Restricted Substances 禁用化學物質 The Importance of Proper Testing and Proper Testing Procedures 適用測試方法及程序 Dongguan, 21 th September 2006 Dr. Helmut Krause Global Manager RSTS

2 Restricted Substances List (RSL) 禁用化學物質清單 Typical Test Parameters of RSL  pH Value － 酸鹼值  Formaldehyde － 甲醛含量  Chlorinated Organic Carriers － 有機氯化載體  Chlorinated Phenols － 氯酚  Allergenic Disperse Dyes － 致敏性分散染料  Pesticides － 農藥  Azo Dye － 偶氮染料  Phthalates in PVC － 鄰苯二甲酸鹽  Extractable Heavy Metals － 金屬  Chrome VI － 六價鉻  Organotin Compounds － 有機錫化合物  Total Cadmium content － 總 鎘量  Volatile Organic Compounds － 揮發性有機化合 物

3 How to select “Proper Test methods” 選用合適之測試方法 Select the Test Methods for RSL according to the needs in the markets where the products are to be sold! 選擇銷售市塲 1)Official or legal test methods that are applied by Governmental authorities 官方訂定 2)Normed test methods to ensure reproducibility! i.e. AATCC, ASTM, EN, ISO or DIN norms that are easily available in all markets! 市塲慣用 3)Make sure that your laboratories that are testing BEFORE shipment and your laboratories that are testing AFTER shipment are in alignment! 出口前及入口後需一貫性

4 How to select “Proper Test methods” 相關之測試方案 Europe: 歐洲 Official (legal) test methods defined by EU directives:  EN 14362, Part 1 & 2 for banned azo dyes (Originally developed in Germany)  EN 1811 & EN for Nickel release Normed Test methods developed in Germany:  Pentachlorophenol in Leather & Textiles  DIN 54231, “Textiles, detection of disperse dyes

5 How to select “Proper Test methods” 相關之測試方案 China: 中國 Imports to China are supposed to comply with Chinese Law. 入口到中國應該依從中國法例 Official test reports issued by Chinese laboratories that are accredited by the Chinese Government are requested. 測試報告要由官方認可的機構發出 GB :1998, Chinese normed test method for banned azo dyes! 中國測試準則是禁止偶氮類染料

6 How to select “Proper Test methods” 相關之測試方案 Japan: 日本 Imports to Japan are supposed to comply with the Japanese Law “ Law for the control of household products containing harmful substances” (Law No. 112, 1973). 根據法例 112 條 Ban on the following chemicals:  Formaldehyde 甲醛  Tri-phenyl-tin and tributyl-tin compounds 有機錫  Flame retardants - (Tris(1-aziridinyl)-phosphine oxide & Tris(2,3-dibromopropyl)-phosphate) Test methods are given in the Law! 法定方法

7 How to select “Proper Test methods” 相關之測試方案 USA: 美國 Business for Social Responsibilty (BSR), an association of apparel companies, has issued a RSL: BSR 行業指引  Global, industry- wide standard  Based on world-wide legislation & regulations Test Methods & limit values: 方法及標準  Based on legal requirements whenever available 按法例 訂定  Recommended test methods 建議方法  Quite in general identical to those used in Europe/Germany! 大部份異於歐洲慣用方法

8 How to select “Technically Proper Test methods” 測試方法之技術要項 Proper Test methods must:  Cover the scope of testing 蓋括性 => tested products are safe, no claim! 測試產品之安全性  Deliver repeatable and reproducible results! 重現性 => test methods need to be updated and/or adjusted according to the changes in the markets! 不斷更新 / 迎合 市塲作適量調節 Typical examples are given in the following slides for: 三個舉例  Formaldehyde 甲醛  AZO 偶氮類染料  Organo-tin compounds 有機錫

9 Formaldehyde 甲醛 Formaldehyde, an organic chemical compound (chem. formula CH 2 O), is found in daily life almost everywhere: 在生活中常出現甲醛  Apples 蘋果 ~ 20 mg/kg  Cabbage 白菜 ~ 15 mg/kg  Exhaust Fumes 廢氣 ~ 150 mg/m 3  Cigarette Smoke 香煙 ~ 1000 mg/m 3  Rainwater 雨水 ~ 0.20 mg/Liter  Human Blood 血液 ~ 2.5 mg/Liter Formaldehyde Synthetic Resins 合成樹脂  Melamine/Formaldehyde Resins  Urea/Formaldehyde Resins  Phenol/Formaldehyde Resins, “Bakelite”  N-Methylol/Formaldehyde Resins

10 Formaldehyde 甲醛 Formaldehyde used in Textile & Leather Finishing Process: 紡織及皮革工藝 Formaldehyde-containing products are used:  Shrinkage-resistance 防縮  Crease-resistance 防雛  Easy-care finishing 洗可穿整理  After-treatment to improve colorfastness of direct or reactive dyes. 加強色牢度  Tanning and re-tanning agent in leather production 鞣革 劑

11 Formaldehyde Test Method ISO 17226,Determination of Formaldehyde in Leather: Free-Formaldehyde and Formaldehyde hydrolyzed ( 可溶於 水 ) during extraction Detection and Quantification either by “HPLC-method” or by “UV-method” 由 “HPLC - 高效液相色谱方法 " 或由 " 紫外光方法 “ 測試和量化 “UV-method” more convenient, but heavily dependent on matrix effects! 紫外光方法 - 更加方便, 但受基質效應影響 “HPLC-method” separates formaldehyde from “matrix effects” and delivers reliable results, especially with staining test materials! 高效液相色谱方法有可靠的結果, 特別是帶有顏色的測試材料 => HPLC method is recommended for leathers and samples with heavy staining! 推薦予皮革和樣品帶有顏色的測試材料

12 Formaldehyde Test Method 甲醛測試方法

13 Azo Dyes 偶氮類染料 Findings: About 5-8 % of the garments tested in our labs contain forbidden amines: 在我們實驗室測試的服裝中， 大約 5-8 % 被檢測到合有被禁止的胺 物  dark blue and black colors, especially in leather 深藍和黑顏色, 特別是在皮革  prints, very often red & brown colors 印花, 紅色 & 棕色  4-amino-azobenzene in polyesters dyed with disperse yellow 23 以分散劑黃色 23 染色的涤綸都含有苯偶氮基對苯胺 － 4-AAB  Recommended test methods: （被推薦的測試方法）  EN &  For 4-amino-azobenzene new German test method! 苯偶氮基對苯胺 － 4-AAB ，以新德國測試方法檢測

14 Organo-tin Compounds 有機錫化合物 - Usage TBT 三丁基錫 is used: anti-fouling agent to repel ( 擊退 ) barnacles and weeds ( 雜草 ) from ships wood preservative 防腐劑 waste water treatment 污水處理 biocide, fungicide in agriculture 殺蟲劑、農業用的殺真菌劑 in sanitary sealing materials 衛生用料 as impurity in substances containing MBT and DBT! DBT 二丁機錫 (and also MBT 一丁機錫 ) are used as catalyst 催化劑 and stabilizer 穩定劑 in a variety of polymeric materials 聚合物材 料 : catalyst and stabilizer in PVC （在 PVC 裡用作催化劑和穩定劑, foils, flooring and piping materials. 瓶、箔、地板和作管子的材料 as catalyst in coatings with PVC, silicones and PU (leather industry!) 在塗層與 PVC 、硅樹脂和 PU 作為催化劑 ( 皮革產業 )

15 Organo-tin Compounds - Experimental Findings （有機錫化合物－實驗性研究結果） Organo-tin compounds tested in footwear materials like Polyester, PVC, TPR:  MBT （一丁機錫 ） typically ranges from 0,2 to 20 mg/kg (almost always with higher DBT amounts)  DBT （ 二 丁機錫 ） typically ranges from 0,5 up to 350 mg/kg  TBT （ 三 丁機錫 ） typically only in samples with DBT amounts higher than 80 mg/kg but also cases where only TBT and then in amounts below 0,5 mg/kg was found  DBT used on technical scale is highest in concentration  MBT degradation product （分解產品） and/or impurity of DBT  TBT almost always as impurity （雜質） of technical DBT  PVC &PU materials for footwear production contain very often large amounts of DBT 鞋類材料  High risk （高危性） of cross-contamination （交叉感染） during production, i.e. cutting oils!

16 Organo-tin Compounds – Test Methods （有機錫化合物－實驗性研究結果） “Bio-availability” （ 生物相容性） : Organo-tin compounds are extracted into simulated human sweat solution. No matter how high the “total amount” is, only the “sweat- extractable” amount will be tested. 用模仿人的汗水來提取有機錫化合物。無論樣品中含有的有機錫化合物 “ 總額 ” 有多少, 只有 “ 汗液可提取的 " 數額將被測試。 => This approach is supposed to be adopted by “Öko Tex 100”. 這種方法被 “Öko Tex 100”. 採用 Total content （總含量）： Organic solvents （有機溶液） are used in order to extract the “total amount” of organo-tin compounds in the test sample. 有機溶液被使用作提取在測試樣品中有機錫化合物的總含量 In case of samples containing the target compounds, the “total amount” quite in general is much higher than the “bio-available” amount. 測試樣品中有機錫化合物的總含量往往比生物相容的 “ 汗液可提取的 " 含量 為高 => Go for the total content! NGO’s as well as Governmental authorities are supposed to do the same! 志願團體與政府應採用一致的測試方法

17 How to Develop a Test Procedure? 怎麼開發測試程序 List of Restricted Substances: 禁用化學物質清單 (RSL) Define the chemicals contained in your RSL. 設定 RSL 之化學品清單 Define the test methods and limit values for your RSL. 設定測試方法及極限值 Define at what stage during the production the test is to be performed, i.e. test on the finished product or test on the raw materials before production. 設定在什麼生產階段執行測試, 即制成品，或原材料在生產之前進行測 試 Consider “Cross-contaminations” （交叉感染） (e.g. organo-tin in cutting oils or lubricants, Chrome VI （六價鉻 ） formation due to alkaline glues （鹼性黏合劑）, biocides （殺菌殺蟲劑） applied during storage & transportation and define measures to avoid them If necessary, define your RSL as well for textile auxiliaries and finishing chemicals. 為紡織料品整染助劑設定 RSL

18 How to Develop a Test Procedure? 怎麼開發測試程序 Control of Restricted Substances (RSL): Identify high risk RS by statistical testing approach. 通過統計測試的方法鑒別高風險的化学物品 (i.e. by country, by supplier, by material) 按國家, 由供應商, 由材料去鑒別 Identify sources of RS. 辨認 RS 的來源 Phase out RS and control success by testing. 逐步淘汰 RS ， 由測試來監控効果 Categorize RS according to their risk level: 根據 RS 的風險級別來分類 check high risk RS more often than low risk RS! 加強高風險的 RS 的檢測 Define a final standard procedure: 訂定標準程序  what tests and when (i.e.. per season, per year..) 哪些測試和什麼時段 ( 即。每季節, 每年。 )  what materials. 哪種材料  how to check finished products randomly for those parameters that are to be tested on the raw materials only 經物料測試，仍需進行對成品之隨機檢測

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