Azocolorants in Textiles and Toys

5 Sampling and Test Results

5.1 Criteria of selection and purchasing
5.2 Survey of samples
5.3 Test procedure
5.4 Test results
5.5 Conclusion

This section describes the criteria for the selection and purchasing of textile articles for the tests. The principal criterion has been to select articles which in use would give the highest possibility that persons could absorb released chemical compounds from the textile products, either by pronounced contact with the skin (adults and babies) or by sucking (babies).

The following types were chosen:

• bedlinen (covers and sheets), bath towels/wash cloths, underwear, nightwear, T-shirts, socks, panty hoses, blouses, trousers, skirts, scarfs, baby clothing, cuddle toys and cloth toys.

The selection of samples within the types of textile products was based on the present knowledge of dyestuffs which can split off aromatic amines commonly considered as harmful, and of the main applications of these dyestuffs.

The fibre content and the colour of the textile products were thus chosen so, that time highest probability of a content harmful dyestuffs was present.

Articles with printed designs and front prints were selected analogously.

Consequently, the selected articles do not constitute a representative random sample of textile products on the Danish market. The selected articles represents rather a worst case situation.

It was attempted to obtain an equal distribution between Danish products and imported articles.

The textile products were purchased in national department stores and chain stores, where a broad section of the population goes shopping.

A survey of the samples is presented in Table 5.1.

Table 5.1
link to tabel
Survey of the samples.

Table 5.2
Origin of the articles

Only five articles are labelled »Made in Denmark«. Twenty articles carry a label definitely showing foreign origin. Of the remaining 24 articles, some may be manufactured in Denmark but the majority is of unknown origin.

Solution »stomach acid« is a hydrochloric acid solution at pH 1.5 (as specifled in DS/EN 71-3:1995 - Safety of toys - migration of certain elements).

This solution simulates the action of stomach acid when babies and infants are sucking textile pro­ducts, and when children and adults are inhaling and swallowing textile dust particles.

Solution »acid sweat« is an artificial sweat at pH 5.5 according to ISO 105-E04:1994 Colour fastness to perspiration.

Solution »alkaline sweat with reduction« is an artificial sweat at pH 8.0 according to above mentioned ISO-standard, in which a reduction treatment is carried out with sodium dithionite.

The two solutions »acid sweat« and »alkaline sweat with reduction« simulate the effects presumed to take place when textiles are in contact with the skin.

Extracts with the alkaline sweat solution were prepared from all articles and analysed for splitt-off aromatic amines by gas chromatography (GC/MS). In certain cases, extracts were also prepared with the stomach acid solution and the acid sweat solution. These extracts were analysed for free aromatic amines.

A detailed description of the test method is given in Enclosure 4, which also lists time detection limits in Table 11.1.

In Table 5.3 the test results are presented. In the table the following notations are used:

• Aromatic amines detected in each sample are listed with the concentration given in brackets.
• Aromatic amines with no marks are included in the IARC-list or in the German Regulations:

• Aromatic amines marked with *) are other aromatic arnines which are neither on the IARC-list nor on the German Regulations list.
• Test results marked with **) was obtained using a different method of analysis (reduction in alkaline liquid according to Oeko-Tex standard 200). The method is not publicly available.

Table 5.3
Test results.

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The full report of the testing is given in the reports Reg.nr. 19721 dated 1996.10.08, 19972 dated 1996.12.19 and 21161 dated 1997.03.05, all issued in Danish by DTI Chemical Technology.

The detection limits are not the same for every one of the aromatic amines and some of the amines are particularly sensitive to the analysing system, while others are not.

On this background it might be reasonable to assume one common detection limit of not less than 2 ppm (2 mg/kg textile). From an analytical consideration, the assumed detection limit should probably be 5 ppm, to be sure to have a realistic overall detection limit for all amines.

The four samples No. 11, 14, 30 and 40 show appreciable amounts of amines split off (more than 5 ppm), amines which are included in the IARC-list as well as in the German Regulations.

For the samples No. 16, 17, and 34 the tendency is the same but the amounts of amines from the list are smaller (sample No. 34 less than 5 ppm but higher tham 2 ppm; sample No. 16 and 17 less than 2 ppm but higher than 1 ppm. However, for sample No. 16 there is an uncertainty about which isomer of anisidine is present).

In the samples No. 11, 14, 16, 17, 30, 34, 37 and 40 the following amines from one or both of the two lists were found:

4-Chloroaniline
2,4-Diaminotoluene
4-Aminobiphenyl
o-Toluidine
o-Diarmisine
o-Tolidin
2-Amino-4-nitrotoluene
o-Anisidine (or p-Anisidine which is not on any of the two lists)
Benzidine (or its isomers which are not on any of the two lists)

Very appreciable amounts (300 ppm) of benzidine or its isomers were found in sample No. 37 and 40. Benzidine is included in both lists, but it was not possible to determine whether benzidine itself was in fact present.

Several samples split off very high amounts of amines which are not included neither in the IARC-list nor in the German Regulations list. This is time situation for the samples No. 2, 15, 16, 22, 23, 26, 28, 30, 37, 40, 43, 46 and 49.

The amines which are not included in any of the two lists but are found in rather high amounts are:

Aniline
m- and p-Toluidine Isomers of Benzidine m- and p-Anisidine
Isomers of Chlorophenylenediamine
p-Phenylenediamine
Aminocresole
Isomers of Trichloroatmiline
Dodecylaniline
p-Phenetidine
Chloroisomers of o-Trifluoromethylaniime

The analysis shows only very little tendency to find free amines in the textiles.

Both dyed and printed textiles were represented in time group of five samples (No 11, 14, 30, 34 and 40) for which listed amines were found in amounts of 2 ppm or more.

One dyed sample was made of polyester, the remaining four were made of cotton and two of these were dyed and two were printed.

It is not known whether the print is pigment printed or printed with a dyestuff.

The thirteen samples (No. 2, 15, 16, 22, 23, 26, 28, 30, 37, 40, 43, 46 and 49) which split off other amines than the listed ones are all dyed, but two of them do have additional print on time dyed fabric.

The majority of thiese dyed samples are made of cotton, but nylon, silk and wool are represented as well.