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Survey and health assessment of selected respiratory sensitizers in consumer products 2 Inventory of consumer products, which may contain any of the five R42 substances
2.1 Glutaraldehyde, CAS 111-30-8Synonyms: Glutaral; 1,5 pentanedial The SPIN database has registered 428 preparations with glutaraldehyde in Finland, Norway, Sweden and Denmark in 2003. Of these, 139 preparations are registered in Denmark. Some of the 428 preparations are registered as consumer preparations in Norway and Sweden. The industrial use for which the preparations are registered in Denmark is:
The use category for which the preparations have been registered in Denmark is:
Glutaraldehyde is permitted in cosmetics as a preservative (no. 26, VI, 1,48). The maximum permitted concentration is 0.1% and it is banned in aerosol and spray products. Labelling with “Contains glutaraldehyde“ is mandatory, if the concentration in the final products exceeds 0.05%. The INCI name for glutaraldehyde is Glutaral. The search on the internet by Google for disinfectants containing glutaraldehyde gave only products intended for use in food industry and agriculture. No sale to private consumers could be identified. A search for glutaral on the internet by Google turned up one body lotion containing Glutaral. This body lotion was sold from a French internet page, claiming that it helps against staphylococci adherence to the skin. A search among the previous surveys of chemical substances in consumer products revealed that glutaraldehyde residues may be present in paper handkerchiefs and toilet paper in concentrations of up to 0.08 kg/t (1). An additional search for cases of respiratory allergy resulting from exposure to glutaraldehyde emission from consumer products was carried out in the database PubMed. Several cases of asthma resulting from occupational exposure to glutaraldehyde containing disinfectants were found, but none were related to private use. Cases of exposure to glutaraldehyde in the private setting, were only found in relation to contact dermatitis, but not to respiratory hypersensitisation. 2.1.1 ConclusionWith regard to glutaraldehyde containing consumer products, we should look for:
2.2 Cyclohexane-1,2-dicarboxylic anhydride (unspec.), CAS 85-42-7Synonyms: hexahydro-1,3-isobenzofurandione hexahydrophthalic anhydride The SPIN database has registered 57 preparations with cyclohexane-1,2-dicarboxylicanhydride (CDA) in the Nordic countries in 2003. Of these, 38 preparations are registered in Denmark. None of the 57 preparations are registered as consumer preparations. The industrial use for which the preparations are registered in Denmark is:
The use category for which the preparations have been registered in Denmark is:
In Sweden, CDA is also used for curing agents in plastic. Hence, CDA may occur as a residual monomer in consumer products. In cosmetics, CDA may occur as a monomer in different film forming polymers used in e.g. nail lacquer. CDA as such is not found on the INCI list. In a declaration, it might be listed as phthalic anhydride in the kind of polymer used, e.g. Phthalic Anhydride/Benzoic Acid/Trimethylolpropane Copolymer. We do not know if CDA or only phthalic anhydride is actually employed in the phthalic anhydride copolymers. In 2002, the information centre for Environment and Health published a list of products containing unwanted substances. Among these were nine nail lacquers containing phthalic anhydride according to the product declaration (3). An additional search in PubMed for cases of respiratory sensitization gave several hits indicating that occupational exposure to epoxy resins and their hardeners is a common reason for respiratory sensitization to CDA (4,5,6). No cases of CDA allergy from private use of epoxy products were found in the PubMed database. However, as two-component epoxy products are available for private use, some of these were sampled for CDA emission testing. 2.2.1 ConclusionWith regard to CDA containing or –emitting products, two-component epoxy adhesives and nail lacquer were considered relevant for emission analysis. 2.3 Hexahydro-4-methylphthalic anhydride, CAS 19438-60-9Synonyms: Hexahydro-4-methylphthalsyreanhydrid, Hexahydro-5-methyl-1,3-isobenzofurandione In 2003, the SPIN database has registered 3 preparations with hexahydro-4-methylphthalic anhydride (HMPA) in the Nordic countries. None of these were registered in Denmark. In fact, all three were registered in Sweden, and none of these were consumer preparations. Industrial use categories are:
Hence, HPMA may occur as a residual monomer in consumer products. In cosmetics, HPMA may occur as a monomer in different film forming polymers used in e.g. nail lacquer. HPMA as such is not found on the INCI list. On a declaration, it might be listed as Phthalic anhydride in the kind of polymer used, e.g. Phthalic Anhydride/Benzoic Acid/Trimethylolpropane Copolymer. We do not know if HPMA or only phthalic anhydride is actually employed in the phthalic anhydride copolymers. In 2002, the information centre for Environment and Health published a list of products containing unwanted substances. Among these were nine nail lacquers, which contained phthalic anhydride according to the product declaration (3). An additional search in PubMed for cases of respiratory sensitization gave a few hits indicating that occupational exposure to epoxy resins, their hardeners, and unsaturated polyester resins (UP resins) is a common reason for respiratory sensitization to HPMA (5,7,8). No consumer product related cases were found during this search. 2.3.1 ConclusionWith regard to HPMA containing or –emitting products, we decided to sample two-component epoxy adhesives and nail lacquer. 2.4 Methyltetrahydrophthalic anhydride, CAS 11070-44-3Synonyms: MTHPA tetrahydromethyl-1,3-isobenzofurandione In 2003, the SPIN database has registered 5 preparations with methyltetrahydrophthalic anhydride (MTHPA) in 2003. None of these were registered in Denmark. In fact, all five were registered in Sweden, and none of these were consumer preparations. Industrial use categories are:
Hence, MTHPA may occur as a residual monomer in consumer products. In cosmetics, MTHPA may occur as a monomer in different film forming polymers used in e.g. nail lacquer. MTHPA as such is not found on the INCI list. On a declaration, it might be listed as phthalic anhydride in the kind of polymer used, e.g. Phthalic Anhydride/Benzoic Acid/Trimethylolpropane Copolymer. We do not know if MTHPA or only phthalic anhydride is actually employed in the phthalic anhydride copolymers. In 2002, the information centre for Environment and Health published a list of products containing unwanted substances. Among these were nine nail lacquers containing phthalic anhydride according to the product declaration (3). An additional search in PubMed for cases of respiratory sensitization gave a few hits indicating that occupational exposure to epoxy resins, their hardeners, and unsaturated polyester (UP) resin is a common reason for respiratory sensitization to MTHPA (5,7,8). No consumer product related cases were found during this search. 2.4.1 ConclusionIn conclusion, with regard to MTHPA containing or –emitting products, we decided to sample two-component epoxy adhesives and nail lacquer. 2.5 Methylene diphenyl diisocyanate, CAS 26447-40-5; 5873-54-1; 101-68-8Synonyms: 1,1’-methylenebis(isocyanato)benzene, MDI In 2003 The SPIN database has registered 308 preparations with MDI in The Nordic countries. Of these, 148 preparations are registered in Denmark. Some of the 308 preparations are registered as consumer preparations in Norway and Sweden. The industrial use for which the preparations are registered is:
The use categories for preparations registered in Denmark are:
Deeming from this, MDI or residues of MDI might be emitted from consumer products, such as boat and car repair kits, furniture (mattresses), two-component adhesives and putties, flooring and wall paper. Polyurethane materials in clothing may also emit MDI. Secondary exposure to MDI may occur when polyurethane materials are processed by grinding or heating (9). MDI has been subject to an EU risk assessment, published in 2005 (10). One of the conclusions for consumers was that there is a need for limiting risks, since health risks due to combined occupational and consumer exposure could not be excluded with regard to sensitization (dermal contact and inhalation exposure). In the EU risk assessment report, possible exposure to free MDI from the following products has been identified:
Spray foam or One Component Foam (OCF): MDI-based OCF is offered in the consumer market and to professional tradesmen for use as a filler in small gaps in buildings (e.g. around window frames, between floor boards etc). In this context, the word ‘spraying’ is not entirely appropriate. The OCF is supplied in pressurised cans and is applied through a pre-expansion tube (always part of the package). The product is released from the nozzle as viscous foam, rather than as a sprayed aerosol. Curing starts immediately and moves from the outside inwards. Therefore, emission and hence potential exposure virtually ceases once the outer coat has been cured. However, Sweden has a warning when using the one-component frothed foam. PU wood adhesives are used for waterproof bonding and on moist wood. Flooring adhesives are used for wood-parquet. PU paint is used as a primer for liquid roof coating, with a long in-service life (10 to 15 years), and for decorative painting. It is confirmed by industry that hot melt adhesives are currently offered to the D.I.Y. (do-it-yourself) market. According to industry, even 2-component products are offered to the D.I.Y. market. One company stated: “Moreover, other products normally offered only to the craftsmen can reach end-consumers by self-service at craftsmen retailers”. However, it is very unlikely that the consumer’s working conditions are ever appropriate for the use of 2-component products containing free MDI (10). A search in the INCI list for the three CAS numbers connected with MDI showed no result. A second search on “MDI” gave three copolymers, in which MDI may have been used, and may therefore emit residual monomer: PEG-8/SMDI copolymer, CAS 39444-87-6 PPG-12/SMDI copolymer, CAS 9042-82-4 PPG-51/SMDI copolymer, CAS 9042-82-4 These substances are copolymers of the respective PEG’s and saturated MDI monomer. They are used as hair conditioning agents, hair fixative, plasticizer, skin-conditioning agent (emollient and miscellaneous), in eye shadows, foundations, miscellaneous makeup preparations , and moisturizing preparations (11). Since the present project deals with the substances as respiratory sensitizers we considered it prudent to test the emission of MDI from aerosol hair fixatives with the above mentioned polymers on the ingredient list. 2.5.1 ConclusionWith regard to MDI containing and –emitting products, we decided to look for samples of the following products:
2.6 Results of inquiriesAnswers to general inquiries about the knowledge of inclusion of any of the five substances in consumer products were given from: COOP Dansk Supermarked A/S The Association of Plastic Industries in Denmark. Danmarks Farve- og Lakindustri Association of Danish Cosmetic, Toiletries, Soap and Detergent Industries (SPT) None of these respondents were aware of the presence of any such products on the Danish market. 2.7 Results of search for products with likely emission of the five substancesGlutaraldehyde The search for products containing glutaraldehyde was very difficult. The search for film and picture developers with content of glutaraldehyde, and not exclusively for occupational use, was negative after several telephone inquiries. One inquiry led us to a company who thought they might provide a developer with glutaraldehyde for youth schools with classes in photography. However, upon further investigation, this company was not able to deliver any such developer. Upon this, we concluded that the use of glutaraldehyde in developers for hobby use seems to have been phased out. Next, we thought glutaraldehyde might be present in disinfectants for home use or mouth washes. Telephone inquiries and store searches revealed no such thing. Finally, since glutaraldehyde according to our investigation may be found in paper towels and paper handkerchiefs we purchased some toilet paper and some kitchen rolls made of recycled paper. Phthalic anhydride derivatives Two component epoxy adhesives were readily available from do-it-yourself-markets, so samples of these products were purchased and sent for analysis for emission phthalic anhydride derivatives. Nail lacquers containing polymers based on phthalic anhydride derivatives were identified in stores by scrutiny of the INCI declaration. The nail lacquers were chosen according to place of the polymers in the INCI declaration, since ingredients are supposed to be mentioned in order of falling concentration. Hence, if the polymer is mentioned as one of the first ingredients the nail lacquer was preferred for sampling rather than the one where the polymer was mentioned later. This was thought to give the best chance of measuring the emission, if any would be present. MDI Consumer products made with polyurethane, MDI-copolymer or MDI was easier to find, although some discrepancy in information regarding the content of residual MDI-monomer in adhesives and joint fillers were found. Cosmetic products were sampled if the ingredient list contained MDI based polymers or copolymers. We purchased samples of car window adhesive, floor adhesive, joint filler, PU-rainjacket, hairspray and conditioner, and mattresses.
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