In April 1992, Germany wrote about the ban on dyes in the first article on the law on daily necessities, but it was not clear and it was published in July 1994, December 1994, July 1995 and July 1996 respectively. The second to fifth amendments were made, and a more detailed supplementary announcement was made in July 1997. According to the analysis of Bayer in Germany in 1994, there are 118 banned dyes in the German market, including 77 direct dyes, 26 acid dyes, 6 disperse dyes, 5 ice dyes, and basic dyes according to their application categories. 3 and 1 oxidation base.
In the 1999 SDC resource file, there were 141 azo dyes that can be reductively cracked out of 22 carcinogenic aromatic amines collected by the German VCI (German Chemical Industry Association) according to the internal research and the third edition of the 1994 “Dye Index”. Compared with 118 banned dyes proposed by Bayer in 1994, 113 dye structures are the same. If the VCI is combined with the banned dye proposed by Bayer, there are 146 banned dyes, including 84 direct dyes, 29 acid dyes, 9 disperse dyes, 7 basic dyes, 5 ice dye chromophores, and oxidized colors. 1 base, 2 mordant dyes and 9 solvent dyes.

According to the new Eco-Tex Standard 100 testing standard for toxic substances in textiles issued in 2000, the banned dyes involved include allergic dyes, direct carcinogenic dyes and acute toxic dyes, in addition to lead, antimony, chromium, and cobalt. Heavy metals such as copper, nickel, mercury, etc. exceeded the limit, formaldehyde content exceeded the limit, organic pesticides exceeded the limit of dyes, and contained environmental hormones, contained environmental pollution chemical substances, contained variability chemical substances, and contained persistent organic pollution. The dyes etc.
From the molecular structure analysis of the dyestuffs and the actual measurement of the dyed fabrics, the dyes synthesized with carcinogenic aromatic amines as intermediates, including azo dyes and other dyes, are not banned even if trace amounts are present. About 70% of the synthetic dyes on the market today are based on azo structures. The widely used direct dyes, acid dyes, reactive dyes, metal complex dyes, disperse dyes, cationic dyes, and polycondensation dyes all contain azo structures. . Azo dyes are used not only for dyeing textiles, but also for dyeing leather, paper, food, etc. It should be pointed out that under normal circumstances the azo dye itself will not have harmful effects on the human body, but some azo dyes synthesized with carcinogenic aromatic amine intermediates will have normal metabolism with the human body after prolonged contact with human skin. The release of substances in combination, and the reduction reaction occurs to break the azo groups and regenerate carcinogenic aromatic compounds. These compounds are reabsorbed by the body. After activation, the structure and function of human cells are changed, thereby transforming adult body lesions. Predisposing factors increase the difficulty of carcinogenesis. At the same time, banned dyes are not limited to azo dyes. Among other structural dyes, such as sulphur dyes, vat dyes and some auxiliaries, they may also be banned because they contain these harmful aromatic amines.
1. The direct dye direct dyes are a relatively large number of dyes used in cellulose fibers. In the first batch of 118 banned dyes in Germany, there were 77 direct dyes, accounting for 65%. Among them, 72 were direct dyes that were synthesized using three derivatives such as benzidine and dimethylbenzidine as intermediates, and 36 were direct dyes with benzidine as the intermediate. The yield was almost 50% of the total direct dye production. . According to statistics, in recent years, 37 direct dyes have been banned in China's direct dyes, accounting for 62.7% of the total direct dyes produced in China.
2. Acid dyes The consumption of acid dyes in the world is second only to vulcanization, direct and disperse dyes, and nearly 30 acid dyes have been banned in Germany. There are many kinds of harmful aromatic amines, which are distributed in benzidine, dimethyl benzidine, o-anisidine, o-toluidine, p-aminoazobenzene, 4-amino-3,2-dimethylammonium Benzene and dyes themselves are carcinogenic, etc. in a wide range. Chromatography mainly focuses on red and black, and other chromatograms on orange, violet, and brown. Including: weak orange R (acid orange 45), weak acid red H (acid red 285), acid black NT29 (acid black 29) and so on.
In addition, there are four new banned acid dyes added in the Eco-Tex Standard 100 released in 2000: There are two known direct carcinogenic dyes, they are CI Acid Red 26, CI Acid Violet 49; The allergenic dye is CI Acid Black 48; the acute toxic dyes involved are CI Acid Orange 156, CI Acid Orange 165, and the like.
3. Disperse dyes Among the 118 dyes that are banned in Germany, six disperse dyes have been banned, and disperse dyes that are not listed but have been banned due to the influence of 22 harmful aromatic amines, according to incomplete statistics, there are 14 types, but not This includes the composition of the compound dye. Prominent among the banned dyes is CI Disperse Yellow 23, which is a red-yellow disazo disperse dye, and our trade name is Disperse Yellow RGFL. Other disabling disperse dyes include Disperse Yellow E-5R (CI Disperse Yellow 7), Disperse Orange 2G (CI Disperse Yellow 56) and CI Disperse Orange 149, CI Disperse Red 151, CI Disperse Blue 1 and others.
In the new version of Eco-Tex Standard 100 released in 2000, there were 26 types of disperse dyes involved in allergenic dyes. In addition, there are two kinds of known disperse dyes in the oncogenic dyes, which are CI Disperse Yellow 3 and CI Disperse Blue 1 .
4. Many of the chromophores used in chromophores and phenol-insoluble azo dyes are themselves MAK(III)A1 (MAK means maximum workplace concentration) and the carcinogenic or suspected carcinogenic aromatic amines in the A2 group should be subject to Disabled. The first batch of banned chromophores published in Germany totaled 5, missing 1 chromophore. There are 9 incomplete statistics based on the synthesis of chromic phenols from harmful aromatic amines. In addition, there are chromophores containing isomers that are harmful aromatic amines, such as: orange-based GC (CI chromophore 2) and yellow-based GC (CI chromophore 44) are m-chloroaniline and o-chloroaniline respectively Chloroaniline is an isoform of the carcinogenic aromatic amine p-chloroaniline. Several other types of disabling chromophores: red-based TR (CI ice-stained 11), large red-based G (CI-stained 12), blue-based B (CI-based ice-stained 48), and deep blue-based R (CI ice-stained 113) and date red base GBC (CI ice base 4) and so on.
Oxidized chromophores are listed as only one of the banned dyes in Germany. They are CI chromophore 14 or CI oxidized chromophore 20 (76035), 2,4-diaminotoluene.
The acute toxicity dyes involved are CI chromophore 20, CI chromophore 24, and CI chromophore 41.
5. There are three basic dyes that were included in the first batch of basic dyes in Germany. They are alkaline brown 4, basic red 42, and basic red 111. Among them: CI Alkaline Red 111 contains p-aminoazobenzene; CI Alkaline Red 42 contains o-aminoanisole; CI Alkaline Brown 4 contains 2,4-diaminotoluene. Another four basic dyes, published by the German VCI, have been banned because they contain harmful aromatic amines. For example, CI Basic Yellow 82 contains p-aminobenzene; CI Basic Yellow 103 contains 4,4'-diaminodiphenylmethane; CI Basic Red 76 contains o-anisidine; CI Basic Red 114 contains o-amino Anisole.
There are six basic dyes involved in acute toxicity dyes: CI Basic Yellow 21, CI Basic Red 12, CI Basic Violet 16, CI Basic Blue 3, CI Basic Blue 7, CI Base Sexual Blue 81. There is one kind of basic dye in the known direct carcinogenic dyes, CI Basic Red 9 .
6. Reactive dyes and vat dyes There are no active and reduced two major classes of dyes in the 118 banned dyes, but starting from 22 harmful aromatic amines. Individual species in these two types of dyes will be affected. Such as reactive dyes active yellow K-R, reactive blue KD-7G, active yellow-brown K-GR, active yellow KE-4RNI. Wait.
The vat dyes are banned even less, but for example, the reduced plum red R (CI reduction red 1,73360) is made from o-aniline as raw material, and the reducing red violet RH (CI reduction violet 2,73385) is also based on o-aniline. , it is also affected by the ban. Corresponding soluble red pigments IR IRH and IRZ IRH of the soluble vat dyes, respectively, are the sulfate esters of reduced pink R and leucochromium RH, which will also be affected.
7. In addition to the aforementioned dyes, other types of dyes are also banned dyes among other commonly used dyes because of the use of certain aromatic amine intermediates in their dyes. Such as sulfurized dyes in the yellow sulfur brown 5G (CI vulcanization 10,53055), vulcanized yellow brown 6G (CI vulcanized orange 1,53050), sulfurized yellowish GC (CI vulcanization yellow 2,53120), vulcanization Black CLG ( CI Sulfur Black 6) and Sulfur Grass Green ZG, Sulfur Black Green GH and other sulphur dyes.
In paint pastes, dyes made from solids containing azo dyes are also banned. Including Evergreen Orange G (CI Pigment Orange 13, 21110), 8205 Dye Golden FGRN, 6103 Dye Golden FG, and 8111 Dye Red FFG.


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