Analysis of Primary Aromatic Amines Derived from Azo Colorants in Textile Products and Determination of Their Source Colorant.

Twenty-four primary aromatic amines (PAAs) derived from azo colorants, which are controlled by the Act on Control of Household Products Containing Harmful Substances by the Japan Ministry of Health, Labour and Welfare, aniline and 1,4-phenylendiamine were analyzed in 86 samples of 40 textile products by GC-MS. Even though these PAAs detected in the samples did not exceed the regulation value (30 μg/g), 14 kinds of PAAs were detected that exceeded the limit of quantification. 4,4'-Methylenedianiline, in amounts that exceeded the limit of quantification, was detected in 20 textile samples containing synthesis fiber (16 samples made from polyurethane, two samples made from polyester, and two samples made from acryl); however, it was not detected in natural fiber textile samples. Of these samples, 4,4'-methylenedianiline was detected in 16 out of 19 samples (84%) made from polyurethane fiber. This suggests that 4,4'-methylenedianiline is formed from polyurethane. The origin of 3,3'-dichlorobenzidine was investigated in three samples releasing more than 3 μg/g (3.9-15 μg/g) of 3,3'-dichlorobenzidine using atmospheric pressure solids analysis probe-mass spectrometry and Pigment Orange 13 was identified as the orange colorant in the textile printing parts. This result suggests that 3,3'-dichlorobenzidine detected in these three samples was generated by the reduction of Pigment Orange 13.