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Kortlægning og vurdering af kemiske stoffer i glas- og porcelænsfarver

Summary and conclusions

Survey
Chemical analysis
Health evaluation
Environmental evaluation

Survey

Glass and porcelain colours are hobby products for children and adults. CE labelled products are intended for children under 14 years. Products with the CE mark must conform to the prevailing requirements for toys and are restricted in regard to content and release of certain substances dangerous to health. As all private consumers are not familiar with the CE mark, the Danish Environmental Protection Agency expects that children below 14 years will have a risk of getting into contact with glass and porcelain colours that are not CE marked and do not conform with the safety requirements for toys.

Exposure to substances in the products can occur in the form of direct contact with fingers, hands and face and by inhalation. Exposure of the environment is possible when brushes and pencils are cleaned and disposed of after use. Therefore there is a need to examine the substances the consumers and the environment may be exposed to during use of the products.

There are about 15 producers of glass and porcelain colour and window colour worldwide and most products from these producers are on the Danish market. There are fewer glass and porcelain colours which are CE labeled or carry some other labelling than window colours.

17 pigments, of which two are intermediates, including both inorganic and organic substances are identified in the survey. Among the organic pigments, azo-pigments and polycyclic pigments have been identified. Only one pigment, copper phthalocyanine, containing heavy metal has been identified. None of the inorganic pigments identified in the survey contain heavy metals.

All glass and porcelain colours except one included in the survey and test are water based. Binders are primarily acrylates, often thermoplastic (meth)acrylates. Acrylates consist of acrylic acid and methacrylic acid and their methyl-, ethyl- and butyl esters.

Additives include among others thickeners, surfactants, biocides, anti foaming agents and solvents (co-solvents). In glass and porcelain colour, biocides like isothiazolones and bronopol are used. These biocides are also used in CE marked products. A range of glycols and alcohols are also found in this type of products.

Chemical analysis

Screening analysis of substances in glass and porcelain colours show in general that it is alcohols, glycols, ketones, esters and simple hydrocarbons, which are the main constituents among the extractable substances. Some of these are identified by chemical name and some as substance groups.

The levels in the tested products vary between few mg/kg to 150,000 mg/kg in one product for methylpyrrolidone corresponding to 15% in the product (P6). In the safety data sheet it is declared that the content is 1-1.5%. Butanoneoxim is found in concentrations up to 2.9%.

A hydrocarbon mixture (C6-C12) of alifatic, alicyclic and aromatic hydrocarbons in concentrations of 17% is found in one product (P12) corresponding to the information in the safety data sheet on the white spirit content.

Examples of other substances identified in relatively high concentrations in a single product are buthoxyethanol (2.4-2.5%) (P9) and phthalic acid anhydride (2.3-3.0%) (P12).

Methoxy(propenyl)phenol (Eugenol) was found in two products in concentrations between 21 and 26 mg/kg (0.0021 and 0.0026%). This substance is considered sensitising by skin contact and is covered by the amendment to the Cosmetic Directive of 27 February 2003 with a requirement to indicate the presence of the substance in the ingredients list when its concentrations exceeds 0.001% in leave-on products, and 0.01% in rinse-off products.

Other substances are found in concentrations ranging from about 0.0004% up to 0.5%, most in the lower end. This is also the case for the substances selected for toxicological evaluation based on the results from the chemical analysis. Most of the concentrations are therefore below the general minimum limits stated in Statutory Order no. 329 of 16 May 2002 from the Ministry of the Environment on classification, packaging, labelling, sale and storage of chemical substances and products (classification order).

Among the metals, lead, zinc, copper, cobalt and titanium have been analyzed. Lead is found in three products in concentrations corresponding to 0.0026 and 0.0027% in the products. Consequently the concentration levels are below 0.15% requires special labelling of lead containing products to be used as paint or lacquers according to the classification order.

Health evaluation

Based on the survey and the results from the chemical analyses, 9 substances have been selected for toxicological evaluation. The substances are:

Of the 9 evaluated substances, three are on the List of Dangerous Substances and one substance is on the Danish EPA's guidance list for self classification. For these substances toxicological literature has been available which supports and to some extent supplements the information expressed through the classification. For the five other substances more limited information or no information on toxicological properties has been available in the searched literature. This is also the situation regarding NOAEL values, and exposure data in relation to human exposure.

Critical effects in relation to the evaluated substances for the intended use are acute toxicity (1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, 2-naphthol, hexamethylene diisocyanate and 5-isocyanate-1-(isocyanatemethyl)-1,3,3-trimethyl-cyclohexane), possible carcinogenic effects (anthraquinone and 2-butanone oxime) and sensitising effects (anthraquinone, 2-butanone oxime, 2-naphtol, 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, diarylide, hexamethylene diisocyanate and chloroisocyanate benzene).

Seven of the 9 substances which are evaluated with regard to health and environmental properties have more or less well documented sensitising potential and four are classified as sensitisers.

In the product P12 phthalic acid anhydride has been identified in concentrations of 2.3 - 3%. This substance must be classified as sensitising by skin contact and by inhalation in concentrations of 1% or more. The substance must be expected to come from alkyd resin in the product. The substance will therefore exist in chemically combined form in the product, but can be released by thermal decomposition.

Methylpyrrolidone is found in concentrations between 0.8 and 15%. The substance must be classified as irritating to skin and eyes in concentrations of 10% or more.

In total, three of the 10 analysed products (P3, P4 and P8) are CE labelled. Based on information from the suppliers and results from the analyses, all three products are considered to comply with the rules.

Environmental evaluation

With regard to the environmental properties, only few data have been found in the literature about the substances. For two of the substances it is known that they are both very dangerous to aquatic organisms and also very persistent in the environment. Hence it is important to minimise the discharge to the water environment.

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Version 1.0 Juli 2005, © Miljøstyrelsen.