Golka Klaus, Kopps Silke, Myslak Zdislaw W
Institut für Arbeitsphysiologie an der Universität Dortmund, Ardeystr. 67, D-44139 Dortmund, Germany.
Toxicol Lett. 2004 Jun 15;151(1):203-10. doi: 10.1016/j.toxlet.2003.11.016.
In the past, azo colorants based on benzidine, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine (o-tolidine), and 3,3'-dimethoxybenzidine (o-dianisidine) have been synthesized in large amounts and numbers. Studies in exposed workers have demonstrated that the azoreduction of benzidine-based dyes occurs in man. The metabolic conversion of benzidine-, 3,3'-dimethylbenzidine- and 3,3'-dimethoxybenzidine-based dyes to their (carcinogenic) amine precursors in vivo is a general phenomenon that must be considered for each member of this class of chemicals. Several epidemiological studies have demonstrated that the use of the benzidine-based dyes has caused bladder cancer in humans. However, in contrast to water-soluble dyes, the question of biological azoreduction of (practically insoluble) pigments has been a matter of discussion. As a majority of azo pigments are based on 3,3'-dichlorobenzidine, much of the available experimental data are focused on this group. Long-term animal carcinogenicity studies performed with pigments based on 3,3'-dichlorobenzidine did not show a carcinogenic effect. The absence of a genotoxic effect has been supported by mutagenicity studies with the 3,3'-dichlorobenzidine-based Pigment Yellow 12. Studies in which azo pigments based on 3,3'-dichlorobenzidine had been orally administered to rats, hamsters, rabbits and monkeys could generally not detect significant amounts of 3,3'-dichlorobenzidine in the urine. It, therefore, appears well established that the aromatic amine components from azo pigments based on 3,3'-dichlorobenzidine are practically not bioavailable. Hence, it is very unlikely that occupational exposure to insoluble azo pigments would be associated with a substantial risk of (bladder) cancer in man. According to current EU regulations, azo dyes based on benzidine, 3,3'-dimethoxybenzidine and 3,3'-dimethylbenzidine have been classified as carcinogens of category 2 as "substances which should be regarded as if they are carcinogenic to man". This is not the case for 3,3'-dichlorobenzidine-based azo pigments.
过去，基于联苯胺、3,3'-二氯联苯胺、3,3'-二甲基联苯胺（邻联甲苯胺）和3,3'-二甲氧基联苯胺（邻联茴香胺）的偶氮染料被大量合成。对接触这些染料的工人的研究表明，人体会发生基于联苯胺的染料的偶氮还原反应。联苯胺、3,3'-二甲基联苯胺和3,3'-二甲氧基联苯胺基染料在体内代谢转化为其（致癌性）胺前体是一种普遍现象，对于这类化学品中的每一种都必须加以考虑。多项流行病学研究表明，使用基于联苯胺的染料已导致人类膀胱癌。然而，与水溶性染料不同，（实际上不溶性的）颜料的生物偶氮还原问题一直存在争议。由于大多数偶氮颜料基于3,3'-二氯联苯胺，现有的许多实验数据都集中在这一组。用基于3,3'-二氯联苯胺的颜料进行的长期动物致癌性研究未显示致癌作用。基于3,3'-二氯联苯胺的颜料黄12的致突变性研究支持了其无遗传毒性作用的观点。在将基于3,3'-二氯联苯胺的偶氮颜料口服给予大鼠、仓鼠、兔子和猴子的研究中，通常在尿液中检测不到大量的3,3'-二氯联苯胺。因此，似乎可以确定，基于3,3'-二氯联苯胺的偶氮颜料中的芳香胺成分实际上无法被生物利用。因此，职业接触不溶性偶氮颜料极不可能与人类患（膀胱）癌的重大风险相关。根据欧盟现行法规，基于联苯胺、3,3'-二甲氧基联苯胺和3,3'-二甲基联苯胺的偶氮染料已被列为2类致癌物，即“应被视为对人类致癌的物质”。基于3,3'-二氯联苯胺的偶氮颜料则并非如此。
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