blended, its applications are wide spread in domestic and industrial applications. Other fibres being used today are polypropylene, polyethylene, polyurethane, aramids etc. Increased awareness of the need to protect the environment and ecosystems is bringing changes to all spheres of human life. The interested parties in the environmental protection policies are no longer just environmental groups, consumers and producers but also retailers, exporters, importers, traders, technological societies and national, regional & international authorities. The large scale use of synthetic chemicals including dyes, in textile processing is not very old, going back only the last 50 or 60 years since the discovery of the first synthetic dye in Rapid industrialization and widespread use of many synthetic chemical compounds has led to many devastating realizations. Effects of their toxicity are only now being felt. Previously unknown allergies are being attributed to the use of chemical finishes on apparel. Consumers and retailers now take purchasing decisions not just on price and quality but also health, environmental and social aspects associated with the products themselves. The scope of this new requirement is through the entire life cycle of the product. Having used synthetic chemicals extensively in the past few decades, not surprisingly, Europe has been at the forefront of eco-awareness and regulations with eco considerations. Finland was one of the first countries to have a regulation for the presence of Formaldehyde. In 1992, Germany banned the use of metallic components in all consumer articles, which contained Nickel. Soon thereafter, followed restrictions on Pentachlorophenol (PCP) and Azo Dyes that liberated Banned Amines. Pollutants, Allergens, Carcinogens are now being severely restricted in the manufacture of consumer goods sold all over Europe. With awareness and demand, ecological parameters for all consumer goods gain significant importance. Market preferences have led buyers to lay down Ecological specifications and Eco Labels have made their presence felt. This treatise is aimed at giving the reader more information on the different specifications commonly encountered in the textile & clothing industry. 5

6 Typical Eco Requirements in Europe Background Requirements follow two basic divisions Government Legislation and Buyer Requirements. Legislation has been enacted by many European countries, which have to be followed by all retailers / importers into that country. However, in many cases, Buyer requirements are far more stringent than legal requirements of the country. These requirements are typically referred to as RSLs (Restricted Substances Lists). A summary of some legal requirements in a few European Countries is given in the table below. LEGAL REQUIREMENTS EU Germany Holland Sweden Azo Dyes liberating banned amines Limits X X X Formaldehyde O Labelling above 1500 ppm Limit O PCP Limit Limit Limit X Nickel in accessories Limit Limit O Limit Chromium +6 X X X Nonyl Phenol Ethoxylates Limit Cadmium O X Legend : X : Prohibition O : Legislation expected, none at this time. Limit: Limits on detection or use. 6

7 Buyers Requirements / RSLs Buyers usually have requirements that are much more detailed than the legal limits and they may widely vary in terms of scope and limits. Each organization has the prerogative to decide limits and specifications, but a typical eco parameter requirement is given in the table below: COMMERCIAL REQUIREMENTS / TYPICAL RSLs Sr. Item Permitted limits / usage 1. Presence of Banned Amines Below 30 ppm (analytical limit) 2. Presence of Pentachlorophenol (PCP) Baby wear : 0.05 mg/kg Others : 0.5 mg/kg 3. Presence of Formaldehyde Items not in direct contact : 300 mg/kg Items in direct contact with skin : 75 mg/kg Baby wear : 20 mg/kg. 4. ph Value of Aqueous Extract Between 4.0 and Residual Pesticides (total) * 0.5 mg/kg (baby wear) ** 1.0 mg/kg (others) 6. Presence of Heavy Metals As detailed * separately. ** 7. Chloro organic Carriers Not detected. 8. Flame Retardants Not to be used. 9. Odour No unnatural odour. 10. Phthalates * Not detected. 11. TBT, DBT Not detected. 12. Chlorine Bleaching Not to be used. 13. Allergenic Dyes * Not to be used. 14. CMR Dyes Not to be used. 15. Chrome Mordant Dyes Not to be used. 16. Metal Complex Dyes Metal complex dyes based on copper, chrome and nickel shall only be permitted for dyeing wool fibres, polyamide fibers and blends of wool/polyamide with man-made cellulose fibres. ** Individual limits of Heavy metals and Pesticides are usually prescribed by buyers. * See lists that follow List of Restricted Heavy Metals Copper Nickel Cobalt Chromium +6 Chromium (Total) Mercury Zinc Arsenic Lead Cadmium Antimony Barium Selenium Tin List of Restricted Pesticides / Herbicides 2,4,5-T 2,4 D Aldrin Carbaryl DDD DDE DDT Dieldrine Endosulfan Endosulfan Endrine Heptachlor Heptachloroexpoide Hexachlorobenzene Hexachlorocyclohexane Hexachlorocyclohexane Hexachlorocyclohexane Lindane Methoxychlor Mirex Toxaphene Trifluralin 7

8 List of Phthalates DINP DNOP DEHP DIBP DIDP BBP DBP DMEP DIHP DHNUP DHP 8

9 EU REGULATIONS Annex 1 of Council Directive 76/769/EEC of 17 July 1976 and its subsequent amendments on approximation of laws, regulations and administrative provisions of the member states relating to restrictions on the marketing and the use of certain dangerous substances or preparations contain the list of substances and preparations covered by the measures provided for in this directive as well as the conditions governing their placing on the market. The list in Annex 1 has been amended several times introducing new substances and preparations. An overview of these Directives relevant for textile processing is listed in Table below. It is important to know that with the introduction of REACH regulation 1907/2006, 76/769/EEC and all its amendments have been incorporated into the Annexe XVII of REACH. These have been most recently amended vide regulations 552/2009 and 276/2010. Information about REACH has been addressed elsewhere in this document. Directive Subject 76/769/EEC Restriction on marketing and use of dangerous substances 1979/663/EEC Tris(2,3-dibromopropyl)phosphate 1982/806/EEC, 1989/677/EEC Benzene 1983/264/EEC Tris-aziridinyl phosphinoxide, Polybrominated biphenyl (PBB) 89/677/EEC Mercury compounds 1991/338/EEC Cadmium and its compounds 94/27/EC Nickel and its compounds 1999/51/EC Pentachlorophenol and its salts and esters 1991/338/EEC Asbestos fibres 97/10/EC, 97/56/EC, 1999/43/EC, 2001/41/EC, Substances classified as carcinogenic, mutagenic and toxic to reproduction (CMR) 2003/34/EC, 2003/34/EC 2002/45 Short chain chlorinated paraffins (SCCPs) 2002/61/EC, 2003/37/EC Azo colorants 2003/11/EC Pentabromodiphenylether (pentabde), Octabromodiphenylether (octabde), 2003/53/EC Nonylphenol, nonylphenol ethoxylate 2005/84/EC Phthalates in toys and childcare articles 98/8/EC* Biocidal products 648/2004/EC* Surfactants in detergents Act marked * are not amending acts of Directive 76/769/EC 9

10 GERMAN REGULATIONS Most of the current requirements of Eco parameters have evolved from legislation in Germany and the Scandinavian Countries. It is useful to therefore list the various laws that are in force with Germany at this time. Some of the legislation that is currently applicable in Germany and the compounds that they cover are: LFBG 30 = Food, Feed and Commodities Code (Lebensmittel, Futtermittel und Bedarfsgegenstande Gesetzbuch) e.g. Allergenic Disperse Dyes & Chromium VI BGVO = Commodities Prohibition Ordinance (Bedarfsgegenstandeverordnung) e.g. Flame retardants; Azo Dyestuffs; Nickel; Formaldehyde; Phthalates Chem. Verbots VO = Chemikaliverbotsverordnung (Chemical Prohibition Ordinance) e.g. DDT; Dioxins and Furans; Mercury; PCB; PCP; Cadmium; Flame-Retardants and Azo Dyestuffs (New). Gefahrstoffe VO = Gefahrstoffverordnung (Ordinance of harmful substances) ElektroG = Elektrogerategesetz (RoHS) 2002/95/EG Bfr = Bundesinstitut fur Risikobewertung (Federal Institute of Risk Analysis) 10

11 RESTRICTED SUBSTANCES LISTS PARAMETERS IN DETAIL Many substances are restricted for use in industry and consumer products. Certain chemicals are now restricted by legislation and so must not be present in the consumer products. Others are restricted by brands and eco-labels. Of late, Restricted Substance List (RSLs) has assumed more and more importance in the globalized textile market. To produce, buy and market products with eco specifications, it is necessary to understand individually each parameter. Understanding would include the possible sources, processes to eliminate the presence, background and history of the chemical compound under consideration, characteristics of the chemical, test methods and known harmful effects. The detailed information of each parameter is given below: Banned Amines in Azo Dyes Azo Dyes Azo Dyes are characterized by the presence of one or more Azo groups (- N=N -) and constitute, numerically, the most important class of synthetic colouring matters, about 70 %. They have no analogues in natural colouring matters and are produced by a common process involving two reactions: 1. Diazotization of a primary amine and 2. Coupling of the diazonium salt with a phenol or aromatic amine with free ortho or para position or components having active methylene groups such as acetoacetanilide, pyrazolones etc. Azo dyes comprise all shades with the exception of bright green colours and are suitable for all natural and synthetic fibres, leather, oils, paper, food and plastics. Their popularity in use is due to lower costs, brilliancy and adequate colourfastness properties. Azo Dyes may be of the following classes: Acid Dyes Basic Dyes Direct Dyes Disperse Dyes Mordant Dyes Pigments Solvent Dyes Chrome Dyes Some amines used in the production of dyes have been found to be carcinogenic and legislation has been introduced to safeguard consumers who may use goods that are in direct contact to the human skin. The amines that are covered in the legislation and other eco criteria are listed below. 11

12 LIST OF BANNED AMINES Sr. No. Name CAS # Other common Names 1 4-Amino biphenyl Para amino diphenyl Xenyl amine 2 Benzidine Para diamino diphenyl Fast Corinth B, BR 3 4-Chloro-o-toluidine Amino-5-chloro toluene 4-chloro-2-methyl amine Red TR Base 4 2-Napthylamine β-naphthylamine Fast Scarlet B Base 2-Amino-5-azotoluene 5 o-amino azotoluene ** Toluazotoluidine Fast Garnet GBC Base 6 2-Amino-4-nitrotoluene ** Fast Scarlet G Base 5-nitro-o-toluidine 7 p-chloroaniline p-aminochlorobenzene 8 2,4-Diamino anisole Methoxy m phenylene diamine; 2,4-diamino phenyl methyl ether 9 4,4 -Diamino diphenyl methane ,4 -Methylene dianiline 10 3,3 -Dichlorobenzidine ,3 -Dimethoxybenzidine o-dianisidine; Di-p-amino dimetamethoxy diphenyl; Fast Blue B Base 12 3,3 -Dimethylbenzidine o-toluidine; Diamino ditolyl 13 3,3 -Dimethyl-4,4 -diamino diphenylmethane ,4 -Methylene bis (o-toluidine) 14 p-cresidine Methoxy-5-methyl aniline 5-Methyl-o-anisidine m-amino-p-cresol methyl ether 15 4,4 -Methylene-bis(2-chloroaniline) ,3 -Dichloro-4,4 -diamino diphenyl methane; 4,4 -Methylene bis(orthochloroaniline) 16 4,4 -Oxydianiline ,4 -Diamnino diphenyl ether 17 4,4 -Thiodianiline ,4 -Diamino diphenyl sulphide 18 o-toluidine ** o-amino toluene 19 2,4-Diamino toluene ** Methyl-1,3-phenylene diamine; Toluene-2,4-diamine 4-meta toluylene diamine 20 2,4,5-Trimethyl aniline Pseudo cumidine; 1,2,4-Trimethyl-5-amino benzene 21 o-anisidine Methoxybenzamine 22 2,4-Xylidine ,4-Dimethylbenzamine 23 2,6-Xylidine ,6-Dimethylbenzamine 24 p-amino azobenzene Chloro-2-methyl aniline Amino-3-chlorotoluene 26 p-phenylenediamine ,4-Diaminobenzene 27 N,N-Dimethylaniline

13 ** Notes on testing for banned amines : In the test procedure, two of the listed amines (numbers 5 & 6) are not detected as themselves. These are: o-amino Azotoluene and 2-Amino-4-nitrotoluene In the test, these are detected as the following amines (numbers 18 & 19 in the list). o-toluidine and 2,4-Diamino toluene Organic compounds may have different names due to the nomenclature systems being different. The list above shows some of the names that are in use today. The last three banned amines (numbers 25, 26 & 27) are included in GOTS ver. 3.0 Summary of Banned amines / Azo Dyes requirements Limits / Restriction: Legal: In Germany: Any Azo Dye that liberates any of the listed amines in the specified test method CANNOT BE USED. As per EU: < 30 mg/kg Analytical & Buyers limits: Up to 30 mg/kg (30 ppm). Chinese Legal Limit : Upto 20 mg/kg Characteristics /Toxicity: Azo dyes when subjected to test conditions that simulate actual wear may break down and liberate these amines. The amines have been found / deemed to be toxic and carcinogenic. Processes where used: Only in Coloration: Dyeing or Printing Regulation/Legislation: In Germany, Holland, Sweden, Turkey etc. 35 LFBG Act. 2002/61/EC 19th amendment to 76/769/EEC (Annex XVII of Regulation (EC) No. 1907/2006 of European Parliament and of the council (REACH). Test Method Specified: Textiles: EN : 2012 ( LFGB B ); GB/T Leather: CEN ISO/TS ( 67 LFBG B ); GB/T Dyes: EN Annex F p-aminoazobenzene: Direct analysis: EN ( 67 LMBG B ) 13

14 Allergenic Disperse Dyes Disperse dyes are used in dyeing of polyester and other synthetic fibres. Some disperse dyes have a sensitizing (allergic) potential, and can be considered a possible threat to health when applied in textile or leather products. Therefore German enforcement authorities strongly advise not to use these sensitizing disperse dyes in textile articles coming into contact with skin. There is no any specific legislation for textile articles for allergenic disperse dyes. In Germany, according to comprehensive 30 LFBG of Food and Commodities law, it is forbidden to manufacture or distribute commodities in such a way, that if used properly or as anticipated, they may constitute a danger to health on account of their material composition, particularly through toxicological substances or impurities. These dyes have been therefore banned from being used by many eco labels and RSLs. Please note that recent German laboratory results show that sensitizing disperse dyes are still being used, for instance in stockings and tights, socks, legging, blouses and lingerie. A typical list of the Dyes that have been restricted is given below. C. I. Generic Name C. I. Structure No. CAS No. C. I. Disperse Blue 1* C. I C. I. Disperse Blue 3* C. I C. I. Disperse Blue 7 C. I C. I. Disperse Blue 26 C. I C. I. Disperse Blue 35* C. I. Disperse Blue C. I. Disperse Blue 106* C. I. Disperse Blue 124* C. I. Disperse Brown C. I. Disperse Orange 1 C. I C. I. Disperse Orange 3* C. I C. I. Disperse Orange 37* C. I C. I. Disperse Orange 76* C. I C. I. Disperse Red 1* C. I C. I. Disperse Red 11 C. I C. I. Disperse Red 17 C. I C. I. Disperse Yellow 1 C. I C. I. Disperse Yellow 3* C. I C. I. Disperse Yellow 9 C. I C. I. Disperse Yellow C. I. Disperse Yellow C. I. Disperse Orange C. I. Disperse Orange 23 C. I Note: Dyes with * mark are banned under German Law ( 30 LFBG) 14

15 Summary of Allergenic Disperse Dyes requirements Limits / Restriction Not to be used. Characteristics / Toxicity Allergenic Processes Dyeing of Polyester. Polyamide, acetate Regulation / Legislation LFBG 30 of Food and Commodities Act, Germany Test Method DIN 54231, BVL B : Carcinogenic Dyes Following dyes are prohibited and listed in RSLs and eco labels. C. I. Generic Name C. I. Structure No. CAS No. C. I. Acid Red 26 C. I C. I. Basic Red 9 C. I C. I. Basic Violet 14 C. I C. I. Direct Black 38 C. I C. I. Direct Blue 6 C. I C. I. Direct Red 28 C. I C. I. Disperse Blue 1 C. I C. I. Disperse Orange 11 C. I C. I. Disperse Yellow 3 C. I Summary of Carcinogenic Dyes requirements Limits / Restriction Not to be used (5 mg/l as per law) Characteristics / Toxicity Carcinogenic Processes Dyeing of textile and leather Regulation / Legislation 1907/2006 REACH; Eco-labelling schemes Test Method DIN 54231, BVL B :

16 Navy Blue (Blue Colourant) Navy Blue colourant (EC No ) is marketed under various trade names and is used as a wool and polyamide dye, and because of its excellent light resistance properties, it is often used in auto upholstery fabric. It consists of two components containing chromium (a heavy metal). Since only one of the two components have been assigned a CAS Number ( ), the substance is only identified via its molecular formula. These two components are as follows: Component 1 Component 2 Disodium-(6-(4-anisidino)-3-sulfonato-2- Trisodium bis-(6-(4-anisidino)-3-sulfonato- (3,5-dinitro-2-oxidophenylazo)-1-2-(3,5-dinitro-2-oxidophenylazo)-1- naphthalto)(1-(5-chloro-2-oxidophenylazo)- naphthalto)chromate(1-) 2-naphthalto)chromate(1-) Molecular Formula: C 39H 23ClCrN 7O 12S.2Na Molecular Formula: C 46H 30CrN 10O 20S 2.3Na Molecular Weight: Molecular Weight: The mixture forms a metal complex containing two azo groups. A recital in the law suggests that the Risk Assessment carried out in EU has identified this substance as highly aquatic toxic, not easily degradable and reaches the environment via waste water. Mot Retailers now include this dye in their Restrictive Substance List. Summary of Navy Blue Colourant requirements Limits / Restriction * Not to be used. Legal Limit: 1000 mg/kg Buyer Limit: 5 20 mg/kg Characteristics /Toxicity Sensitization by inhalation and skin contact Very toxic to aquatic organisms 16

17 Processes Dyeing of textiles and leather Regulation / Legislation EU directive 93/32/EEC, 7th amendment to Directive 67/548/EEC Test Methods Extraction with solvent and Detection with HPLC-DAD 17

18 Pentachlorophenol (PCP) & Tetrachlorophenol (TeCP) PCP has been used traditionally as a preservative in starch where starch is used as a yarn sizing compound. It prevents fungal growth and mould formation on natural materials. PCP may also be used in printing gums and can be a constituent of leather processing because of the anti-fungal / anti-mould properties. Some latex based finishes using natural rubber; elastic rubber accessories also may contain traces of PCP. It has been reported that PCP is used as a preservative in pigment emulsions, adhesives, glues, vegetable and mutton tallow. PCP may also be used as a biocide for transportation and or storage of textiles in humid conditions. TeCP is the lower derivative of PCP and has similar properties. Since the PCP restrictions came into force, many production techniques switched to TeCP. These chlorinated phenolic compounds are harmful to the environment. In addition, synthesis of PCP produces, as a side reaction, dioxins and furans. In addition, like all other chlorinated compounds, they degrade to dioxins on combustion. Dioxins are considered to be one of the most toxic, non degradable substances on earth. PCP and dioxins are not always easily removed from fabrics. It is therefore advisable not to use products that have PCP content. Summary of PCP / TeCP requirements Substances CAS No. Pentachlorophenol ,3,5,6-Tetrachlorophenol ,3,4,6-Tetrachlorophenol ,3,4,5-Tetrachlorophenol Limits / Restriction * EU limit: 0.1 % (1000 mg/kg) by weight German limit: 5 mg/kg Common Commercial requirements: 0.5 mg/kg (ppm) for adult wear 0.05 mg/kg (ppm) for children s wear. Characteristics /Toxicity Organic Compound Environmental toxin Processes Degrade to dioxins on incineration. Preservation of natural materials such as size, leather, preservative in natural printing gums, adhesives, glues. Biocides in transportation and storage. Regulation / Legislation Germany: Chemicals Act 1993 Holland: PCP Law 1994 Sweden: Chemical Products Act, 1985, amended EU directive 1999/51/EC, 5th adaptation to 76/769/EC (Annex XVII of Regulation (EC) No. 1907/2006 of European Parliament and of council (REACH) Test Methods 35 LFBG B for textiles & leather or KOH extraction ISO / DIN (leather -Steam Distillation), Extraction, derivatization and detection with GC-MS / GC-ECD 18

19 Orthophenylphenol (OPP) o-phenyl phenol (CAS No ) may be found in printing textiles and is a common substance in water based thickeners of printing pastes as well as in leather. Other applications for OPP include swimwear made of polyamide. The carrier based on OPP is also restricted in eco-label. OPP is suspected to be carcinogenic and may provoke allergic reactions. Summary of OPP requirements Limits / Restriction * Characteristics /Toxicity Processes where used Regulation / Legislation Test Methods Special Remarks 100mg/kg. Suspected to be carcinogenic Carrier in polyester dyeing; preservative in water/paste print thickeners. Eco labels and RSLs BVL B (modified) or KOH extraction, derivatization followed by GC-MS analysis. High temperature dyeing of polyester by aqueous or continuous dyeing techniques only should be used. 19

20 Heavy Metal Residues / Total Heavy Metal Content The metals of immediate concern from a toxicity standpoint include Antimony, Arsenic, Bismuth, Cadmium, Cerium, Chromium, Cobalt, Gallium, Gold, Iron, Lead, Manganese, Mercury, Nickel, Platinum, Silver, Tellurium, Thallium, Tin, Uranium and Vanadium. Several sources may contribute to the trace metal impurities in textiles. Residues of mercury, copper and chromium in dyestuffs are possible from the use of catalysts in the synthesis of some dye intermediates. Some reactive dyes contain metal complexes such as that of copper, nickel, cobalt and chromium. It is also possible for dyestuffs with metal free chromophores to contain metallic impurities, originating from the raw materials used in manufacture. Metals are also used as catalyst in polymers e.g. antimony in polyester, lead and cadmium in plastics like PVC used in plastisol prints and plastic accessories like trims, sequins etc. Metallic accessories also contribute to metals like lead, cadmium, chromium etc. Prolonged exposure to heavy metals may cause health problems such as kidney failure, emphysema, allergies and even cancer. Currently there are limits for total heavy metals in textile and textile auxiliaries. This requires extraction using microwave digestion prior to detection using AAS or ICP. Testing is usually done using the Atomic Absorption Spectrophotometer or ICP for detection & quantification, after extraction in artificial sweat and/or saliva. Some buyers may ask for extraction and detection as per EN 71-3 (Safety of toys) which uses hydrochloric acid for extraction. The possible sources of heavy metal in Textiles are - Dyes and Textile Auxiliaries. Cadmium has been known to be used as a stabilizer in plastic zippers and buttons. Summary of Heavy Metals requirements Heavy metals, Extractable Most eco-labels and retailers specify requirements for extractable heavy metals in textiles. Toys materials also should meet requirements EN 71 standards for extractable metals (88/378/EEC). a. Eco labels, organic textiles and RSLs Extractable metals Antimony (Sb), Arsenic (As), Lead (Pb), Cadmium (Cd) Chromium (Cr and Cr VI), Cobalt (Co), Copper (Cu), Nickel (Ni), Mercury (Hg) Processes Metallic impurities from dyes, pigments and auxiliaries used in processing of garments and auxiliaries. Legal background Eco-labels, organic labels (GOTS), RSLs. Test method 1. Extraction by ISO 105-E04 (2008) in acid perspiration (1hr. at 37 o C) and detection by AAS, ICP for all metals except Cr VI, spectrophotometer for Cr VI. 2. Extraction with saliva solution according to 64 LFGB B for baby wear and detection by AAS or ICP. 20

21 b. Toys Limits Baby wear With skin Without skin Accessories contact contact Antimony (Sb) Arsenic (As) Lead (Pb) Cadmium (Cd) Chromium (Cr) Chromium VI Not detectable (Detection limit 3 mg/kg) Cobalt (Co) Copper (Cu) Nickel (Ni) Mercury (Hg) Extractable metals Antimony (Sb), Arsenic (As), Lead (Pb), Cadmium (Cd), Chromium (Cr and Cr VI), Mercury (Hg), Selenium (Se), Barium (Ba) Processes Metallic impurities from dyes, pigments and auxiliaries used in processing of garments and auxiliaries. Legal background 88/378/EWG Test method Limits Chromium (Cr) Arsenic (As) Selenium (Se) Cadmium (Cd) Antimony (Sb) Mercury (Hg) Lead (Pb) Barium (Ba) Total heavy metals EN 71-3; Extraction with dilute HCl (0.07 M) and detection by AAS or ICP 60 mg/kg 25 mg/kg 500 mg/kg 75 mg/kg 60 mg/kg 60 mg/kg 90 mg/kg 1000 mg/kg a. Garment accessories (Total) Metal Legislation Test Method Requirement Applicable for EU Directive Digestion by EN 91/338/EEC, 1122 method 1907/2006 Detection by REACH AAS/ICP Cadmium(Cd) and its compounds, cadmium stabilizers 100 mg/kg Plastic components (buttons, zippers), coated or laminated fabrics i.e. imitation leather 21

22 b. Dyes and pigments ETAD has recommended the following limits for dyes and pigments. The test method is by microwave digestion and detection by AAS or ICP Metal Dyes/(mg/kg) Pigments (mg/kg) Antimony (Sb) Arsenic (As) Cadmium (Cd) Chromium (Cr) Lead (Pb) Mercury (Hg) 4 25 Zinc (Zn) Copper (Cu) Nickel (Ni) Tin (Sn) Barium (Ba) Cobalt (Co) Iron (Fe) Manganese (Mn) Selenium (Se) Silver (Ag)

23 Nickel Release in Extended Wear Nickel presence is known to cause contact dermatitis in approximately 10 % of the European population. Therefore, a regulation restricting the amount of Nickel that is released by metal accessories such as rivets, zippers, buttons was necessary. Use of Nickel was restricted in metallic accessories by many countries in Europe, due to the potential to cause skin allergies. Until January 2000, the presence of Nickel on metal accessories was tested by the qualitative Dimethyl glyoxime test. This test was used only to determine presence of Nickel on the surface of the metallic component. Very often a superficial coat of suitable material masked the exposure of the nickel containing metal and gave acceptable results when tested. On routine wear, this coating progressively abraded, exposing the nickel once again, leading to problems at the consumer s end. In order to eliminate such possibilities a new test method for nickel presence was developed to simulate extended wear, designated as EN The new method for quantifying the Nickel release is designated EN Summary of Ni Release requirements Limits / Restriction* Not more than 0.5 μg/cm 2 /week Characteristics / Toxicity Highly Allergenic : Causes contact dermatitis in an estimated 10 % of the European populace Processes Used in alloying to improve hardness of metals such as brass etc. Regulation / Legislation 94/27/EC 12 th Amendments to 76/769/EC Consumers Protection Act, Germany, Appendix 9, 1992 Test Method EN 1811 / which incorporates: Wear simulation Corrosion simulation Extraction in artificial sweat Detection & Quantification with AAS. 23

24 Organotin Compounds Organotins find uses in following applications Biocides preservative for cotton & polyester textiles As biocides for the protection against odour in sports textile Stabilizer or catalyst in PVC, polyurethane and polyester foams PVC used as a binder for prints sometimes contain DOT or other organotin stabilizer Anti-microbial finishing, i.e. preventing the bacterial degradation of sweat and the corresponding odour. To improve grip, polysiloxane softeners were used for polyester fabrics. Polysiloxane may contain low amount of organotin stabilizers. An organotin compound, Tributyltin (TBT) was detected in January 2000 in some branded sportswear in Germany. Thereafter, the requirements for TBT / DBT and MBT were introduced in some European Countries. Later, it was also found that there was a presence of organotin compounds in some diapers being sold in Europe. TBT is known to have caused mutations in sea snails and other sea creatures. It is therefore a suspected mutagen. On 4 th June 2009, a new European Commission Decision 2009/425/EC restricting the use of Organotins was published. Highlights are given below: Trisubstituted Organotins such as TBT & TPT DBT compounds DOT compounds Requirement Effective from Article or part thereof < = 0.1% Mixture 2. Article or part thereof (except food content material) 3. Fabrics coated with PVC containing DBT as stabilizers, when intended for outdoor applications 1. Textile articles intended to come in contact with skin 2. Gloves 3. footwear or part thereof coming in contact with skin 4. Wall and floor coatings 5. Children articles 6. Female hygiene products 7. Nappies < = 0.1% < = 0.1% < = 0.1% Summary of Organotin requirements Limits / Restriction* 0.5 mg/kg for TBT and 1.0 mg/kg for DBT. Characteristics / Toxicity Mutagen Processes In specific specialty finishes Regulation / Legislation EU commission decision 2009/425/EC. Test Method Solvent extraction, derivatization, detection & quantification using GC-MSD based on ISO

25 Chlorinated Organic Carriers Chlorotoluenes and chlorobenzenes with their different patterns of chlorine substitution belong to the class of chlorinated organic carriers. These are used in dyeing of chemical fibres (Polyester acetates, polyacrylic polyamides etc.) with disperse dyestuffs. These are listed below: Compound CAS No. Compound CAS No. 2-Chlorotoluene ,2-Dichlorobenzene Chlorotoluene ,3-Dichlorobenzene Chlorortoluene ,4-Dichlorobenzene ,3-Dichlorotoluene ,2,3-Trichlorobenzene ,4-Dichlorotoluene ,2,4-Trichlorobenzene ,5-Dichlorotoluene ,3,5-Trichlorobenzene ,6-Dichlorotoluene ,2,3,4-Tetrachlorobenzene ,4-Dichlorotoluene ,2,3,5-Tetrachlorobenzene ,3,6-Trichlorotoluene ,2,4,5-Tetrachlorobenzene ,4,5-Trichlorotoluene Pentachlorobenzene Pentachlorotoluene Hexachlorobenzene Summary of Chlorinated Organic Carriers requirements Limits / Restriction* <1.0 mg/kg (ppm) Characteristics / Toxicity These substances have different toxic effects. Can affect the nervous system and might also have an irritating effect on the skin and the mucous membranes. Hexachlorobenzene is classified as carcinogenic group 2 and 1,4- dichlorobenzene is classified as carcinogenic group 3. Processes Carrier in dyeing of synthetic fibres and blends. Regulation / Legislation Section 30 of German Food and Commodities Act and RSLs. Test Method DIN 54232, solvent extraction from fabric and detection using GC-MS 25

26 Formaldehyde Formaldehyde is a gas. It is present in nature in small quantities. For example, human blood has traces of formaldehyde and so do apples. However in larger quantities, formaldehyde can be the cause of skin allergies or skin irritations. In textiles, formaldehyde has traditionally been used in anti-shrinking treatments, resin finishes for wrinkle/crease free properties and dye fixing agents. Formaldehyde was first restricted by law in Japan. Regulation in Finland limiting values was the first legal directive in Europe. Today there are regulations in place for many European countries and the limits on formaldehyde are common for most buyers. Formaldehyde may be tested as Free Formaldehyde or Released Formaldehyde. Legal limits are quite high, though buyers ask for lower limits for their purchases. Summary of Formaldehyde requirements Limits / Restriction* Legal limit: 1500 mg/kg (labelling) Typical buyer limits are: 16 or 20 mg/kg (ppm) for baby wear 75 mg/kg (ppm) for items with direct contact with human skin 300 mg/kg (ppm) for outerwear Characteristics / Toxicity When in contact with skin, it may cause allergies and irritation Processes Anti-shrinking processes Wrinkle-free / Crease-free Resin Finishes (DMDHEU Resin) Dye fixing agents for reactive dyes Fixer in pigment printing Regulation / Legislation Finland in 1998, Germany in 1993, Norway in 1999, Holland in 2000 Test Method Free formaldehyde: ISO ; ISO (leather using HPLC), ISO (leather using UV-VIS) Released formaldehyde: ISO , ISO (leather) 26

27 Glyoxal Glyoxal is used as chemical intermediate in the production of dyestuffs. It is used as crosslinking agent in the production of range of different polymers. As a cross linking agent or building block for cross linker it is used in textiles to produce softer and less wrinkled textiles. Cross linking in tanning process preserves the leather quality. It is also used as a biocide and as a disinfecting agent. Glyoxal is supplied in the form of aqueous solution at 40% (w/w) in which hydrated oligomers are present. The aqueous solution is colourless to pale yellow. Glyoxal can undertake rotational isomerization between the planar cis- and trans- conformations, with trans-glyoxal being the more stable isomer. Summary of Glyoxal requirements Limits / Restriction* Banned for use as input chemical in GOTS ver. 3.0 Residual Limit Value for GOTS Goods: 20 mg/kg Residual Limit Value for accessories and additional materials: 20 mg/kg for baby wear 75 mg/kg for items in direct contact with human skin 300 mg/kg for outerwear Characteristics / Toxicity Mutagenic, Category 3; Possible risk of irreversible effects; May cause sensitization by skin contact; Irritating to eyes and skin Processes As a cross linking agent or building block for cross linking agent in textile finishing auxiliaries such as anti-crease, wrinkle free finishes. Cross linking in tanning process preserves the leather quality. Regulation / Legislation EU Directive 67/458/EEC in the EU Chemical legislation (since 25 th 28 th ATP; annex I index # ) Test Method Extraction with solvent, detection using GC-ECD 27

28 Alkyl Phenol Ethoxylates APEOs are non-ionic surfactants made of branched chain alkyl phenol that has been reacted with ethylene oxide to produce an ethoxylate chain. The length of the ethoxylate chain in NPEOs can vary between 1 and 50, depending on application. The most important APEOs or alkyl phenol ethoxylates for the textile industry are NPEOs (Nonylphenol ethoxylates) and OPEOs (Octylphenol ethoxylates) due to their detergent properties. APEOs are usually present in detergents, cleaning agents as well as other chemicals used for textile or leather production. For cleaning products, the most common APEOs are either 9-mole or 10-mole NPEOs. APEOs have hormone disruptive properties and they are toxic to aquatic organisms. APEOs degrade by losing ethoxylate groups and eventually form extremely harmful Nonylphenol or Octylphenol (NP/OP). NP mimics oestrogen, a human hormone and this has been found to cause hormonal disturbances in aquatic life. Legislation and labelling Textile eco-labels such as the EU Flower have forbidden the use of APEO. By the 26 th amendment of the Council Directive 76/769/EEC, a new Directive, 2003/53/EC was passed on 18 th June 2003 which was made effective January 17, 2005 restricting APEOs in consumer products. Substance CAS No. Nonyl phenol (NP) Nonyl phenol ethoxylate (NPEO) Octylphenol (OP) Octylphenol ethoxylate (OPEO) While the EU legislation is applicable to all consumer goods, buyers usually set their own limits for ecological parameters. The EU limit is 1000 mg/kg (ppm, or 0.1%) whereas buyer s requirement for APEO (NPEOs and OPEOs) are stricter than EU limits. Summary of APEOs requirements EU Regulation : 0.1 % on weight of product (1000 mg/kg) Limits / Restrictions* EU Ecolabel : Not to be used Buyer requirements : 100 mg/kg Characteristics / Toxicity Oestrogenic. Hormonally Disruptive. Used in detergents, industrial cleaners, dispersants wetting agents Process etc. in the textile industry / 53 / EC (26 Regulation / Legislation th Amendment to 76/769/EEC) Eco Labels and Restricted Substances Lists Extraction in solvent, detection and quantification using liquid Test Method chromatography and mass spectrometry * Limits mentioned here are typical. Each Buyer may have own limits. 28

29 Fluorocarbons PFOS And PFOA Perfluooctanesulphonate (PFOS) and perfluorooctanoic acid (PFOA*) belong to the group of perfluorinated chemicals (PFCs), in which fluorine is strongly bonded to variable lengths of carbon chain (e.g. Teflon). PFOS and PFOA are synthetically produced or PFOA forms as breakdown product of PFCs. PFOS PFOA Perfluorooctane sulfonate (PFOS) PFOS is a substance for surface treatment applications for giving the surface material with repellent properties against water, oil and soil and softer hand feeling. In textile industry, this finds application such as rainwear, upholstery fabric, curtain material, work wear, bed sheets etc. Although PFOS are regarded as inert chemicals and biologically inactive, were classified by Scientific Committee on Health and Environment Risks (SCHER) as very persistent, bio accumulative and toxic (PBT) chemical compounds. Therefore, new EU Directive 2006/122/EC was issued. EU Directive 2006/122 of December 12, 2006, amending for the 30 th time Directive 76/769 on approximation of laws, regulations and administrative provisions of the Member States relating to the marketing and use of certain dangerous substances and preparations (perfluorooctane sulfonates with the chemical formula C 8F 17SO 2X, where X can be OH, metal) salt (O-M+), halide, amide, and other derivatives including polymers. The directive imposes two restrictions relative to PFOS: PFOS may not be placed on the market or used as a constituent of preparations in a concentration equal to or higher than 0.005% by mass Semi-finished product or articles, or part thereof, may not be placed on the market if the concentration of PFOS is equal to or higher than 0.01% by mass 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 higher than 1 µg/m 2 of the coated material. Remarks *PFOA is also related substance of PFOS, which chemical at the heart of this is Ammonium Perflurooctanoate, commonly referred as C8, C-8 or APFO 29

30 Perfluorooctanoic Acid (PFOA) PFOA (C 8HF 15O 2) is a completely fluorinated organic chemical that can be produced synthetically or through the degradation or metabolism of other fluorochemical products. PFOA is primarily used as a reactive intermediate, where its salts are used as processing aids in the production of fluoropolymers and fluoroelastomers (used as non-stick coatings) and in other surfactant uses. Perfluorooctanoic acid (PFOA) and its salts are suspected to have similar risk profile to PFOS. Therefore, the European Union s Directive has charged the commission to keep under review the ongoing risk assessment activities and the availability of safer alternative substances or technologies related to uses of PFOA and related substances. Summary of PFOS and PFOA requirements Limits / Restriction* EU regulation for PFOS: =<1 µg/m 2 of the coated material/textile Buyer s requirement for PFOA: 1 mg/kg Characteristics / Toxicity Persistent, bio-accumulative and toxic Processes Regulation / Legislation Test Method Oil/water and water repellent finishes on textiles EU Directive 2006/122/EC (30 th Amendment to 76/769/EEC), Annex XVII of Regulation (EC) no. 1907/2006 of European Parliament and of the council (REACH) Draft CEN/TS (Extraction with organic solvent and detection by LC/MS); ISO/DIS

31 Phthalates Phthalates are group of chemicals (oily, colourless liquids) that are used, among other things, to make polyvinyl chloride (PVC) and other plastics soft and flexible. Many types of phthalates are in use today. PVC can be found in plastic items and trim in apparel and textiles. In addition, PVC can often be found in screen prints and inks. Phthalates are suspected carcinogens and are known to disturb the endocrine system in humans and animals. They are restricted in plasticized materials in toys and child care articles, however some retailer groups place restrictions on plasticized materials on apparel. The following phthalates are legally restricted for children s products and child care articles both in EU and CPSIA. Name CAS No. Di-(2-ethylhexyl) phthalate (DEHP) Dibutyl phthalate (DBP) Butylbenzyl phthalate (BBP) Di-iso-nonyl phthalate (DINP) and Di-isodecylphthalate (DIDP) and Di-n-octyl phthalate (DNOP) Di-isobutyl phthalate (DIBP) Summary of Phthalates requirements Limits / Restriction* 0.1 % (1000 mg/kg) Characteristics / Toxicity Carcinogenic and endocrine disruptors Processes Used in plastic packaging, decorations and accessories. Regulation / Legislation 1907/2006 REACH, 2004/781/EU, 2005/54/EEC (22 nd Amendment to 76/769/EEC) on toys and child care Products; CPSIA Children and child care articles. Test Method CPSC-CH-C or ISO 15777: Solvent extraction, Detection with GC/MS 31

32 Polyvinyl Chloride (PVC) Polyvinyl chloride is produced by polymerization of monomer vinyl chloride. It is a thermoplastic polymer, which can be made softer and more flexible by the addition of plasticizers. In the textile industry PVC is often found in accessories such as zip pullers, coatings, and accessories such as badges etc. It is also used in plastisol prints on textiles. It may be found either as artificial or coated leather. PVC is cheaper than rubber and latex, so these materials may be substituted, too. Another use of PVC is for preparation of packaging. PVC has many impacts on the environment. The monomer vinyl chloride, which PVC is produced from, is highly toxic and carcinogenic organic compound. Summary of PVC requirements Limits / Restriction* Not to be used. Characteristics / Toxicity PVC items are environmentally persistent, and their manufacture and disposal often results in other highly toxic wastes (e.g. Dioxins) Processes Plastisol prints; can be used for accessories like badges, sequins and zip pullers or as a coating on textiles for rainwear and prints Regulation / Legislation Not for textiles specifically. Test Method i) Burning test by Beilstein method ii) FTIR (Qualitative) 32

33 ph of Aqueous Extract ph is the measure of hydrogen ion concentration in the solution. ph = 7 equates pure water and /or neutral solutions ph < 7 equates a solution with acid impacts ph > 7 equates a solution with basic impacts The ph of a water extract depends on the chemical treatment previously given to the textile. Normally, the ph will be higher after caustic boiling than after bleaching. If the textile is scoured after bleaching, the ph will be lower. Textiles with higher ph may exhibit yellowing tendencies or create shade changes. Human skin has a ph of about 5.5, so weakly acidic. This acid mantle is a fine film acting as a barrier to bacteria, viruses and contaminations. High ph (alkaline) can cause skin sensitivity, very high ph can cause burns to skin. Low ph (acidic) can also cause skin irritations. There are no laws on the matter and ph can be easily controlled in processing at any stage of garment manufacture. Summary of ph requirements Limits / Restriction* Between 4.0 and 7.5 Characteristics / Toxicity Skin irritant Processes Various, but mainly from the final washing processes. Regulation / Legislation None Test Method ISO 3071; EN 1413 method B 33

34 Residual pesticides Pesticides are used during cotton plants cultivation to protect the plants from pest s attack. Similarly wool producing animals are protected from parasites using bath containing pesticides. It is possible to absorb pesticides from textiles through the skin and also orally by sucking on the garments (children). A variety of poisoning symptoms can appear from the various pesticides such as headache, nausea, dizziness, vomiting etc. right up to the fatality, depending upon the dose. In the long term contact, pesticides have a carcinogenic effect, are mutagenic and or teratogenic. Some are identified as being persistent organic pollutants (POPs) and contribute to severe environmental pollution because of the length of time they take for them to biodegrade. Some affect animals, plants and aquatic life causing genetic malformations. Hence the use of pesticides is regulated in various countries by the Acts for the protection of crop plants. There have been no known problems in textile end products with pesticide content as of today. Preliminary experimental work shows that even if restricted pesticides are used in cotton cultivation, their traces do not remain on the end product. There is no standard legal regulation for pesticide residue in textiles. The prohibition of Chemical Ordinance applies to DDT, but other pesticides and other substances are only mentioned in the highest concentration of Residue Ordinance of the Food and Consumer Goods Act. Most buyers follow common requirements for effluent/water. Summary of Residual Pesticide requirements Limits / Restriction* < 1.0 mg/kg (ppm) Characteristics / Toxicity Most are chlorinated or organophosphorous compounds. Pollutant/ Toxic/Environmentally hazardous. Also toxic to human life. Processes Cotton cultivation; Caretaking of wool producing animals using pesticides Regulation / Legislation None for textiles. However certain chlorinated pesticides (Aldrin, Dieldrin, Chlordane, Endrin, Heptachlor, Hexachlorobenzene, Mirex, Toxaphene, Hexachlorocyclohexane, gamma) are banned under POP Convention and consequentially globally banned. Test Method Solvent extraction from fabric and detection on GC/MS 34

35 A Typical list restricted pesticides is as follows: No. Pesticide CAS No. No. Pesticide CAS No. 1 2,4,5-T Endosulfan, beta ,4-D Endrin Azinophosmethyl Esfenvalerate Azinophosethyl Fenvalerate Aldrin Heptachlor Bromophos ethyl Heptachloroepoxide Captafol Heptachlorobenzene Carbaryl Heptachlorocyclohexane, alpha Chlordane Heptachlorocyclohexane, beta Chlordemeform Heptachlorocyclohexane, delta Chlorfenviphos Lindane Coumaphos Malathion Cufluthrin MCPA Cyhalothrin MCPB Cypermethrin Mecoprop DEF Metamidophos Deltamethrin Methoxychlor DDD , Mirex DDE , Monocrotophos DDT , Parathion Diazinon Parathion methyl Dichloroprop Phosidrin/Mevinphos Dicrotophos Propethamphos Dieldrin Profenphos Dimethoate Quinalphos Dinoseb and salts Toxaphene Endosufan Trifluthrin

36 Flame Retardants Flame retardants are applied to textiles for protective clothing to be worn at workplaces with a particularly high fire hazard and are also important for protecting curtains and upholstery furniture in rooms open to the public and for car interior furnishings. There are flame retardant modified polyester fibres where there is practically no exposure of the user to flame retardants. There are also permanent flame retardants made of fibre-reactive compounds, where minor exposure is assumed to exist. Semi-permanent flame retardants also include substances which involve health risks, and some of these have been banned by the Regulations on Specific Commodities under the Foods etc, Act (Bedarfsgegenstandeverordnung, BGVO), i.e. (tri-(2,3-dibromopropyl)-phosphate (TRIS), tris- (aziridinyl) phosphine oxide (TEPA) and polybrominated biphenyls (PBB). The commodities Ordinance, Annex 1 (to 3) states that the flame retardant substances are prohibited in commodities manufactured from textiles (in Chemical Ordinance REACH on cotton or polyester textiles, as unwanted in consumer goods. FRs can be divided in to various groups with different chemical bases and functional behaviour. Inorganic FRs (e.g. Al(OH) 3), organophosphorous FRs (e.g. tris(2-chloroisopropyl)phosphate) and halogenated organic FRs (e.g. polybrominated diphenyl ether (PBDE) are the most important groups. Sr. No. Name CAS No. 1 Polybrominated biphenyls (PBB) Penta-bromodiphenyl ether (pentabde) Octa-bromodiphenyl ether (octabde) Deca-bromodiphenyl ether (decabde) Tris(2,3-dibromopropyl)phosphate (TRIS) Tris(1-aziridinyl)phosphine oxide (TEPA) Hexabromocyclododecane (HBCDD) Summary of requirements for Flame Retardants Reasons for Restriction Legal Background Restrictions Test Method Potential to bio-accumulate in the environment. Also suspected of having effects on human reproductive and immune systems. In case of incinerating products containing flame retardant substances dioxins and furans can form. BGVO, 83/264/EEC, Chem. Verbots VO, Directive 2003/11/EC (24 th Amendment to 76/769/EEC) Legal Restriction; Not detectable - < 5 mg/kg. Solvent extraction and detection by GC/MS or LC/MS 36

37 Polychlorinated Biphenyls (PCBs) and Polychlorinated Terphenyls (PCTs) Polychlorinated biphenyls and polychlorinated terphenyls are classes of organic compounds where chlorine atoms are attached to the benzene rings as shown below: PCB PCT These are mainly found as impurities in Copper phthalocyanine pigments. But also find applications as softeners, carriers and flame retardants. These are all listed under Persistent Organic Pollutants (POPs). Accumulation in organisms and environment, affects on hormone system, liver, immunity and nervous system. The production processes on a large scale may create dioxins and furans as side products which are harmful to environment. Summary of PCBs and PCTs requirements Limits / Restrictions Characteristics / Toxicity Process Regulation / Legislation Test Method Restrictions from Buyers and Retailers. Toxic. Dioxins and Furans may be formed upon thermal decomposition. Impurities in phthalocyanine pigments Chemical Verbots VO., 76/769/EEC REACH 1907/2006 and amendments. DIN ; DIN ; EN ISO 6468; DIN ISO Solvent Extraction, Detection and Quantification by GC/MS. 37

38 Polyaromatic Hydrocarbons Polycyclic Aromatic Hydrocarbons (PAH) are organic compounds containing fused rings of carbon and hydrogen. e.g. Phenanthrene Anthracene Benzo(a)pyrene These are used as a raw material to make dyes, rubber, plastics and pesticides. These are also classified as Persistent Organic Pollutants (POPs). Benzo(a) pyrene is a class II carcinogen, mutagen and reprotoxin. Sixteen PAHs listed by EPA are: Sr. No. Substance CAS No. 1 Acenaphthene Acenaphthylene Anthracene Benzo(a)anthracene Benzo(a)pyrene Benzo(b)fluoranthene Benzo(ghi)perylene Benzo(k)fluoranthene Chrysene Dibenzo(a,h)anthracene Fluoranthene Fluorene Indeno(1,2,3-cd)pyrene Naphthalene Phenanthrene Pyrene The limit value for these substances on consumer products is 1 mg/kg for benzo(a)pyrene and 10 mg/kg for total of different PAH (16 chemicals as defined by EPA) 38

39 Summary of PAH requirements Limits / Restrictions 1 mg/kg for benzo(a)pyrene 10 mg/kg for total PAHs defined by EPA. Characteristics / Toxicity Carcinogenic, Mutagenic, Teratogenic Processes Regulation / Legislation Test Method Softeners or plasticizing Oils used in the manufacture of plastic / rubber products. 2005/69/EC; 27 th amendment to 76/769/EC. ZEK (Solvent Extraction and Detection by GC/MS) 39

40 Dioxins & Furans Dioxin is a common name for a group of persistent and very toxic chemicals, also called as dioxins and furans. These include 75 chlorinated dibenzo dioxins and 135 chlorinated dibenzo furans. The most toxic amongst these is 2,3,7,8-tetrachlorodibezo-p-dioxin, also known as TCDD Dioxin is a by-product of many chemicals manufacturing and combustion processes. The use of chlorine in the process or the combustion of a chlorine containing material may result in the formation of dioxin. European regulations prohibit sales of any product that has more than specified limits of Dioxins or Furans. Dioxins and Furans are said to be some of the most toxic substances known to man. They are extremely lethal in laboratory testing controls and are reported to cause foetal damage, genetic mutation and are carcinogenic. The possible sources of Dioxins and Furans in Textiles are as impurities in some dye intermediates, brominated flame Retardants, PCP / TCP etc. and some chlorinated pesticides. Additionally, dioxins and furans may be formed due to incineration and incomplete combustion of chlorinated plastics such as PVC Summary of Dioxins and Furans Limits / Restrictions From 1µg/kg to 100µg/kg Characteristics / Toxicity Extremely toxic, Lethal, Mutagenic, Carcinogenic Processes Regulation / Legislation Test Method Mainly found as impurities or by-products of chlorinated compounds used in processing. Chem Verbots VO. REACH Annex XVII and amendments Extraction with organic solvent, detection with GC/MS Method VDI 3499, DIN EN 194. EPA Method 1613, EPA Method 8290, EPA Method 8280, EPA Method 613, EPA Method 23, EPA method TO-9, NCASI Method 551 and CARB Method 428 List Of Dioxins And Furans & Limits Sr. No. Name CAS No. Limits A Group 1 1 2,3,7,8-Tetrachlorodibenzo-p-dioxin ,2,3,7,8-Pentachlorodibenzo-p-dioxin µg/kg for Group 1 3 2,3,7,8-Tetrachlorodibenzofuran ,3,4,7,8-Pentachlorodibenzofuran

41 B Group 2 1 1,2,3,4,7,8-Hexachlorodibenzo-p-dioxin ,2,3,7,8,9-Hexachlorodibenzo-p-dioxin ,2,3,6,7,8-Hexachlorodibenzo-p-dioxin ,2,3,7,8-Pentachlorodibenzofuran ,2,3,4,7,8-Hexachlorodibenzofuran ,2,3,7,8,9-Hexachlorodibenzofuran ,2,3,6,7,8-Hexachlorodibenzofuran ,3,4,6,7,8-Hexachlorodibenzofuran C Group 3 1 1,2,3,4,6,7,8-Hexachlorodibenzo-p-dioxin ,2,3,4,6,7,8,9-Octachlorodibenzo-p-dioxin ,2,3,4,6,7,8-Heptachlorodibenzofuran ,2,3,4,7,8,9-Heptachlorodibenzofuran ,2,3,4,6,7,8,9-Octachlorodibenzofuran D Group 4 1 2,3,7,8-Tetrabromodibenzo-p-dioxin ,2,3,7,8-Pentabromodibenzo-p-dioxin ,3,7,8-Tetrabromodibenzofuran ,3,4,7,8-Pentabromodibenzofuran E Group 5 1 1,2,3,4,7,8-Hexachlorodibenzo-p-dioxin ,2,3,7,8,9-Hexachlorodibenzo-p-dioxin ,2,3,6,7,8-Hexachlorodibenzo-p-dioxin ,2,3,7,8-Pentabromodibenzofuran µg/kg for sum of groups 1 & µg/kg for sum of groups 1,2 & 3 1 µg/kg for sum of Group 4 5 µg/kg for sum of groups 4 & 5 41

42 Chlorinated Paraffins Chlorinated paraffins are produced for use as plasticizers and flame retardants as well as extreme-pressure additives in lubricating oils and as a lubricating agent for the treatment of leather. These are persistent compounds having a potential to bio-accumulate in aquatic organisms. Short chain chlorinated paraffin causes adverse effects in fish and aquatic invertebrates at concentration below 1 mg/l in laboratory studies. It has also caused cancer in experimental animals, although relative data for humans is not available. Therefore these are considered to be non-threshold toxicants. Summary of Chlorinated Paraffins (CPs) requirements Limits / Restrictions* 100 mg/kg in RSLs Characteristics / Toxicity Persistent and bio-accumulative, toxic to aquatic organisms. Processes Regulation / Legislation Test Method Used as plasticizers, lubricants and flame retardants. Directive 2002/45/EC (20 th amendment to 76/769/EEC); also included in EU REACH SVHCs Extraction with organic solvent using ultrasonic bath, detection with GC/MS using NCI (Negative Chemical Ionization) 42

43 Dimethyl Formamide (DMF) N,N-Dimethyl formamide is a polar aprotic solvent, miscible with water and majority of organic liquids. Pure liquid is odourless, however technical grade or degraded one often has fishy smell. Dimethyl formamide is used in production of acrylic fibres and polyurethane products as well as in manufacture of artificial leathers, films and surface coatings. DMF is harmful by inhalation and in contact with skin because it may cause harm to the unborn child and is classified as CMR substance of category 2. Summary of DMF requirements Limits / Restrictions* 10 mg/kg in RSLs Characteristics / Toxicity Harmful by inhalation and in contact with skin Processes Regulation / Legislation Test Method Manufacture of acrylic fibres and in PU coating. Identified and included in the Candidate List of Substance of Very High Concern (SVHC) on 19 the Dec 2012 following ECHA s decision ED/169/2012, according to Article 57 (c) as it is classified in Annex VI, part 3, Table 3.1 (the list of harmonised classification and labelling of hazardous substances) of Regulation (EC) No 1272/2008 as toxic for reproduction Extraction with organic solvent, detection with GC/MS 43

44 Dimethyl Fumarate (DMFu) Dimethyl fumarate is a methyl ester of fumaric acid. Dimethyl fumarate is used as biocide to inhibit mould during storage or transport and may be added to desiccant packs like silica gel. DMFu is often contained in pouches fixed inside furniture or added to footwear boxes, where it sublimates protecting the product from mould. Often the pouches look similar to those used to contain silica gel, a non-harmful desiccant frequently used in leather products. The DMFu crystals when exposed to heat sublimate into toxic gases which then pass through clothes to cause the rash. The presence of DMFu in consumer products such as leather sofas has been blamed for causing damage to health. The European Commission has now produced legislation that effectively bans DMFu from the European Market. European Directive 2009/251/EC was published on 17 th March 2009 and requires that the products containing DMFu are not placed on the market; this means the presence of DMFu in one or more pouches or in concentration greater than 0.01mg/kg of the weight of the product or part of the product. The directive also requires any product containing DMFu that has already been placed in the market be withdrawn by May1, 2009 and consumers to be made aware of potential risks. Summary of DMFu requirements Limits / Restrictions* < 0.1 mg/kg Characteristics / Toxicity Highly sensitizing to skin Processes Anti fungal/biocidal agent in leather goods (mainly used in humidity reducing sachets like silica gel) Regulation / Legislation EU Directive 2009/251/EC Test Method Extraction with organic solvent, detection with GC/MS 44

45 Acrylamide In the textile industry, polyacrylamide based additives are used to size and shrinkproof material and as water repellents. There is a posiibility of residual acrylamide monomer in such material. Acrylamide is white crystalline colourless solid. It is stable under normal conditions, but may decompose or polymerise when heated. When heated for decomposition, emit acrid fumes and nitrogen oxides. Acrylamide is mostly used to synthesize polyacrylamide which is further modified to water soluble polymers and having many industrial applications. The potential routes of human exposure are ingestion, dermal contact and inhalation. Being carcinogen and mutagen of catagory 2, the European Chemical Agency (ECHA) has added acrylamide to the list of substances of very high concern (SVHC) on 30th March Summary of Acrylamide requirements Limits / Restrictions* Restricted as per REACH; Legal Limit: 1000 mg/kg Characteristics / Toxicity Mutagenic and Carcinogenic of category 2 Processes Used in auxiliaries to prepare shrink-proof textiles and water repellent coated textiles. Regulation / Legislation Article 57 (a) and (b) of Regulation (EC) No. 1907/2006 (REACH) Test Method Extraction with organic solvent, detection with GC/MS Others In addition to the parameters mentioned so far, there are few more also requested by some Buyers and Eco labels. Few of them are listed below: Sr. No. Parameter Test method Requirements 1 Biocide Finishes - Not to be used 2 Emission of volatiles (For floor GC/MS Within Limits coverings and carpets) 3 Odour SNV (Panel Odour Test) No abnormal odour to be perceived 4 Chlorine bleaching - Not to be used 45

46 CPSIA LEAD AND PHTHALATE COMPLIANCE The landmark legislation Consumer Product Safety Improvement Act (CPSIA) of 2008 is designed to establish consumer products safety standards and to reauthorize the US Consumer Product Safety Commission (CPSC). The law expands the commission s role in ensuring the safety of consumer products, especially those intended for children. The Act has amended four already existing laws: (1) The Consumer Product Safety Act (CPSA) (2) The Federal Hazardous Substances Act (FHSA) (3) The Poison Prevention Packaging Act (PPPA) (4) The Flammable Fabrics Act (FFA) CPSIA addresses new product safety and chemical requirements for lead, flammability, small parts and sharp point-edges. Under CPSIA, new chemical substances requirements were enacted on 14 th August, Lead containing paint and lead in substrate are banned in all children s products in order to prevent children from being poisoned fro eating or licking any lead-containing products. Legislation on Lead (Sec. 101): Section 101 of the CPSIA covers Children s products with Lead in Paint and Lead in Substrates, which include metal jewellery. Lead in paint (Children can eat paint chips or dust from paint chips after ageing of paints) containing lead, or lick their fingers after playing with or touching certain lead-containing products) Lead in Substrate (accessible parts, i.e. accessible by mouth in children articles or child care products) Applicable to Limits Test Method The paint (lead containing 90 ppm CPSC-CH-E : plastic coatings, e.g. multi Standard Operating colour painted zipper and the Procedure for pull, slide and stop) which can Determining Lead in be scrapped from the Paint and Other substrate on a children s Similar Surface product Coatings Apparel products such as screen printing, zippers (metal or plastic) buttons, snaps, gemstones and other embellishments 300 ppm CPSC-CH-E : Standard Operating Procedure for Determining Lead in Non-metal children s products 46

47 Legislation on phthalates (Sec. 108): The prohibition on phthalates is one of the new requirements in the CPSIA. Mandatory and interim bans on phthalates apply to toys for children and child care articles. Children Toys means products designed or intended by manufacturer for a child upto age 12 for use or play by a child. Child care articles are defined as a consumer product designed or intended by manufacturer to facilitate sleep or the feedings of the children upto age 3, or to help such children for sucking or teething. Placed in a mouth is defined as a toy, or a part of a toy, in one dimension is smaller than 5 cm. f the children s products can only be licked; it is not regarded as able to be placed in the mouth. Group 1 (Permanent ban) Group 2 (Interim ban) Scope: For children up to age 12 or child care Scope: Toys for children up to age 12 articles up to age 3 Di-(2-ethylhexyl)-phthalate (DEHP) < 0.1% Di-iso-nonyl phthalate (DINP) < 0.1% Dibutyl phthalate (DBP) < 0.1% Di-iso-decyl phthalate (DIDP) < 0.1% Butylbenzyl phthalate (BBP) < 0.1% Di-n-octyl phthalate (DNOP) < 0.1% Remarks: According to CPSIA, section 102, certifications are mandated for all consumer products sold in USA, both imported and domestic those are subjected to any of the other Acts for which CPSC has the jurisdiction. Importers and domestic manufacturers in the US are now required to issue a general certificate of conformance stating that their product complies with all bans, standards or regulations enforced by the CPSC. Mandatory testing is expected to be required from authorized 3 rd party laboratories, which will create a lot of testing requirements and possible delays. It is said that textiles may be exempted from the mandatory testing and just the GCC would be adequate, however, all GCCs are expected to be backed by a reasonable testing programme or test report. For more information on this fast changing requirement, visit the following pages: Home Page CPSIA Legislation FAQ for Small Businesses Conformity Certificates Search for an authorized 3 rd Party Laboratory

48 REACH & SVHCs REGISTRATION, EVALUATION, AUTHORIZATION OF CHEMICALS & SUBSTANCES OF VERY HIGH CONCERN The EU REACH regulations, to have a proper instrument in place to protect human health & the environment and to enforce better competitiveness in the Chemical Industry and to increase the transparency, were published in December 2006 and came in to force in June The REACH requirements are designed to make sure that Use of a chemical substance does not adversely affect either human health and /or the environment by providing documented safety information on the substance in question. To make sure that all risks for potentially causing injury and /or health concern to both humans and the environment by the chemical itself are identified and managed. Key elements are Registration of substances > 1 tonne/year Increase information and communication throughout the supply chain Evaluation of some registered substances Authorization of substances of very high concern Restrictions of unacceptable substances REACH replaces numerous EU laws related to chemicals (amending Directive 1999/45 EC and repealing Council Regulation (EEC) No. 793/93 and Commission Regulation (EC) No. 1488/94 as well as Council Directive 76/769/ EEC and Commission Directive 91/155/EEC, 93/67/EEC, 93/105/EC and 2000/21/EC). This is complementary to other environmental and safety legislation but it will not replace sector specific legislation. REACH affects substances, preparations and articles in a variety of consumer goods from different sectors such as Chemicals, Cosmetics, Electrical and Electronics, Textile, Toys, Food contact etc. Under REACH, textile products such as jackets, T-shirts, footwear, bags etc. are defined as Article. Articles means an object giving a special shape, surface or design during production that determines its function to a greater degree than does its chemical composition. According to REACH regulation, article itself is not the right candidate for registration, unless SVHC found in article. Moreover two criteria should be fulfilled if registration can be triggered as following condition: Substances in Article, if a. Not intended to be released No registration b. Intended to be released and less than 1 t/a No registration c. Intended to be released and more than 1 t/a Registration 48

49 The concept Intended to be released is crucial for manufacturers or importers to consider whether the textile articles are involved in REACH registration process. Intended release is a deliberate action and has added value function for the article. Below two examples of Intended Release 1. Chemical substances such as dyestuffs, softener and some agent are applied in textile production and it will be released after washing and finishing cycles, but it is not intended to be released. 2. Some chemicals (e.g. Aloe Vera) added on the fabric and it has a value added function for skin care by this chemical released from the fabric during wearing. This substance in product is intended to be released Further European Union Marketing & use Directive (76/769/EEC) has been officially repealed by the REACH regulation with the restriction requirements on the manufacturer, use or placing on market of over 50 categories of hazardous substances from 76/769/EEC have been incorporated into Annexure XVII of REACH. The substances that are of interest to textiles covered in Annexure XVII of REACH are: 1) Organo stannic compounds 2) Phthalates 3) Azo colorants 4) Mercury compounds 5) Nickel release 6) PFOS 7) Methylenediphenyl diisocyanate (MDI) 8) Cyclohexanone In Article 57 of the REACH regulation, substances of very high concern (SVHC) are defined as follows: Carcinogenic, mutagenic or toxic to reproduction (CMR), meeting the criteria for classification in category 1 or 2 in accordance with Directive 67/548/EEC Persistent, bio-accumulative and toxic (PBT) or very persistent and very bioaccumulative (vpvb) according to the criteria in Annex XIII of the REACH regulation, and/or Identified, on a case-by-case basis, from scientific evidence as causing probable serious effects to human health or the environment of an equivalent level of concern of those above (e.g. endocrine disrupters) The European Chemical Agency (ECHA) released the first Candidate List of 15 SVHCs for authorization in Aug 2008, the second in Jan 2010 and the third in June Companies are encouraged to check potential duties because once substances are officially published, on the candidate list they are immediately subject to certain REACH requirements including information in supply chain for substances, preparations, and particularly articles. Since the proposal is dynamic and ongoing process the candidate list is subject to change in the future and will include more substances as suggested by member states for inclusion. 49

50 REACH SVHC candidate list as of June 2014 No. Substance EC No. CAS No. 1 Anthracene ,4-Diaminodiphenylmethane Dibutyl phthalate (DBP) Relevance/Likelihood of Use for Textile End Products For dye preparations For dyes and polyurethane Plastisol prints; PVC binders 4 Cobalt dichloride No; 5 Diarsenic pentoxide No; 6 Diarsenic trioxide No; 7 Sodium dichromate dihydrate tert-Butyl-2,4,6-trinitro-m-xylene (Musk xylene) No; 9 Bis(2-ethylhexyl)phthalate (DEHP) Hexabromocyclododacane (HBCDD) 11 Alkanes, C10-C13, (Short chain chlorinated paraffins) Plastisol prints; PVC binders Flame retardant Yes In leather, Flame retardant 12 Bis(tributyltin) oxide No; 13 Lead hydrogen arsenate No; 14 Benzyl butyl phthalate (BBP) Plastisol prints; PVC binders 15 Triethyl arsenate No; 16 Anthracene oil No; Anthracene oil, Anthracene paste, Distn. Lights Anthracene oil, Anthracene paste, Anthracene Fraction No; No; 19 Anthracene oil, Anthracene low No; 20 Anthracene oil, Anthracene paste No; 21 Coal tar pitch, high temperature No; 22 Zirconia Aluminosilicate, refractory ceramic fibres No; 23 2,4-Dinitrotoluene Diisobutyl phthalate (DIBP) Lead chromate Lead chromate molybdate sulphate (C. I. Pigment Red 104) Polyurathane Foam Plastisol prints; PVC binders Pigments and dyes Pigments and dyes 27 Lead sulphochromate yellow (C. I, Pigment Yellow 34) Pigments and dyes 50

51 28 Tris(2-chloroethyl)phosphate Acrylamide Plasticizer and flame retardant Textile processing, coating and paints 30 Ammonium dichromate Boric acid Glaze paste, Flame Retardant 32 Disodium tetraborate, anhydrous Potassium chromate Potassium dichromate Sodium chromate Tetraboron disodium heptoxide hydrate Trichloroethylene Cobalt(II) sulphate Cobalt(II) dinitrate Pigments and inks Oxidizing agent, Leather tanning Oxidizing agent, Mordant Flame Retardant Stain remover, scouring aids Pigments and inks Pigments and inks 40 Cobalt(II) carbonate Cobalt(II) diacetate Methoxyethanol Pigments and inks Pigments and inks Solvents and adhesive coating 43 2-Ethoxyethanol Solvents 44 Chromium trioxide No; 45 Chromic acid Oligomers of chromic acid and dichromic acid Dichromic acid Pigments, ink, catalyst for polyester 46 2-Ethoxyethyl acetate Solvent for pigment removal 47 Strontium Chromate No; 1,2-Benzenedicarboxylic acid, di-c branched and linear alkyl esters Plasticizers 49 Hydrazine Methyl-2-pyrrolidone Fibre modification agent Solvent for paint removal and surface treatment in textiles 51

52 51 1,2,3-Trichloropropane Solvent for paint removal and surface treatment in textiles such as degreasing 52 1,2-Benzenedicarboxylic acid, di-c6-8- branched alkyl esters, C7- rich Plasticizers 53 Aluminosilicate, refractory ceramic fibres - Are fibres covered by Index No in Annex VI Part3, Table 3.1 of Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December No; 54 Calcium arsenate No; 55 Bis(2-methoxyethyl)ether Used in water based dyes, dispersant for plastics 56 Zirconia Aluminosilicate, refractory ceramic fibres Are fibres covered by Index No in Annex VI Part3, Table 3.1 of Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December No; 57 Potassium hydroxy octaoxodizincate dichromate Used in anticorrosion pigments 58 Lead dipcrate No; N,N-Dimethyl acetamide Used in paint strippers and ink removers 60 Arsenic acid Methoxyaniline; o-anisidine Used in Desiccant for cotton Used in azo dyes,pigments and fragrances. 62 Trilead diarsenate No; 63 1,2-Dichloroethane Used in leather cleaning 64 Pentazinc chromate octahydroxide No; 65 4-(1,1,3,3-tetramethylbutyl)phenol Used in textile auxilliaeries as surfactants. 66 Formaldehyde, oligomeric reaction products with aniline No; 67 Bis(2-methoxyethyl)phthalate Used as a plasticizer in printing ink. 52

53 68 Lead diazide, Lead azide No; 69 Lead styphnate No; 70 2,2'-Dichloro-4,4'-methylenedianiline No; 71 Phenolphthalein No; Catalyst in yarn 72 Dichromium tris(chromate) mordanting 73 1,1-Bis(2-methoxyethoxy)ethane (TEDGME); triglyme) No; 74 1,2-Dimethoxyethane; ethylene glycol dimethylether (EGDME) No; 75 Diboron trioxide Formamide Glass fibres, flame retardants, adhesives, inks/paints, detergents and cleaners Plasticizer 77 Lead(II)bis(methanesulphonate) No; ,3,5-Tris(oxiranylmethyl)-1,3,5-triazine- 2,4,6-(1H,3H,5H)-trione (TGIC) 1,3,5-Tris[(2S and 2R)-2,3-epoxypropyl]- 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (β- TGIC) Hardner in resins and coatings, silk screen printing coating, stabilisers for plastics Hardner in resins and coatings, silk screen printing coating, stabilisers for plastics 80 4,4'-Bis(dimethylamino)benzophenone (Michler's ketone) Intermediate in triphenylmethane dyes 81 N,N,N',N'-Tetramethyl-4,4'- methylenedianiline (Michler's base) Intermediate in triphenylmethane dyes 82 [4-[[4-Anilino-1-naphthyl][4- (dimethylamino)phenyl]methylene]cyclo hexa-2,5-dien-1- ylidene]dimethylammonium chloride (C. I. Basic Blue 26) [with > 0.1% of Michler's ketone (EC No ) or Michler's bse (EC No )] Formulation of textile dyes 83 [4-[4,4'- Bis(dimethylamino)benzhydrylidene]cyclo hexa-2,5-dien-1- ylidene]dimethylammonium chloride (C. I. Basic Violet 3)[with > 0.1% of Michler'e ketone (EC No ) or Michler'e base (EC No )] No; 53

54 84 4,4'-Bis(dimethylamino)-4"- (methylamino)trityl alcohol [with > 0.1% of Michler'e ketone (EC No ) or Michler'e base (EC No )] No; 85 α,α-bis[4-dimethylamino)]-4- (phenylamino)naphthalene-1-methanol (C. I. Solvent Blue 4) [with > 0.1% of Michler'e ketone (EC No ) or Michler'e base (EC No )] In formulation of printing ink 86 Bis(pentabromophenyl ether; Decabromophenyl ether; DecaBDE Pentacosafluorotridecanoic acid Tricosafluorododecanoic acid Henicosafluoroundecanoic acid Heptacosafluorotetradecanoic acid Diazene-1,2-dicarboxamide; C,C'- azodi(formamide) In formulation of flame retardants In production of fluoropolymers and fluorotelomers which is further used in coating material. In production of fluoropolymers and fluorotelomers which is further used in coating material. In production of fluoropolymers and fluorotelomers which is further used in coating material. In production of fluoropolymers and fluorotelomers which is further used in coating material. In production of fluoropolymers and fluorotelomers which is further used in coating material. 92 Cyclohexane-1,2-dicarboxylic anhydride[1] cis-cyclohexane-1,2-dicraboxylic anhydride[2] transcyclohexane-1,2-dicraboxylic anhydride[3] {Individual cis-[2] and trans-[3] isomer substances and all possible combinations of the cisand trans- isomers[1] are covered by this entry} In production of phthalates which in turn are used as plasticizers 54

55 93 Hexahydromethylphthalic anhydride[1] Hexahydro-4-methylphthalic anhydride[2] Hexahydro-1-methylphthalic anhydride[3] Hexahydro-3-methylphthalic anhydride[4] {Individual isomers[2], [3] & [4](including their -cis and -trans isomeric forms) and all possible combinations of isomers[1] are covered by this entry} No; 94 4-Nonyl phenol (branched & Linear) (Substances with linear and/or branched alkyl chain with a carbon number of 9 covalently bound in position 4 to phenol, covering also UVCB- and well defined substances which include any one of the individual isomers or a combination thereof) --- Textile related auxilliaries 95 4-(1,1,3,3)-Tetramethylbutyl phenol, ethoxylated (covering well-defined substances and UVCB substances, polymers and homologues) Textile related auxilliaries 96 Methoxyacetic acid N,N-Dimethylformamide Dibutyltin dichloride (DBCT) Textile related auxilliaries, plasticizer and colouring agent Solvent in manufacture of dyes, paint removers etc. Used as stabilizers and antifouling agents. 99 Lead monoxide (Lead Oxide) No; 100 Orange lead (Lead tetroxide) Used as pigment for primer paints, 101 Lead bis(tetrafluoroborate) Used as catalyst in the production of linear polyesters 102 Trilead bis(carbonate)dihydroxide No; 103 Lead titanium trioxide No; 104 Lead titanium zirconium oxide No; 105 Silicic acid, lead salt No; 55

56 106 Silicic acid (H 2 Si 2 O 5 ), barium salt (1:1), lead doped [with lead (Pb) content above the applicable generic concentration limit for toxicity for reproduction 'Repr, 1A (CLP) or category 1 (DSD); the substance is the member of the group entry of lead compounds, with index number in Regulation (EC) No. 1272/2008] No; Bromopropane (n-propylbromide) No; Methyloxirane (Propylene oxide) Used in polyurathane plastics 109 1,2-Benzenedicarboxylic acid, dipentyl ester, branched and linear Plasticizer in plastics 110 Diisopentyl phthalate (DIPP) No; 111 N-pentyl-isopentyl phthalate No; Use as excellent solvent, 112 1,2-Diethoxyethane textile conditioning, solvent for dyes, plasticizer 113 Acetic acid, lead salt, basic No; 114 Lead oxide sulphate No; 115 [Phthalato(2-)]dioxotrilead No; 116 Dioxobis(stearato)trilead No; 117 Fatty acids, C16-C18, lead salts No; 118 Lead cyanamidate No; 119 Lead dinitrate Pentalead tetraoxide sulphate Pyrochlore antimony lead yellow Additives in printing fabric. In paint preparation No; Used as a pigment in ceramic, glass and plastics 122 Sulphurous acid, lead salt, dibasic No; 123 Tetraethyl lead No; 124 Tetralead trioxide sulphate In paint preparation 125 Trilead dioxide phosphonate No; 126 Furan Resins from furan are used in natural fibre composite applications. 127 Diethyl sulphate Used as a a chemical intermediate to produce other products for coating, pharmaceuticles, personal care, detergents and textiles. 56

57 128 3-Ethyl-2-methyl-2-(3-methylbutyl)-1,3- oxazolidine Used as moisture scavenger in urethanes 129 Dinoseb(6-sec-butyl-2,4-dinitrophenol) ,4'-Methylenedi-o-toluidine '-Oxydianiline and its salts Aminoazobenzene Used as fungicide and weedicide in cotton crops For dye preparations For dye preparations For dye preparations Methyl-m-phenylenediamine (toluene- 2,4-diamine) For dye preparations Methoxy-m-toluidine (p-cresidine) Biphenyl-4-ylamine In dyes preparation In dyes preparation 136 o-aminoazotoluene[(4-o-tolyazo-otoluidine)] In dyes preparation 137 o-toluidene N-Methylacetamide Cadmium Cadmium oxide Ammonium pentadecafluorooctanoate (APFO) Pentadecafluorooctanoic acid (PFOA) Dipentyl phthalate (DPP) 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 UVCBand well-defined substances, polymers and homologues, which include any of the individual isomers and/or combinations thereof] In dyes preparation As plasticizer In textile accessories and jewellery In pigments, dyes, stabilizers in plastics In fluoropolymers and fluorotelomers used in coatings In fluoropolymers and fluorotelomers used in coatings As solvents for dyes and plasticizer in nailpolish as surfactants in various formulations used in textile industry 57

58 145 Cadmium sulhide Disodium 3,3'-[[1,1'-biphenyl]-4,4'- diylbis(azo)]bis(4-aminonaphthalene-1- sulphonate) (C.I. Direct Red 28) Disodium 4-amino-3-[[4'-[(2,4- diaminophenyl)azo][1,1'-biphenyl]-4- yl]azo] -5-hydroxy-6- (phenylazo)naphthalene-2,7- disulphonate (C.I. Direct Black 38) Dihexyl phthalate as mordant in dyeing and printing textiles as a dye in textile and paper industry as a dye in textile industry, direct dye for cotton as plasticizer 149 Imidazolidine-2-thione (2-imidazolidine- 2-thiol) No; 150 Lead diacetate Trixylyl phosphate Cadmium chloride ,2-Benzenedicarboxylic acid, dihexyl ester, branched and linear Sodium peroxometaborate Sodium perborate; Perboric acid sodium salt as mordant in dyeing and printing textiles, as a fixative in some dyes as a lubricant and lubricant additive, flame retardant as a lmordant in dyeing and printing of textiles, mfg og cadmium yellow pigment as plasticizer As a source of active oxygen in detergent, laundry detergent, cleaning products. As a source of active oxygen in detergent, laundry detergent, cleaning products Producers, importers and other suppliers of articles containing SVHC included in the candidate list in a concentration above 0.1% (w/w) have to provide information about the SVHC to the recipients of the articles. According to article 33, the information can be automatically provided, or it must be available upon request by consumer, free of charge and within 45 days. As of June 2011, producers, importers and other suppliers will be required to notify ECHA when a SVHC in the candidate list is present in articles above a concentration of 0.1% (w/w) and in an amount totalling over 1 tonne per year per producer or importer. 58

59 GREENPEACE: DIRTY LAUNDRY REPORTS AND JOINT ROAD MAP Greenpeace International is an independent global campaigning organisation that acts to change attitude and behaviour, to protect and conserve the environment and to promote peace. Greenpeace is campaigning to stop industrial pollution of our water with hazardous, persistent and hormone-disrupting chemicals by demanding that companies and governments take action to Detox our future. The organisation has published related reports under the title Dirty Laundry. The first Dirty Laundry report, profiles the problem of toxic water pollution resulting from the release of hazardous chemicals by the textile industry in China. Greenpeace is calling on the brands and suppliers identified in this investigation to become champions for a toxic-free future, by eliminating all releases of hazardous chemicals from their supply chains and their products. The latest research into toxic water pollution released August 23rd, by Greenpeace International, reveals the presence of nonylphenol ethoxylates in clothing items bearing the logos of 14 global brands, including Adidas, H&M and Abercrombie & Fitch. Launched August 23rd 2011, in Beijing and Manila, Greenpeace s second Dirty Laundry report presents the results of analysis of clothing and fabric-based shoes sold internationally by major clothing brands. Of the 78 articles tested, 52 were found to contain nonylphenol ethoxylates, chemicals which breaks down into the hormone-disrupting nonylphenol. The findings provide a snapshot of the kind of toxic chemicals that are being released by the textile industry into waterways all over the world and are indicative of a much wider problem. In response to getting rid of toxic water pollution problem, six major brands viz. Adidas Group, C&A, H&M, LiNing, Nike and Puma issued a Joint Road Map towards zero discharge of Hazardous Chemicals by Later few more members have also joined the group viz. Esprit, G-Star Raw, Inditex, Jack Wolfskin, Levi Strauss & Co., M & S and New Balance Athletic Shoe, Inc. Thus the total number of ZDHC group members as on June 11, 2013 are 13. The Joint Roadmap communicates the ZDHC Programme s long-term vision and goals and is a high-level strategic document supported by actionable plan that focuses on goals, milestones, deliverables and responsibilities. Approach of elimination and discharge of hazardous chemicals is segmented in to two categories. 1. Priority chemical groups Ortho phthalates Brominated and chlorinated Flame Retardants Azo dyes releasing carcinogenic amines. Organotin compounds Chlorobenzenes Chlorophenols Chlorinated solvents Short-chained chlorinated paraffins Heavy metals viz. Cadmium, Lead, Mercury and Chromium VI APEOs/NPE Perfluorinated chemicals 59

60 2. Other hazardous chemicals restricted or controlled under national legislations, identified by appropriate existing black lists, or as identified by hazard/use protocol. By 2013, a plan will be developed to evaluate the chemical inventory by intrinsic hazard and a sector wise list of hazardous chemicals will be established. This list will be used to identify alternative (greener) chemical formulations that are needed. The current examples of this activity are water based adhesives and water based inks. By end of 2013, a shared dye house and printer audit protocol will be developed with the competent third party and by the end of 2014, Leather Working Group will develop a programme to incentivize the suppliers to fulfil the dye house and printer audit protocol. By 2015, ZDHC Group will develop a publicly available list of chemicals targeted for phase out and /or research, set up evaluation and substitution process, starting with PFCs through Joint Road map version 2. A mechanism will be developed to facilitate disclosure by chemical industry that will lead to a list of chemical formulations that meet ZDHC MRSL. Outline parameters to monitortotal water discharge, water and energy consumption per kilo of product. Thus by 2020, apparel and footwear industry will deliver high quality product while using safe chemistries and operating in ways that keep communities free from unintended negative environmental impacts. 60

61 ECO LABELS Eco labels serve to lay down criteria for ecological parameters and are used as certification tools for products. In textiles, there are many eco labels. Some are more popular than others. The European Commission has reported that 4 out of 5 European consumers would prefer environmentally friendly products provided they are controlled by independent organizations. Labels therefore seek to provide such assurance to consumers. There is a wide variety of eco-labelling schemes covering a wide variety of textile product groups. Each has developed criteria that vary in approach from full life cycle analysis to schemes that addresses only the quality of the final product. Types of organizations involved in eco labelling schemes are shown in table below: Some Government Labels Germany: Blue angel Canada: Env.Choice Japan: EcoMark Nordic Countries: White Swan US: Green Seal India : Eco Mark France: NF Environment Netherlands: Stichting Milieukeur EU: European Flower Some commercial Labels ÖkoTex 100 ToxProof: TuV, Germany AKN: Natural Textile Assn. Germany EPG: European Prod. Guarantee (ELTAC) GuT: Carpets, Germany GuW: Furnishing, Germany 61

62 GLOBAL ORGANIC TEXTILE STANDARD (GOTS) The organic textile standard was born from the following needs expressed both by consumers and manufacturers: The will to fight against the negative environmental impact of conventional industry. The will to promote production and use of organic fibres. The difficulty for consumers to clearly recognize the eco-friendly processed textile products. The aim these standards is to define requirements to ensure organic status of textiles, from harvesting of the raw materials through environmentally and socially responsible manufacturing up to labelling in order to provide a credible assurance to the end consumer. The GOTS certification is issued by certification bodies such as Control Union Certifications, IMO, One-Cert etc. Texanlab is able to test products as per GOTS requirement and certification can be done only by certification bodies. For detailed information on GOTS, contact us at thane@texanlab.com The parameters related to GOTS testing are discussed below: Adsorbable Organic Halogens (AOX) Adsorbable organically bound halogens (AOX) are a group of chemicals which can be adsorbed from water on to activated carbon. Most AOXs are compounds containing chlorine, but some contain elements such as bromine or iodine. There are growing concerns with regard to the use of products and processes using halogen containing compounds, as it can give rise to effluents with high levels of Adsorbable Organic Halides (AOX). AOX are difficult to breakdown as they are not easily biodegradable. AOX is also associated with toxic dioxins and furans that can be the result of chlorine used during the bleaching process. In view of the above reasons, most organic textile standards and various eco labels prohibit AOX or any ingredients and processes that might produce AOX compounds in effluents / wastewater. (Permanent AOX) Possible sources of AOX in textile production are: Halogen containing dyestuffs (e.g. chlorinated reactive dyes / vat dyes /disperse dyes) Halogen containing solvents and auxiliaries Dye accelerators (carriers) / levelling agents used to dye synthetic fibres Certain finishing auxiliaries Chlorinated bleaches Anti-felting finishing of wool 62

63 Summary of AOX requirements < 1.0 % for any input in the manufacturing processes that contribute to primary effluent and < 5.0 mg/kg in organic textiles and additional material and Limits / Restrictions* accessories < 250 ppm on man made cellulosic fibres (EU Eco label) < 40 ppm in bleaching agents (Eco labels) Characteristics / Toxicity Non biodegradable; persistent; carcinogenic Chlorinated dyes, dye accelerators, solvents, chlorinated Processes bleaches etc. Regulation / Legislation EU Directive on water/waste water; DIN ISO : 1997 (controlled combustion and Test Method microcoulometry) * Limits mentioned here are typical. Each Buyer may have own limits. Biodegradability & Bioaccumulation The main environmental concern in the textile industry is about the amount of water discharged and the chemical load it carries. The chemicals used in the textile industry give rise to a wide range of environmental and toxicological impacts. The impact of chemicals on aquatic environment can be minimized by using biodegradable products in the various textile processes. What is biodegradation? Biodegradation is a process by which organic substances are broken down by microorganisms (bacteria) in aquatic environment resulting in elimination of the ingredient. If the ingredient no longer exists, there is no concern about its potential to affect the environment. Biodegradability is therefore considered an important attribute for chemicals and most organic textile standards / various eco labels stipulate biodegradability limits and insist on use of chemicals that can be biodegraded or ecologically purified. A large number of chemicals and auxiliaries are used by the textile industry. Most of them are complex chemicals and biodegradability information is scant or unknown for majority of them. A list of such chemicals is given below: Spin finishes and lubricants used on fibres Sizing chemicals on yarns Pre-treatment chemicals Water soluble Dyes Dyeing and printing auxiliaries Finishing auxiliaries 63

64 Summary of Biodegradability requirements Limits / Restrictions Characteristics / Toxicity Processes Min. 70% (Less than 70% allowed if aquatic toxicity (LC 50) >100 mg / l) If not sufficiently biodegradable, they become persistent and enter the food chain All water soluble and organic auxiliary chemicals and dyes Regulation / Legislation EU Directive on water/waste water; OECD 301A to E, 302A or 302B; ISO 7827, ISO 9887 or Test Method ISO 9888 In this context, a substance is usually considered sufficiently bio-degradable or eliminable: If when tested one of the methods (OECD 301A, OECD 301E, ISO 7827, OECD 302A, ISO 9887, OECD 302B or ISO 9888) it shows a percentage degradation of at least 70% within 28 days If when tested one of the methods (OECD 301B, ISO 9439, OECD 301C, OECD 301D, ISO or ISO 14593) it shows a percentage degradation of at least 60% within 28 days If when tested one of the methods (OECD 303A or ISO 11733) it shows a percentage degradation of at least 80% within 28 days Degradability is one of the important intrinsic properties of chemical substances that determine their potential environmental hazard. Non-degradable substances will persist in the environment and may consequently have a potential for causing long-term adverse effects on biota. In contrast, degradable substances may be removed in the sewers, in sewage treatment plants or in the environment What is Bioaccumulation? Bioaccumulation is uptake of chemicals in organisms from the surrounding medium (water, pore water) by gills, skin, etc. or by ingestion of particle-bound chemicals. This property is assessed by octanol-water partition coefficient at a specified temperature. Octanol is an organic solvent that is used as a surrogate for natural organic matter. The determination of bioaccumulation (K ow) or more specifically (K ow), can either be done by the shake-flask method (OECD 107) or directly by Reversed Phase HPLC (OECD 117). In HPLC method, the retention time of the chemical of interest is compared to retention times of reference samples with similar structures and known log K ow values. Higher the log K ow value, more potential for a chemical to bio accumulate. A log K ow > 4 is classified as highly bio accumulative. 64

65 Toxicity Currently laws in many countries require manufacturers of chemicals to assess the hazard potentials, i.e. toxicity to both environment and human health for each of their substances and it is also required to be incorporated in Material Safety Data Sheets (MSDS) for the information of down stream users in the manufacturing chain. Most organic textile standards and eco labels also insist on the use of chemicals which are safe and non-hazardous. A large number of chemicals, dyes and auxiliaries are used by the textile industry. The hazardous property in terms of toxicity is not sufficiently known or established for majority of them. It is therefore necessary to check toxicity for each of these chemicals to the following species in aquatic environment. In addition, it may also be required to assess for oral toxicity (LD50). Aquatic Toxicity Acute fish toxicity (LC50) Acute Daphnia toxicity (EC50) Acute toxicity to algae (IC50) Summary of toxicity requirements Limits / Restrictions Characteristics / Toxicity Processes Aquatic toxicity (LC50, EC50, IC50) > 1 mg/kg Some of the chemicals used in processing are known to be toxic to environment and human health All chemical products used in the industry Regulation / Legislation EU directives on labelling, Organic textile standards, Eco labels LC50 fish : OECD 203 Test Method EC50 daphnia : OECD 202 LC50 algae : OECD 201 The toxicity is assessed relative to the degradability / eliminability of the respective substance. The basic idea is that a higher toxicity can be tolerated when the substance is easily eliminable / degradable. In the same way, a substance of low eliminability /degradability may only have a low toxicity. It must be taken into account here that the toxicity is low when the stated value for the toxicity in mg / l or mg / kg is high. A value of 100 mg / l means a lower toxicity than a value of 10 mg / l. This means that only higher concentrations of this chemical have a toxic effect on organisms. Biodegradability and toxicity of chemicals are generally assessed against the following criteria - A chemical is permitted for use in processing provided: Biodegradability / eliminability Aquatic Toxicity < 70 % > 100 mg/l > 70 % 10 to 100 mg/l (Harmful) > 95 % 1 to 10 mg/l (Toxic) X < 1 mg/l (Extremely Toxic) 65

66 Not permitted for use if the substance has < 20% eliminability, with an aquatic toxicity LC 50 < 10 mg / l and oral toxicity LD 50 < 2000 mg / kg. Acute Toxicity: Oral (LD 50) This is a test to carry out lethality testing by measuring how much of a chemical is required to cause death. The test is also referred as quantal test. The LD 50 test evaluates acute lethality from exposure to a substance or product. It is the value at which 50% of the test animals are expected to die. The smaller the LD 50 value, more toxic the chemical is. The test substance is classified according to Globally Harmonized System (GHS) for classification and labelling of chemicals which cause acute toxicity: LD50 GHS (Hazard) Category > 0-5 Category 1 > 5-50 Category 2 > Category 3 > Category 4 > Category 5 > 5000 Unclassified LD 50 of > 2000 mg/kg is considered as non-toxic In addition to these requirements, no input or material is approved if it is: Carcinogenic Mutagenic Toxic to mammals LD50 < 2000 mg / kg is not allowed Known to be bio-accumulative and not biodegradable An endocrine Disrupter Special Note : GOTS ver. 3.0 has removed the requirement of new testing for toxicity and suggests alternate methods to determine aquatic and oral toxicity of all substances. 66

67 THE EU ECO LABEL: THE FLOWER The EU countries have developed an EU eco-label valid over the Union, thus creating an environmental labelling system in accordance with Regulation No. 880 dated 23 rd March 1992 from the EU council. This is purely a voluntary scheme to encourage business products and services that are kinder to the environment and European consumers- including public and private purchasers- making it easy to identify them. The priority emphasis of the label is on achieving the following: Limited use of substances harmful to the environment and health Reduced water and air pollution Textile shrink resistance during washing and drying Colour resistance to perspiration, washing, wet and dry rubbing and light exposure. It can be awarded to all kind of textile clothing and accessories, interior and textiles, fibres, yarn and fabric. Each Member State of the EU has designated a Competent Body which is responsible for receiving applications from manufacturers, retailers, service providers or importers and granting the label. Criteria The criteria and relevant options for testing and methods are periodically revised (every 4 years). The criteria given in Committee Decision 2009/567/EC, July 2009 (valid up to June 2014) are revised and replaced by Commission Decision 2014/350/EU, 5 th June 2014 and are summarized below. Environmental requirement for types of fibre used (criteria 1 9) Environmental requirement for types of components and accessories used (criteria 10 12) Environmental requirements for processes and chemicals ( criteria 13 16) Requirement for fitness for use of finished textiles (criteria 17 25) For a product to receive the EU Ecolabel, it needs to satisfy all the criteria specified. Because this is a legally formulated requirement, no changes or deviation is allowed. Some basic information about the EU Ecolabel is given below. Testing The EU Flower requires most of the criteria to be verified with declarations and verification of paperwork. Testing is mandated in a few cases and is suggested in some. Any testing verification, wherever required, may be done only by ISO accredited laboratories, by the methods specified under relevant category. Introduction The European Eco-label encourages businesses to market products and services that are kinder to the environment. The European Eco-label is symbolised by the Flower. 67

68 The European eco-label, which is the only sign of environmental quality both certified by an independent organisation and valid throughout Europe, presents a unique opportunity to satisfy your customer s expectation. The Eco Label Applies to all textile products including textile clothing and accessories, fibres, yarn and fabrics and interior textiles except wall and floor coverings. For which products can an application be made? Applications can be made for the following textile products 1) Textile clothing consists of at least 90 % by weight of textile fibres. 2) Accessories for textile clothing (such as handkerchiefs, scarves, bags, shopping bags, rucksacks, belts, etc.) consist of at least 90 % by weight of textiles fibres. 3) Interior textiles (home textiles) consisting of at least 90 % by weight of textile fibres. Wall and floor coverings are excluded. 4) Fibres, yarn, and fabric intended for use in textile clothing and accessories for textile clothing or interior textiles. Note: For textile clothing and accessories for textile clothing and interior textiles applies that down, feathers, membranes and coating need not to be taken into account in the calculation of the percentage of textile fibres. Who can apply for Ecolabel? Applications for the Ecolabel may be submitted by manufacturers, importers, services providers, traders and retailers. Traders and retailers may submit applications in respect of products placed on the market under their own brand names. Applying for the Flower When applying for the European Eco-label: Select relevant competent authority within the EU to whom application would be submitted. Commence correspondence; get all updates and a quote for the application fees. All chemicals and processes used in production should be identified. Documentation required for the application should be completed. These need to be supported by test reports or declarations as required. Application along with relevant fees to be submitted to any competent authority within the EU. List of these authorities and their jurisdiction are available on the EU Flower website. A copy of all material submitted should be retained. Note that the applicant has the responsibility for the product(s) being in continued compliance with the European Eco-label criteria. All rules and regulations regarding the use of EU Flower label need to be understood and followed. 68