German Legislation - Greenrivertech.com.tw ...

1 ECOLOGYG erman Legislationon Azo DyesEnvironmental protection and productsafety are becoming increasingly impor-tant criteria in the purchase of textiles,due to the emotive nature of the debateand greater consumer publication provides general infor-mationaboutazodyestohelpputtheissu e on a more factual basis. Here youwill find some background notes aboutthe German Consumer Goods Ordinance,together with a list of the amines anddyestuffs involved. Information is alsoprovided about the test methods usedfor textiles, as well as an overview of othernational regulations relating to azo 's products are continuously mo-nitored to make sure they meet statutoryrequirements throughout the sets standards in environmentalresponsibility. DyStar has not had tomake any changes to its product rangeto comply with the amendments to theGerman Consumer Goods better evidence could there be thatBy buying and using dyes and pigmentpreparations from DyStar, you can besure you comply with the GermanConsumer Goods Ordinance and otherstatutory regulations.

2 None of our azodyes generate banned amines followingazo bond cleavage. So consumers can beconfident that textiles dyed and printedcorrectly with DyStar products are DyStar productsyou re on the safe us if you would like further information. Your local DyStarrepresentative or our central ecology team will be happy to help backgroundAzo dyesThe German Consumer Goods OrdinanceListed aminesDraft for 6 AmendmentAnalytical detectionof banned azo dyesthList of banned azo dyesAzo pigmentsConsumer goodsInternational legislationAnnex:Tables of banned azo colourants234556788912 Azo dyestuffs2 Amendments to the GermanConsumer Goods OrdinanceIn 1994, the German Consumer GoodsOrdinance (Bedarfsgegenst ndeverordnung)was amended to ban specific azo dyes,triggering widespread discussion abouttextile ecology. The German amendmentalso had an international impact, withheadlines such as German Azo Ban .Textile finishers and the trade wereconfronted overnight with a ban on azodyes which release specific amines as aresult of reductive cleavage of azo bonds.

3 This definition was only understood by dyechemists initially, as only these experts hada concrete idea which dyestuffs would beaffected by the ban. But even the expertscould not agree about the details of the law,because some single regulations and phra-ses were rather backgroundMAK aminesThe first serious reports about an increasedrisk of cancer of the bladder for peopleworking in dyestuff production were pub-lished in trade journals as long as 100 yearspreviously. The cause of these malignantdiseases was soon thought to be certainaromatic amines widely used in the pro-duction of synthetic dyes in those )The MAK list was set up by the German Senate Committee for Testing of Occupational Hazardous Substances, and is updated annually (MAK =maximum workplace concentration). Group III of the MAK list summarizes carcinogenic chemicals (for carc. cat. 1 and 2 substances no workplace concentration is specified, though). The earlier divisions A1 and A2 of Group III have been renamed Category 1 and Category2 in 1998, in keeping with the EU classification system for carcinogenic 2 Reductive Cleavage of Azo DyestuffsFigure 1 Synthesis of Azo DyesAzo dyestuffs3In particular, benzidine (basis of benzidinedyes) was thought to play a leading scientifically based epidemiologicalevidence shows that four aromatic amineshave a carcinogenic effect in humans: benzidine 2-naphthylamine 4-aminodiphenyl 4-chloro-o-toluidineThese four compounds are listed as sub-stances definitely known to be carcinogenicin humans in Category 1, Section III of theMAK1) studies have shown that other aro-matic amines are also carcinogenic underconditions, such as would indicate a carci-nogenic potential for humans too.

4 Thesesubstances make up Category 2, Section IIIof the MAK dyesAzo dyes are synthesized by the diazoti-zation of aromatic amines, followed bycoupling to a further aromatic compound(known as the coupling component). Thisresults in the formation of the so-called azogroup two nitrogen atoms joined by adouble bond N = N (see Figure 1).Azo groups in dyestuffs can be easilyclea-ved using a reducing agent, whichresults in the decolorization of the azo a result of this azo cleavage, the aro-matic amine that had been used as a diazocomponent in the dyestuff synthesis is setfree again; also the coupling component isreleased, but now substituted with an addi-tional amino group (see Figure 2). Thisreaction can be technically useful the last 40 years, additional evidencehas accumulated that azo dyes can alsobe metabolically cleaved by bacteria in thehuman digestive tract or by enzymaticreduction in some organs. Several studiescarried out with textile workers handlingbenzidine dyes showed the presence oftraces of free benzidine in the urine.

5 MAKamines released in the human organismfrom azo dyestuffs can have a carcinogeniceffect there. Epidemiological studies existwhich describe an increased incidence ofcarcinomas of the bladder among paintersand dye factory workers who had neverhad contact with free MAK amines, butonly with the related azo dyes. It shouldbe emphasized here that benzidine dyesand MAK-dyes in general can only havea carcinogenic effect where there is suffi-cient exposure, , when these dyes actu-ally enter the human organism as a resultof improper handling or low occupationalsafety German Law on Hazardous Sub-stances classifies those azo dyes as carcino-genic where a carcinogenic arylaminecan be formed following reductive azocleavage. The strict workplace protectionrules which apply when handling carcino-genic substances apply to these dyes, MAK Committee recommends that allazo dyes which can form MAK aminesfollowing cleavage should be avoided ingeneral.

6 German Legislation has adoptedthis recommendation in TRGS 6142) Technical Regulation for HazardousSubstances , thereby putting this into recommendation is widely followedin Germany. DyStar as well as its parentcompanies stopped producing and marke-ting benzidine dyes in 1971. Marketingof other dyes based on Cat. 1 or 2 aminesof the MAK list also ceased several yearsago. However, numerous non-traditionalsstill produce and market these dyes world-wide and even in Europe )TRGS: Technische Regeln f r Gefahrstoffe (= Technical Regu-lation for Hazardous Substances). Up to May 1999, the TRGS 614contained a list of 20 carcinogenic amines (identical with theGerman Consumer Goods Ordinance list, see Table 1). From May1999, four further amines were added to the TRGS list: 6-amino-2-ethoxy-naphthaline; 4-amino-3-fluorophenol; 2-methoxyanaline(o-anisidine); p-amino azobenzene. Only the last two mentionedamines, already classified by the EU as carcinogenic since years,are relevant to dyestuffs4 Amendments to the ConsumerGoods OrdinanceNevertheless, with preventative consumerprotection in mind, the German ConsumerGoods Ordinance was amended in 1994to prevent any potential health risk fromtextiles dyed with dyestuffs based oncleavable carcinogenic amines.

7 Theamendment to the regulations then read: Textiles and other articles withprolonged skin contact shall notbe dyed with azo dyestuffs which,by cleavage of one or more azobonds, can release any of 20 listedaromatic amines. Furthermore,such textiles may not be importedor brought into circulation. The regulations were re-amended severaltimes over the next few years due to pro-blems with the wording of the regulation,and other difficulties in the enforcementof the statutory transition of April 18, 1997 the current 5th amend-ment to the Consumer Goods Ordinancecame into force:The German Consumer GoodsOrdinanceImplementation of the recommendationsof the MAK Committee and the TRGS 614not to use dyestuffs based on MAK amines,together with the strict workplace protec-tion rules of the Hazardous Substances Lawand corresponding EU Directives, offers aneffective protection to dye factory workersfrom health risks which could result frominhalation of dust-forming MAK dyes or from direct skin contact with these dyeswhere they are still in textiles have been dyed, azo dyestuffsbased on MAK amines do not representa real health risk to the consumer.

8 In orderto enter the consumer s organism, the dyemust migrate from the textile to the skin,and must then be absorbed by the bodythrough the skin. This risk is negligiblewhere the fastness of the dye is high genuine risk may exist where babies orinfants suck on textiles or soft toys so thattraces of the dye can enter the body with 1, No. 7 column 3 of the German Consumer GoodsOrdinance, as of 18. 4. 1997 presp. 23. 12. 1997 (abbreviated): The following may not be used in the commercial production or treatment of con-sumer goods: Azo dyestuffs which, on cleavage of one or more azo groups, releaseany of twenty listed amines (see list in Table 1).Pigments are exempted from this regulation, provided none of the following amines(see list in Table 1) can be detected after cleavage of one or several azo groups (usingthe analysis method described in Annex 10, No. 7).Consumer goods which do not comply with these regulations may not be imported orbrought into circulation.

9 Azo dyestuffs5 Table 1 Listed aminesThe following 20 aromatic amines are listed in the German Consumer Goods Ordinance. Allare also listed in Group III of the MAK list under Category 1 or 2:Aromatic aminesCAS Group III under2-naphthylamine .. Cat. 14-aminodiphenyl .. Cat. Cat. 1benzidine .. Cat. 12,4,5-trimethylaniline .. Cat. 22,4-diaminoanisol .. Cat. 22,4-toluenediamine .. Cat. Cat. 23,3 -dichlorobenzidine .. Cat. 23,3 -dimethoxybenzidine [3,3 -dianisidine] .. 119-90-4 .. Cat. 23,3 -dimethyl-4,4 -diaminodiphenylmethane .. Cat. 23,3 -dimethylbenzidine [o-tolidine] .. 119-93-7 .. Cat. 24,4 -diaminodiphenylmethane .. Cat. 24,4 -methylene-bis-(2-chloroaniline) .. Cat. 24,4 Cat. 24,4 -thiodianiline .. Cat. Cat. Cat. 2p-chloroaniline .. Cat. 2p-cresidine .. Cat. 2 AromaticCAS based on either of these twoamines have not yet been banned by theGerman Consumer Goods Ordinance todate. However, o-anisidine was includedin the MAK list in textile traders now prohibit theirsuppliers from using dyes based on the lasttwo mentioned December 23rd, 1997 the ConsumerGoods Ordinance was re-published in-cluding all the five amendments enacteduntil that date.

10 On March 8th, 2000 the 6thamendment was enacted. It contains noessential dyestuff-related following two aromatic amines, whichcan also be used in dyestuff production,have been classified by the European Unionas carcinogenic (see also footnote 2 onpage 3)Azo dyestuffs6 Draft for 6th Amendment to GermanConsumer Goods OrdinanceIn March 1999 a draft 6th Amendment to theGerman Consumer Goods Ordinance waspublished, that proposed the following newregulations for list of 20 carcinogenic amines(Table 1) was to be expanded by4 further amines: o-anisidine, p-aminoazobenzene and two xylidine prohibition on using azo dyesby the German Consumer GoodsOrdinance was to be extended tocover children s toys (children s toyswere previously not considered tobe consumer goods under theOrdinance). transition period within whichconsumer goods based on used orrecycled fibers which do not meet withthe Ordinance requirements may bemanufactured, imported and marketedwas to be extended to 31.