KOTITI Environmental & Hazardous Substances Analysis Center

Transcription

1 KOTITI Environmental & Hazardous Substances Analysis Center

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3 reparation

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8 Substances Preparation Article?? BOM 1? SVHC??? Article 0.1%? 1?

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32 THE LEADING INSTITUTE OF TESTING, INSPECTION & R&D

33 CONTENT INTRODUCTION KOTITI LIST OF RESTRICTED SUBSTANCES COMPANY PROFILE Azo dyes Carcinogenic / Sensitizing dyes Formaldehyde Organotin compounds Phthalates Cr6 Flame retardants Phenols APEO PAHs DMF SUMMARY

34 INTRODUCTION Worldwide Trend on Green Requirement to Industry

35 WHY INTRODUCTION Regulations NGO s (GreenPeace, Öko-Tex etc.) Safety for: The workers The consumers The environment Social Responsibility BRAND name protection (vs Media)

36 Legal Product Demands INTRODUCTION Dangerous Substances Directive, 76/769/EEC REACH German Food and Commodity Law(LFGB) US California Proposition 65 65

37 Legal Product Demands INTRODUCTION US Consumer Product Safety Commission website Product Recall

38 Legislation INTRODUCTION If your product do not comply with regulation Recall and compensation Lose your business Lower your competitiveness Destroy your brand??? Barbie Dream Puppy House (lead paint on dog)-recall 675,000 unit

39 Restricted Substances Briefing

40 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 Leather Textile Plastic Metals Products Paper Most restrictions are based upon legislations in Europe and USA.

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42 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 Benzidine Carcinogen NH 2 SO 3 Na N N N N SO 3 Na REDUCTION H 2 N NH 2 NH 2 H 2 N 2 SO 3 NaNH 2

43 AZO DYES Azo dyes 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.

44 AZO DYES No. Substances CAS No. 1 o-toluidine ,4 Xylidine ,6 Xylidine Methoxyaniline p-chloroaniline p-kresidine ,4,5-Trimethylaniline Chloro-o-Toluidine ,4-Toluylenediamine ,4-Diaminoanisole Naphthylamine Amino-4-nitrotoluene Aminodiphenyl p-aminoazobenzene ,4 -Oxydianiline Benzidine ,4 -Diaminodiphenylmethane o-aminoazotoluene ,3 -Dimethyl-4,4 -diaminodiphenylmethane ,3 -Dimethylbenzidine ,4 -Thiodianiline ,3 -Dichlorobenzidine ,4 -Methylene-bis-(2-Chloraniline) ,3 -Dimethoxybenzidine

45 AZO DYES Test methods 64 LFGB (Textile) 64 LFGB (Leather) 64 LFGB (Polyester) 64 LFGB (4-aminoazobenzene if Aniline or Phenylenediamine is detected.) EN part 1: 2003 (Textile) EN part 2: 2003 (Polyester) ISO 17234: 2003 (Leather) KS K 0147:2003 (Textile) KS K 0734:2007 (Polyester)

46 AZO DYES Test Process Column Extraction Rotary Evaporation Dye Extraction for Polyester Leather Oil Degreasing LC-DAD GC-MS Aging directly for Natural fiber LC-DAD Result GC-MS Result

47 Disperse dyes Sensitizing disperse dyes are used for dyeing manufactured /synthetic fibers. (polyester, acetate and polyamide). These dyes are suspected to cause allergenic and carcinogenic reactions

48 Disperse dyes Before After Swedish newspaper Aftonbladet 15 November 2001

49 Disperse dyes LIST OF ALLERGENIC DYES SUBSTANCES SUBSTANCES SUBSTANCES C.I. Disperse Blue 1 C.I. Disperse Brown 1 C.I. Disperse Red 17 C.I. Disperse Blue 3 C.I. Disperse Orange 1 C.I. Disperse Yellow 1 C.I. Disperse Blue 7 C.I. Disperse Orange 3 C.I. Disperse Yellow 3 C.I. Disperse Blue 26 C.I. Disperse Orange 11 C.I. Disperse Yellow 9 C.I. Disperse Blue 35 C.I. Disperse Orange 37 C.I. Disperse Yellow 23 C.I. Disperse Blue 102 C.I. Disperse Orange 76 C.I. Disperse Yellow 39 C.I. Disperse Blue 106 C.I. Disperse Red 1 C.I. Disperse Yellow 49 C.I. Disperse Blue 124 C.I. Disperse Red 11 LIST OF CARCINOGENIC DYES SUBSTANCES SUBSTANCES SUBSTANCES C.I. Acid Red 26 C.I. Basic Red 9 C.I. Basic Violet 14 C.I. Direct Black 38 C.I. Direct Blue 6 C.I. Direct Red 28 C.I. Disperse Blue 1 C.I. Disperse Orange 11 C.I. Disperse Yellow 3

50 Disperse dyes Test Process DIN Solvent addition Fabric samples Cut sample into small pieces Extraction with methanol under ultrasonication at moderate temperature for 1 h Filter the extract using 0.45 m nylon filter Ultrasonic Extraction Analysis with LC-MS Confirm with DAD detection Syringe Filtration

51 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....,, O. H H

52 Formaldehyde Spot test process sample Drops Solution # 1 pink color indicates the presence of formaldehyde Drops Solution # 2 Inspect the white tissue and the white paper toweling below the fabric.

53 Formaldehyde Test Process Released Formaldehyde (ISO , AATCC 112) Sample Preparation Water Extractable Formaldehyde (ISO , JIS L041, ISO 17226) Incubation at Elevated Temperature Solution Filtration

54 Formaldehyde Test Process(continued) Color Development Processes UV/Vis Spectrophtometer Analysis (UV/Vis) UV Spectrum Result

55 Organotin Compounds

56 Organotin Compounds Organotin compounds are a class of chemical combining tin and organics such as butyland 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. C 4 H 9 Sn C 4 H 9 C 4 H 9 Tributyltin Sn Triphenyltin

57 Organotin Compounds Test Process Extraction : Ethanol Extraction Analysis : GC-MS Fabric samples Ultrasonic Extraction Cut sample into small pieces Silica Cleanup Extraction with Solvent Liquid-liquid Derivatisation of Organotin extraction Matrix Clean up GC-MS analysis

58 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 carcino genic and to disturb the hormone system.

59 Phthalates Examples Substances CAS No. Di-iso nonyl phthalate DINP Di(ethylhexyl) phthalate DEHP Di-n-octyl phthalate DNOP Di-iso-decyl phthalate DIDP Butyl benzyl phthalate BBP Di butyl phthalate DBP O O O DNOP O O O O O DIDP O O O O BBP O O O O O O O O O O DINP O DEHP O DnBP DiBP

60 Phthalates Related Legislations DIRECTIVE 2005/84/EC All plasticizer materials in toy and childcare article 0.1 % of DEHP, DBP & BBP All plasticizer materials in toy and childcare article that can be placed in the mouth by children 0.1 % of DINP, DIDP, DNOP

61 Phthalates Related Legislations California Health and Safety Code, Section (SB 1713) Effective on January 1, ) Any toy and child care article 0.1 % of DEHP, DBP & BBP Any toy and child care article intended for use by a child under 3 if that product can placed in the child s mouth % of DINP, DIDP, DNOP

62 Phthalates Test Process Cut sample into small pieces Dissolve the sample into solvent Precipitate the polymeric materials by another solvent Filter the extract Dissolve the sample GC-MS / LC-MS analysis Precipitation Filtration Made up with solvent

63 Heavy Metal 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 and can cause skin allergy. It is also corrosive. Cr (VI) is the side product in the tanning process of leather manufacturing industry. Conversion of Cr (III) to Cr (VI) in the leather material can be eliminated by addition of chemical, e.g. Ascorbic acid. Cr (0) + Cr (III) + Cr (VI) 3.Cr (0), Cr (III), Cr(VI) Cr (III), Cr (0) Cr (VI). Cr (VI),.. Cr (VI). Cr (III) Cr (VI).

64 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...

65 Nickel Release Related legislations Directive 94/27/EC Maximum permissible limit: 0.5 μg/cm 2 /week Directive 2004/96/EC of 27 Maximum permissible limit: 0.2 μg/cm 2 /week Test methods EN1811(Non-coated item) EN EN 1811(Coated item) Additional information Beware of alloy composition Screening solution is useful on pre-test

66 Nickel Release Test Process EN 1811 (Non-coated item) EN EN 1811 (Coated item) Non-coated item Clean the surface with detergent Put the sample into corrosion media at 50 for 2 h Abrasion for 4 h at room temp. Immerse into sweat solution for 7 days ICP analysis

67 Flame retardants 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. PBBs PCBs

68 Flame retardants Examples O Br O Br Br Br O Br OH O Br Bis(2,3-dibromopropyl) phosphate Br Br Br Br Pentabromodiphenyl ether Br O O P O O Br N O P N Br Br Br N Tris(2,3-dibromopropyl) phosphate Tris(1-aziridinyl)phosphine oxide Octabromodiphenyl Ether

69 Flame retardants Related legislations Directive 83/264/EEC Tris-(2,3-dibromopropyl)phosphate (TRIS) & Polybrominated Biphenyls(PBBs) Maximum permissible limit: (TRIS, PBB) (5 mg/kg) Directive 2003/11/EC pentabromdiphenyl ether, octabromdiphenyl ether Maximum permissible limit: (PentaBDE, OctaBDE) 0.1 % Directive 2002/95/EC (RoHS) Polybrominated Biphenyls(PBBs) & Poly bromodiphenyl ether (PBDEs) including DecaBDE in electrical and electronic equipment. Maximum permissible limit: 0.1 % (1000 mg/kg) Directive 2002/45/EC Short-chain chlorinated paraffins Maximum permissible limit: 1 % (1000 mg/kg)

70 Flame retardants Related legislations Norwegian Product Regulations (PoHS) Restriction of the use of Medium-Chained chlorinated paraffins, C14-C17(MCCP), Tetrabrombisphenol A(TBBPA) and Hexabromcyclododecane(HBCCD) Maximum permissible limit: 0.1 %(MCCP), 1 %(TBBPA), and 0.1 % (HBCCD) Öko-Tex Requirement(for PBB, TRIS, TEPA, pentabde, octabde) Maximum permissible limit: Not detected(<10 mg/kg)

71 Flame retardants Related legislations U.S - State laws Effective now, consumer products containing more than 0.1 % of penta-bde or octa-bde are prohibited in the following states : ( 9, Maryland ) California, Hawaii, Illinois, Maine, Michigan, New York, Oregon, Phode, Minnesota, Maryland will be effective on 1 October 2008

72 Flame retardants Related legislations U.S - State laws Only the state of Maine bans the use of Deca-BDE in consumer products ( Effective 1 January 2008, the following products that have plastic fibers shall not contain deca mixture of PBDE A mattress of mattress pad Upholstered furniture intended for indoor use in a home or other residential occupancy Effective 1 January 2010, a television or computer that has plastic housing shall not contain deca mixture of PBDE

73 Flame retardants Test Process Weighing GC-MS Analysis Ultrasonic Extraction SPE Cleanup Soxhlet Extraction Concentrate

74 Phenol Phenols are organic compounds used for their mouldicide properties. The most important reason for banning phenol (PCP, TeCP, OPP) is that the combustion of them will release dioxins known as some of the most toxic substances in the world. They may also cancer inducing They are sometimes used to prevent mould when growing cotton and when storing / transporting fabrics. They can also be used as preservative in print pastas.

75 Phenol Examples

76 Phenol Related legislations Directive 91/173/EEC Maximum permissible limit: 0.1 % (1000 mg/kg) Germany: Chemicals Act (Chemikalien Verbotsverordnung) of October 14, 1993, Bundesgesetzblatt III ). (10/14/1993) Maximum permissible limit: 5 mg/kg (leather) Öko-Tex Requirement Maximum permissible limit: 0.5 mg/kg (PCP,TeCP), 100 mg/kg(opp) Maximum permissible limit for baby product: 0.05 mg/kg (PCP,TeCP), 50 mg/kg(opp)

77 Phenol Test methods 64 LFGB B (Modified) for textile and leather

78 Phenol Test Process Weighing Alkaline Extraction GC-MS Analysis Internal standard addition

79 APEO APEO are used as emulsifier, household cleaning / disinfection agents, Industrial washing agents, textile / leather finishing additives; APEO is cancer suspect, to have hormonal effect, to cause abnormalism and to have effects on human fertility NP has been detected in human breast milk APEO APEO

80 APEO Related legislations Directive 2003/53/EC Maximum permissible limit: 0.1 % Industrial and institutional cleaning Domestic cleaning Textiles and leather processing (wetting agents, dispersing agents and degreasing ) Emulsifiers in agricultural teat dips Metal working Manufacturing of pulp and paper Co-formulants in pesticides and biocides Test methods Organic solvent extraction; GC-MS(AP)/LC-MS(APEO)

81 APEO Test Process Cut samples into small pieces Extract with MeOH Ultrasonic Extraction Filter the extract Filtration Clean up GC-MS / LC-MS Analysis

82 PAHs PAHs Polycyclic aromatic hydrocarbons Persistent organic compound Bioaccumulative Naturally occurred Over 100 different substance Pure PAHs is colourles, white or pale yellowish green solid Common sources Coal tar from petroleum refining process Organic substances from incomplete burning of coal, oil, gas or tabacco Presence in raw material to make rubber, plastics Present in BBQ s food 100,,

83 PAHs Way of exposure Inhalation Air pollution indoor or outdoor Hazardous wastes center Food Skin contact Toxicity Carcinogenic Reproductive harmful Affect immune system Affect animal skin

84 PAHs UV, PAHs. Picture 1 : Hand,slightly treated with moisturizing cream, after one-time touching of a rubberized hammer-handle. Under UV-light fluorescence is visible at the points of contact. The perforated pattern of the handle is clearly discernible.

85 PAHs Related legislations 2005/69/EC Restrictions on the use of PAHs in extender oils and tyres Benzo(a)pyren, Benzo(e)pyren, Benzo(a)anthracene, Chrysen, Benzo(b)fluoranthene, Benzo(j)fluoranthene, Benzo(k)fluoranthene, Dibenzo(a,h) anthracene Total : < 10 mg/kg Benzo(a)pyren < 1 mg/kg Up to now, no any EU directive for Consumer Products

86 PAHs List of PAHs No. Chemical name CAS No. 1 Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benzo(a)Anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Benzo(a)pyrene Indeno(1,2,3-cd)pyrene Dibenzo(a,h)anthracene Benzo(g,h,i)perylene

87 PAHs Related legislations Requiement of PAHs in consumer products on Germany BfR Plastic will be touched normally for more than 30 seconds e.g. steering wheel, handles, etc. 16 PAHs(sum) < 10 mg/kg Benzo(a)pyrene < 1 mg/kg Plastic will be touched now and then for less than 30 seconds e.g. plugs, switch, etc. 16 PAHs(sum) < 200 mg/kg Benzo(a)pyrene < 20 mg/kg ü Touched part

88 DMF Dimethyl Fumarate allergic sensitizer antifungal pronounced eczema as low as 1 ppm may produce 1ppm allergic reactions. December 2008, France adopted In January 2009, Belgium

89 SUMMARY Apparel Product Natural fibres Synthetic fibres Print, Plastic, Rubber Metal Item Leather Paper Azo dyes Formaldehyde Pesticides Phenols ph Heavy metals APEO/AP Azo dyes Disperse dyes Formaldehyde Phenols ph Heavy metals APEO/AP PVC Phthalates Organotin Formaldehyde Heavy metals Phenols APEO/AP Azo dyes Cr6 PAH Heavy metals Ni release Azo dyes Cr6 Heavy metals Organotin APEO/AP Phenols Formaldehyde ph DMF Heavy metals Formaldehyde Phenol

90 SUMMARY Suggestions to avoid restricted substances Training Material / composition / chemical review Supplier s responsibility (e.g. provide MSDS, declaration, etc.) Production process control (e.g. use of APEO,PFOS) Pay attention to accessories like buttons, badges, zippers, etc. Database management Monitoring and testing Risk analysis (e.g. some dyes used in silk, wool, nylon contain chromium as dye-fixing agent) Seek professional advice.

91 KOTITI

92 COMPANY PROFILE KOTITI KOTITI was established to contribute in developing Korean Textile Industry through its Services of R&D, Technical Guidence, Education & Training, Diffusion of Textile Technology, and Testing & Inspection for Textile products,...etc. Founded September 28, 1961 Office : Present in 3 countries, with 8 offices and labs supported by 200 employees. Korea : Seoul, Daegu, Busan China : Shanghai, Qingdao, Yantai, Dalian

93 COMPANY PROFILE KOTITI International Accreditation Korea Laboratory Accreditation Scheme (KOLAS) ISO 9001 BV KAKEN Samsung : Eco-partner ship LG : Green partner ship

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