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Testing Restricted Chemicals in Textiles. 200 5. B UREAU VERITAS Hong Kong Ltd Consumer Product Services Division. Dr. Ben Man. For the benefit of business and people. SUMMARY. 1 Introduction List of Restricted Substances I. Azo dyestuffs II. Carcinogenic / Sensitizing dyes

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  1. Testing Restricted Chemicals in Textiles 2005 BUREAU VERITAS Hong Kong Ltd Consumer Product Services Division Dr. Ben Man For the benefit of business and people

  2. SUMMARY 1 Introduction List of Restricted Substances I.Azo dyestuffs II.Carcinogenic / Sensitizing dyes III. Formaldehyde IV. Organotins V. Phthalates VI. PVC identification VII. Heavy Metals Content VIII. Nickel release IX. Flame retardants X. Phenols XI. Pesticides XII. APEO

  3. INTRODUCTION With the concern for the health of the customers as well as for the environment and working conditions in the factories, the establishment of CHEMICAL RESTRICTIONS for 1) Leather, 2) Textile, 3) Plastic and 4) Metals Products. Most restrictions are based upon legislation in Europe and USA. Bureau Veritas Consumer Products Services, Inc.

  4. Europe, 76/769/EEC Business for Social Responsibility (BSR) is a global organization that helps member companies achieve success in ways that respect ethical values, people, communities and the environment. INTRODUCTION Bureau Veritas Consumer Products Services, Inc.

  5. 2 LISTS OF RESTRICTED SUBSTANCES

  6. 2.I AZO DYES

  7. AZO DYES I. AZO DYES Azo dyes incorporate one or several azo group (-N=N-) bound with aromatic compounds. Some of the amines cleavage from azo colorants may be carcinogenic or potential carcinogens. Congo red Bureau Veritas Consumer Products Services, Inc.

  8. I. AZO DYES Azo dyestuffs may not be used in textile and leather articles which may come into direct and prolonged contact with human skin or oral cavity such as: - clothing, bedding, towels, hairpieces, wigs, hats, nappies and other sanitary items, sleeping bags; - footwear, gloves, wristwatch straps, handbags, purses/wallets, briefcases, chair covers; - textile or leather toys and toys which include textile or leather garments; - yarn and fabrics intended for use by the final consumer. Bureau Veritas Consumer Products Services, Inc.

  9. I. AZO DYES • Related Legislations • 2002/61/EC on 19 July 2002 – amendment for the 19th Council Directive 76/769/EEC relating to restrictions on the marketing and use of certain dangerous substances and preparations (azo colorants) • Maximum permissible limit: 30 mg/kg in finished articles or in dyed parts, 70 mg/kg in recycled fibres • 35 German Commodity Good Act (Bedarfsgegenständeverordnung, Bundesgesetzblatt I, nr. 24, 1997, page 796 – 800) • Maximum permissible limit: 30 mg/kg Bureau Veritas Consumer Products Services, Inc.

  10. I. AZO DYES • Test methods • 35 LMBG 82.02 (TEXTILE MATERIALS) • 35 LMBG 82.03 (LEATHER MATERIALS) • 35 LMBG 82.04 (POLYESTER MATERIALS) • EN 14362 part 1: 2003 • Methods for the determination of certain aromatic amines derived from azo colorants – Part I: Detection of the use of certain azo colorants accessible without extraction • EN 14362 part 2: 2003 • Method for the determination of certain aromatic amines derived from azo colorants – Part II: Detection of the use of certain azo colorants accessible by extracting the fibres • ISO 17234: 2003 • Determination of certain azo colorants in dyed leathers Bureau Veritas Consumer Products Services, Inc.

  11. I. AZO DYES Identify the material type of sample Cut sample into small pieces Textile Material 35 LMBG 82.02 Polyester Material 35 LMBG 82.04 Leather Material 35 LMBG 82.03 Stream extraction by CHLOROBENZENE for 30 min Degreased by Hexane Extraction / Reduction at pH 6 (70 oC) for 30 min Column Extraction using MTBE Pre-concentrate using rotatory evaporator to 1 ml If failed, consult client for dye information GC-MS, followed by HPLC confirmation Bureau Veritas Consumer Products Services, Inc.

  12. 2.II SENSITIZING DISPERSE DYES

  13. II. CARCINOGENIC / SENSITIZING DISPERSE DYES • Sensitizing disperse dyes are used for dyeing manufactured fibers (polyester, acetate and polyamide). • These dyes are suspected to cause allergenic and carcinogenic reactions LIST OF SENSITIZING DISPERSE DYES Bureau Veritas Consumer Products Services, Inc.

  14. II. CARCINOGENIC / SENSITIZING DISPERSE DYES • Related Legislation • § 30 of the German Food and Commodities Law • Maximum permissible limit: Not detected (<5 mg/l) • Test methods • DIN 54231 Bureau Veritas Consumer Products Services, Inc.

  15. II. CARCINOGENIC / SENSITIZING DISPERSE DYES Cut sample into small pieces Extraction with methanol under ultrasonication at moderate temperature for 1 h Filter the extract using 0.45 mm nylon filter Analysis with LC-MS Confirm with DAD detection Bureau Veritas Consumer Products Services, Inc.

  16. 2.III FORMALDEHYDE

  17. III. FORMALDEHYDE • Formaldehyde is a volatile compound used widely in apparel and textile manufacturing as an anti-creasing and an-anti-shrinking agent. It also acts as a cross-linking agent or a preservatives • Formaldehyde is a suspected carcinogen. It is an irritant to eyes, nose, lung and may cause allergenic reactions. Bureau Veritas Consumer Products Services, Inc.

  18. III. FORMALDEHYDE • Related Legislations • Norway: Regulations concerning the regulation of certain chemicals and textiles (4/9/1999) • Maximum permissible limit: 30 ppm (below 2 years), 100 ppm (direct contact skin), 300 ppm (Indirect contact skin) • Finland: The Trade and Industry Ministry Decision on the Maximum Content of Formaldehyde in Certain Textile Products (11/18/1996) • Maximum permissible limit:30 ppm (below 2 years), 100 ppm (direct contact skin), 300 ppm (Indirect contact skin) • Japan: Japan Law for the control of household products containing harmful substances, Law no. 112 (10/12/1973) • Maximum permissible limit: 0.03 Abs (Infant), 75 ppm (Adult) • Test methods • ISO 14184 part 1: Determination of formaldehyde – Free and Hydrolized formaldehyde (water extraction method) • ISO 14184 part 1 = JIS (B) = JIS L1041 = Law 112 Bureau Veritas Consumer Products Services, Inc.

  19. III. FORMALDEHYDE • Test methods • ISO 14184 part 1: Determination of formaldehyde – Free and Hydrolized formaldehyde (water extraction method) • ISO 14184 part 1 = JIS (B) = JIS L1041 = Law 112 (Textile material) • ISO 14184 part 2 = AATCC 112 (Textile material) • In house method (plastic / metal component) Cut sample into small pieces Weigh 1 g of sample Extraction with distilled water in a sealed flask for 40 oC for 1 h Color development with NASH reagent Spectrometric analysis Bureau Veritas Consumer Products Services, Inc.

  20. 2.IV ORGANOTIN COMPOUNDS

  21. IV. ORGANOTIN COMPOUNDS • Organotin compounds are a class of chemical combining tin and organics such as butyl- and phenyl groups. Organotin compounds are predominantly found in the environment as antifoulants in marine paints, but they can also be used as biocides (antibacterials), and / or heat stabilizer in plastics • Organotin compounds are suspected to be endocrine disrupters. Bureau Veritas Consumer Products Services, Inc.

  22. IV. ORGANOTIN COMPOUNDS LIST OF ORGANOTIN COMPOUNDS (Nike request) • Related Legislation • Japan: (Organotin) Law for the Control of Household Products Containing Harmful Substances (Law no. 112 – 10/12/1973) • Test method • Extraction : Ethanol Extraction • Analysis : GC-MS • Tributyl tin chloride TBTCl, C12H27Sn+ • Triphenyl tin TPhSn+ Bureau Veritas Consumer Products Services, Inc.

  23. IV. ORGANOTIN COMPOUNDS Cut sample into small pieces Extraction with Solvent Derivatisation of Organotin Matrix Clean up GC-MS analysis Bureau Veritas Consumer Products Services, Inc.

  24. 2.V Phthalates

  25. DNOP DIDP BBP DEHP DBP V. PHTHALATES • Phthalates are a class of organic compounds added to plastics to increase flexibility. • In textile and apparel products, phthalates may associated with flexible plastic components, trims and screen print. • Previous literature showed that phthalates can migrate from a plastic into the body of a child sucks or chews on the plastic. They are suspected to be carinogenic and to disturb the hormone system. DINP Bureau Veritas Consumer Products Services, Inc.

  26. V. PHTHALATES LIST OF PHTHALATES • Related Legislations • Sweden: Amendment to Ordinance (1998:944) on the Prohibition Etc. in Connection with Handling, Importation and Exportation (Certain Cases) of Chemical Products. Section 16 was amended and a new Section 16a was added. The amendment now also includes child articles, which broadens the application (8/1/1999) • Maximum permissible limit: 500 ppm for individual, 1000 ppm for total Bureau Veritas Consumer Products Services, Inc.

  27. V. PHTHALATES • Related Legislations (Continue) • 1999/815/EEC • Maximum permissible limit: 1000 ppm for total (0.1 %) • Test method • BVCPS In House Method Cut sample into small pieces Dissolve the sample into solvent Precipitate the polymeric materials by another solvent Filter the extract LC-MS analysis Bureau Veritas Consumer Products Services, Inc.

  28. 2.VI PVC Identification

  29. VI. PVC IDENTIFICATION • PVC is thermoplastic that can be soft or hard, transparent or colored. Many of the compounds involved PVC production and in the ready PVC products are toxic and suspected to be toxic • In the textile industry, PVC is used for soft plastic accessories like badges or zip pullers, as coating on textiles for rainwear, as prints etc. • PVC items are environmentally persistent, and their manufacture and disposal often results in highly toxic wastes (e.g. DIOXINS) • Related Legislation: None Bureau Veritas Consumer Products Services, Inc.

  30. VI. PVC IDENTIFICATION Cut a small piece of sample FT-IR Scanning Direct Scanning Solvent Method Hot Press Method Put the sample on the glass window Add a few drops of THF on the FTIR glass window Put the sample on the heat plate to form a thin plastic thin Put the film on the glass window Press the sample on the glass window and remove it after 10 sec Scanning by FTIR and check the wave number at 830 – 835 nm (weak), 954 – 959 nm (moderate), 740 – 747 nm (moderate) Bureau Veritas Consumer Products Services, Inc.

  31. VI. PVC IDENTIFICATION Confirmation Test Beilstein Test HCl Release Test Dissolution Test Put the sample into solvent and dissolve the samples completely Heat up the copper wise and then scratch the sample surface for 10 sec Ignite the sample and put a wet pH paper on the top Add excess solvent (B) to precipitate the polymeric material Check if pH paper change to red in color Ignite the Cu wire again and examine if there is any green flame Scanning the precipitate with FT-IR and check the wave no. 600-700, ~1250 and ~1330 nm Bureau Veritas Consumer Products Services, Inc.

  32. 2.VII Heavy metal Content

  33. VII. HEAVY METALS CONTENT • Cadmium (Cd) • It is a naturally occurring and abundant metal that does not easily corrode (rust). It is often used for pigments, metal coatings, plastics (as a heat stabilizer), photographic films and batteries. • It and its containing compounds are carcinogenic. • Related legislation • Sweden: KIFS 1998:8 part 4, Chapter 9, Section 1 – 5 with appendix 2 (Limits Cd to prohibited) (1/1/1999) Bureau Veritas Consumer Products Services, Inc.

  34. VII. HEAVY METALS CONTENT • Chromium (Cr (0) + Cr (III) + Cr (VI)) • It is a naturally occurring metal that exists in three forms (Cr (0), Cr (III) and Cr (VI)). • Cr (III) is the most stable form, while Cr (0) and Cr (VI) are much rare • Cr (VI) and certain Cr (VI) containing compounds are known carcinogenic. It is also corrosive. • Related legislation • § 30 of the Food and Commodities Law • Maximum permissible limit: Not detected (< 3 mg/kg according to DIN 53314 (leather only)) Bureau Veritas Consumer Products Services, Inc.

  35. VII. HEAVY METALS CONTENT • Lead (Pb) • It is a naturally occurring metal important to the production of batteries, fuels, paints, plastics (as heat stabilizer), ceramics, caulking and solders • It and its containing compounds are reasonably anticipated to be carcinogens. • Lead can affect the central nervous system (particular children) and can damage the kidneys and immune system. • Related legislation • Denmark: Statutory Order on the Prohibition, Sales, Import and Manufacture of Lead and Products Containing Lead (12/1/2000) • Maximum permissible limit: 100 ppm Bureau Veritas Consumer Products Services, Inc.

  36. VII. HEAVY METALS CONTENT • Related Legislation (Continue) • US 16 CFR 1303 Ban of Lead – Containing Paint and Certain Consumer Products Bearing Lead Paint. • Maximum permissible limit: 0.06 % Bureau Veritas Consumer Products Services, Inc.

  37. VII. HEAVY METALS CONTENT • Mercury (Hg) • It is a naturally occurring metal. • It can exist as metallic mercury (liquid), gas (when heated) or as solids (inorganic / organic compounds) • It and its containing compounds can damage the central nervous system including the brain, and it is reasonably anticipated carcinogens • Related legislation • Denmark: Ministry of the Environment, Danish EPA. Statutory Order No. 692 of September 22, 1998 on the prohibition of Sale of Mercury Containing Products. (Electronic product only) • Maximum permissible limit: Not detected (< 50 ppm) Bureau Veritas Consumer Products Services, Inc.

  38. VII. HEAVY METALS CONTENT • Other heavy metals (Antimony (Sb), Arsenic (As)) • These metals may be associated with synthetic fibers, accessories for textile and clothing, paints, inks, trims, plastic and metal components, and may produce negative effects on human health. • Related Legislations • Europe: EN 71 part III • Maximum permissible limit: (Cd: 75 ppm, Pb: 90 ppm, Hg: 60 ppm, Total Cr: 60 ppm, Sb: 60 ppm, As: 25 ppm, Ba: 1000 ppm, Se: 500 ppm) • Denmark: Statutory Order No. 1199 of December 23, 1992 on the prohibition of Sale, Import and Manufacture of Cadmium containing products (1/1/1993). • Maximum permissible limit: 75 ppm Bureau Veritas Consumer Products Services, Inc.

  39. VII. HEAVY METALS CONTENT • Other test methods • ISO 105 E04: Textiles – Test for color fastness part E04: Color fastness to perspiration • Specimens of the textile in contact with adjacent fabrics are treated in two different solution containing histidine, drained and placed between two plates under a specified pressure in a test device. The specimen and the adjacent fabrics are dried separately. The change in color of each specimen and the staining of the adjacent fabrics are assessed with the grey scales. • Total Heavy metal content by Microwave digestion • The fabric sample is put into conc. acidic media in a quartz vessel and then the quartz vessel is transferred into a microwave digestor and the sample matrix is digested under high pressure. Bureau Veritas Consumer Products Services, Inc.

  40. Ext. heavy metals (EN 71 part III) Total Cadmium EN 1122 Chromium VI DIN 53314 Samples are separate for different colors / materials Cut samples into small pieces Digestion with H2SO4 Extraction with 0.07 N HCl Oxidation of organic matter by H2O2 Keep 37 oC for 1 h Filter the matrix UV/ Vis ICP AAS VII. HEAVY METALS CONTENT VII. HEAVY METALS CONTENT Heavy Metal Test Extraction with pH 6 buffer Filter with C18 pre-treated filter Bureau Veritas Consumer Products Services, Inc.

  41. 2.VIII Nickel Release

  42. VIII. NICKEL RELEASE • Nickel (Ni) • It is an abundant metal often combined with other metals to create alloys with increased hardness and resistance to corrosion • It and its containing compounds are reasonably anticipated carcinogens. • It can cause allergenic reaction to human beings. • Related legislation • Directive 94/27/EC (12th Amendment of Directive 76/769/EC on restrictions on the marketing and use of certain dangerous substances and preparations) of June 30: 1994. Official Journal of the European Community, Nr. L 188/1. • Maximum permissible limit: 0.5 mg/cm2/week Bureau Veritas Consumer Products Services, Inc.

  43. VIII. NICKEL RELEASE • Test methods • EN 1811 (Non-coated item) • EN 12472 + EN 1811 (Coated item) Non-coated item Clean the surface with detergent Coated item Put the sample into corrosion media at 50 oC for 2 h Abrasion for 4 h at room temp. Immerse into sweat solution for 7 days ICP analysis Bureau Veritas Consumer Products Services, Inc.

  44. 2.IX Flame retardants

  45. IX. FLAME RETARDANT • Flame retardants are chemical compounds that can be incorporated into textiles or applied by sprays to prevent burning. • The listed flame retardants are persistent in the environment and are suspected of affecting the immune system. One class of flame retardants, polybrominated biphenyls (PBBs), is structurally similar to toxic polychlorinated biphenyls (PCBs) compounds. Bureau Veritas Consumer Products Services, Inc.

  46. IX. FLAME RETARDANT Bureau Veritas Consumer Products Services, Inc.

  47. IX. FLAME RETARDANT • Related legislations • Directive 1976/769/EEC of 27 July 1976 on restriction on the marketing and use of certain dangerous substances and preparations. Last relevant amendment 83/264/EC – existing law implemented July 27, 1976. • Maximum permissible limit: (TRIS, PBB, TEPA) None detected (5 mg/kg) • Directive 2003/11/EC of the European Parliament and of the Council of 6th February 2003 amending for the 24th time Council Directive 76/769/EEC relating to restrictions on the marketing and use of certain dangerous substances and preparations • Maximum permissible limit: (PentaBDE, OctaBDE) None detected (5 mg/kg) Bureau Veritas Consumer Products Services, Inc.

  48. IX. FLAME RETARDANT • Related legislations • Law for the Control of household products containing harmful substances; Law no. 112, October 12, 1973. Partially amended in 1978 and 1981 (Japan) – existing law implemented October 12, 1973 • Maximum permissible limit: (Bis(2,3-dibbromopropyl)phosphate) None detected (5 mg/kg) • Directive 2002/45/EC of the European Parliament and of the Council of 25 June 2002 amending for the twentieth time Council Directive 76/769/EEC relating to restrictions on the marketing and use of certain dangerous substances and preparations (Short-chain chlorinated paraffins) • Maximum permissible limit: 1 % Bureau Veritas Consumer Products Services, Inc.

  49. IX. FLAME RETARDANT Flame retardant PBB / SCP PentaBDE, OctaBDE Bis(2,3-dibromopropyl)phosphate TRIS TEPA Cut samples into small pieces Extraction with methanol KOH digestion Extraction with solvent Filter the extract Filter the extract Headspace GC-MS LC-MS GC-MS LC-MS / GC - MS Bureau Veritas Consumer Products Services, Inc.

  50. 2.X PHENOLS

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