Occupational contact allergy to components of polyester resin systems

Transcription

1 Contact Dermatitis riginal Article CD Contact Dermatitis ccupational contact allergy to components of polyester resin systems Kristiina Aalto-Korte and Katri Suuronen ccupational Medicine, Finnish Institute of ccupational Health (FIH), Helsinki, Finland doi: /cod Summary Background. Allergic contact dermatitis caused by polyester resin is considered to be rare. bjectives. To describe 11 new patients diagnosed with occupational contact allergy to components of polyester resin systems in Methods. Data on occupations, patch test results, symptoms and exposure to polyester products were retrieved from patient files, covering 1994 to February Results. Five patients reacted to unsaturated polyester resin putties. In 3 of these cases, putties were considered to be the main cause of the dermatitis. Four patients had cobalt allergy resulting from cobalt salts that were used as accelerators in polyester resins. Three patients were sensitized to triglycidyl isocyanurate (TGIC), a cross-linker in polyester powder paints. Conclusions. Two product types are of particular importance in contact allergy to polyester resin: powder paints cured by heat with TGIC as the cross-linker, and car putties. Car putties are used not only in repair car painting, but also in some industrial trades to smoothen surfaces before painting. As commercial patch test substances of polyester resin putties are lacking, patients own products need to be tested. Cobalt salts are used in several types of polyester resin product as accelerators, and these must be considered as a possible cause of cobalt sensitization. Key words: 4-tert-butyl catechol; car putties; cobalt; powder paints; triglycidyl isocyanurate; CAS no Polyester resins are condensation products of difunctional or polyfunctional monomers containing hydroxyl groups and carboxyl groups (1). Contact allergy to raw materials or components of polyester resin systems is quite rare (2). A total of 8 cases of occupational contact allergy caused by polyester putties (cements) have been reported by the Finnish Institute of ccupational Health (FIH) (3, 4). We have tested a polyester putty in a special resin patch test series since Triglycidyl isocyanurate (TGIC) (CAS no ; Fig. 1) is a trifunctional epoxy compound that is used as a curing agent in polyester powder paints. In the literature, we found several reports of occupational contact allergy to TGIC among people working on the production and use of polyester powder paints (5 9). Reports also exist of cobalt sensitization caused by cobalt salts, which are used as accelerators in polyester products (10, 11). At the FIH, polyester putties, TGIC and cobalt salts have been the most significant causes of polyester-related allergic contact dermatitis, and we wanted to report 11 new cases caused by these three substances. Correspondence: Kristiina Aalto-Korte, ccupational Medicine, Finnish Institute of ccupational Health (FIH), Post box 40, FI Helsinki, Finland. Tel: ; Fax: kristiina.aalto-korte@ttl.fi Conflicts of interest: The authors declare no conflict of interests. Accepted for publication 23 January 2016 Patients and Methods This analysis covers patients at the FIH between December 1993 and February All patch tested patients at the FIH have a suspected occupational skin disease. They 14 Contact Dermatitis, 75, 14 19

2 ALLERGYTPLYESTERRESINSYSTEMS AALT-KRTE & SUURNEN N N Fig. 1. The chemical structure of triglycidyl isocyanurate (CAS no ). N Cobalt was analysed from the material samples by atomic absorption spectrometry with a graphite oven. The method was based on NISH method 7027 for cobalt and cobalt compounds (12). The result showed the total amount of elemental cobalt in the sample. Results In Table 1, we show details of the 11 cases of occupational contact allergy to components of polyester resins. Testing of the first polyester putty resin in the resin series yielded two irritant reactions (0.9%), while the Viapal putty resin yielded none. TGIC provoked one irritant reaction (0.1%). come from all parts of Finland. We performed the patch tests with Finn Chambers (SmartPractice, Phoenix, AZ, USA) according to ICDRG recommendations. The application period was 2 days. We read the tests two or three times: on day (D)2, D3, and D4, on D2, D3, and D6, or on D2 and D5, depending on the day of application (Monday, Tuesday, or Wednesday). We asked patients to inform us if they noticed new reactions after the final reading. We tested the patients with a modified Finnish baseline series, and with special series or individual allergens according to the exposure. Between April 1997 and ctober 2002, a polyester putty resin was tested in a special resin series (which also contained formaldehyde resins from the plywood industry), at a concentration of 5% pet., in a total of 231 patients. In 2001, its cobalt content was analysed by atomic absorption spectrometry, and the result was negative (< mg/g). Unfortunately, we no longer have the information regarding the trade name of this putty, but it must have been a product of some of the previous polyester putty-allergic patients at the FIH (4). ne patient (no. 1 in Table 1) reacted to this test substance. In November 2002, it was replaced by Viapal polyester putty resin (Allnex, Brussels, Belgium; 5% pet.). By February 2015, we had tested Viapal putty resin in 249 patients, and noted allergic reactions in 4 (1.6%) of these (nos. 2 5 in Table 1). Since December 1993, we have tested TGIC (0.5% pet; Chemotechnique, Vellinge, Sweden) 699 times, and 5 patients have had allergic reactions to it (0.7%). Three of these cases have been related to polyester powder paints (nos in Table 1). We did not investigate all patients with contact allergy to cobalt chloride; we only included 4 patients with identified exposure to polyester products (nos. 5 8). ne of these reacted to Viapal putty resin in addition to cobalt chloride. Discussion Cobalt allergy and polyester resins Cobalt salts, cobalt 2-ethylhexanoate (cobalt octoate; CAS no ) and cobalt naphthenate (CAS no ) are used as accelerators in unsaturated polyester resins. We found several case reports of cobalt sensitization caused by polyester products in the literature. The causative products have included lamination resins and reinforced plastic resins (10, 11, 13 15). Patients have usually reacted to cobalt chloride in the baseline series. The present study population comprises 4 cobalt-allergic patients who had used cobalt-containing polyester resins at their work: putties used in repair car painting (no. 8), industrial painting (no. 5), and mould manufacture (no. 7); and lamination resin used in boat building (no. 6). The safety data sheet of the putty of patient no. 8 declared cobalt salts of branched C6 C19 fatty acids (CAS no ), and not cobalt 2-ethylhexanoate or cobalt naphthenate. Patient no. 5 also reacted to resin in the resin series, and it is possible that he was sensitized to other components of polyester putties in addition to cobalt. We have not analysed Viapal putty for cobalt, but it usually gives negative test results in cobalt-allergic patients, and, according to the safety data sheet, does not contain cobalt salts. The former polyester putty resin test substance in our resin series also did not contain cobalt (analysed with atomic absorption spectrometry). Cobalt is a frequent sensitizer, and it is difficult to determine the cause of sensitization with absolute certainty. None of our patients had nickel allergy, and their skin symptoms were work-related. TGIC TGIC is a trifunctional epoxy compound that is mainly used as a curing agent in thermosetting one-component Contact Dermatitis, 75,

3 ALLERGYTPLYESTERRESINSYSTEMS AALT-KRTE & SUURNEN Table 1. Eleven patients with polyester resin-related occupational allergic contact dermatitis: year of investigation, occupation, exposure time, location of dermatitis, consequences of occupational allergy, patch test reactions, and exposure to polyester resin Patient no. Year of investigation ccupation; trade Time in same work before symptoms appeared; location of dermatitis; consequences of contact allergy Patch test reactions to polyester-related substances in routine test series (other contact allergies) Polyester resins used at work (composition): patch test reactions and concentrations in pet Car repairman 6 months; hands; left job Polyester putty resin ++ (Myroxylon pereirae, fragrance mix I) Car painter 7 years; hands, upper extremities, face; could not continue working Manufacture of door frames 2 years; hands, forearms and face; healed after changing to packing tasks; epoxy and acrylate-based putty was probably the main cause of dermatitis Car repairman 10 years; face, hands, widespread; consequences unknown Industrial painter of cabins of mining machines Glass fibre sprayer in the manufacture of plastic boats 1 year; face, hands; could not continue working; epoxy products were the main cause of dermatitis 1 month; hands, face, neck, widespread; no symptoms after leaving job Fitter in a foundry 2 years; hands, upper extremities, face; could not continue working; polyester products were not the main cause of dermatitis Car painter 20 years; hands, upper extremities, face, legs; no symptoms after leaving job Painter of tractor cabins 7 years; hands, face, neck; no symptoms after changing to assembling tasks resin + resin ++; 4-tert-butyl catechol ++ (nickel sulfate, colophonium, DGEBA-R, DGEBF-R, acrylates) Viapa polyester putty resin + resin ++ (DGEBA-R, DGEBF-R, tris-dmp, PTBPGE) polyester putty resin?+ (analysis: cobalt < mg/g) (thiurams, MDA, formaldehyde/ liberators/resins) 4-tert-butyl catechol +++ (epoxy compounds, PPD, black rubber chemicals, thiurams, colophony, fragrances, PTBPFR, phenol formaldehyde resin, acrylates) resin TGIC 1% + (cycloaliphatic epoxy resin) Glasurit ratio-spachtel weiss: 5% ++ K2 putty dust: 100% R Multifunction putty, Dupond: 5% + Car System Flex polyester filler Wosschemie: 5% ++ Dust from the workplace: 20% ++ Car System Elastic polyester fine putty Wosschemie: 5% ++ Repair extra+ polyester resin cement: 1.64% +, 0.5%+ Weekly exposure to polyester car putties: NT Endyne D polyester resin (analysis: cobalt mg/g): 5% +++ Interox MEKP-HA-2 polyester hardener: 1% Norpol polyester lamination resin: NT Norpol Accelerator 9802 (SDS: 5 10% cobalt octoate): NT Ferro Elastic beige polyester putty Vosschemie: NT BP hardener: NT Raderal Fuellgrund 3508 Graubeige 2K-polyestersystem putty (SDS: % cobalt salts of branched C6 C19 fatty acid CAS no ): NT Infralit polyester powder paint (SDS: TGIC 4%): 10% +, 1% 16 Contact Dermatitis, 75, 14 19

4 ALLERGYTPLYESTERRESINSYSTEMS AALT-KRTE & SUURNEN Table 1. Continued Patient no. Year of investigation ccupation; trade Time in same work before symptoms appeared; location of dermatitis; consequences of contact allergy Patch test reactions to polyester-related substances in routine test series (other contact allergies) Polyester resins used at work (composition): patch test reactions and concentrations in pet Spray painter of bicycles 8 months; hands, face, foot; could not continue painting (not even with non-powder paints) Car painter 1 year; face; no symptoms after changing tasks TGIC 1% ++ (formaldehyde/liberators) TGIC 1% ++ (PTBPFR, phenol formaldehyde resin) Polyester powder paints (SDS: TGIC 5 10%): NT Infralit polyester powder paint CM 7000 black (SDS: TGIC 1 5%): 10% ++, 3.2% ++, 1%++ DGEBA-R, diglycidyl ether of bisphenol A resin; DGEBF-R, diglycidyl ether of bisphenol F resin; MDA, 4,4 -diaminodiphenylmethane; NT, not tested; PTBPGE, p-tert-butylphenol glycidyl ether; PTBPFR, p-tert-butyl phenol formaldehyderesin; PPD, p-phenylenediamine; SDS, safety data sheet; TGIC, triglycidyl isocyanurate; tris-dmp, 2,4,6-tris-dimethylaminomethylphenol. Cobalt chloride was tested in the baseline series, TGIC in a special epoxy compound series, 4-tert-butyl catechol in the plastics and glue series, and polyester putty resins (Viapal and the preceding putty resin) in a special resin series that contains formaldehyde resins used in the plywood industry. Polyester putty resin in special resin series, name unknown. wn polyester products were not tested because the patient did not bring them for patch testing. The products were found in exposure assessment after diagnosis of allergies in patch testing. Liquid lamination resin that was mixed with hardener and glass fibre before spraying. The uncured resin part was used in patch testing and analysed. polyester powder coatings. Allergic contact dermatitis has been reported among people working in the manufacture of TGIC (16), in people working in the the manufacture of polyester powder paints (5, 6), and in painters using powder coatings (7 9). In addition, occupational allergic contact dermatitis caused by TGIC has been reported among people working in the manufacture and product development of circuit boards in the electronic industry (17, 18). In this application, TGIC was used as a hardener for epoxy acrylate-based ultraviolet-curable solder-resistant coatings, which were applied with a silk screen printing method. In the present article, we describe 3 new cases of TGIC allergy in spray painters using polyester powder paints. All of the patients had eczema on their faces and had negative test results with diglycidylether of bisphenol A resin. During the same time period, we also investigated two silk screen printers working in the manufacture of circuit boards, who had contact allergy to TGIC. TGIC is available as a commercial test substance. Polyester powder paints can be tested at a concentration of 10% pet. Unsaturated polyester putty resins Unsaturated polyester resins are widely used as cements (putties) in car repair painting, to produce a smooth surface before painting. The same car cements are also used in other industrial trades: for example, in mould manufacturing, they are used to fill out small holes or imperfections in the mould surface. A total of 6 car painters and 2 mould manufacturers with contact allergy to polyester cements have been previously reported by the FIH (3, 4). Diethyleneglycol maleate (DEGM) was identified as the causative allergen in 2 of the 6 painters (4, 19). DEGM was purified by thin-layer chromatography specifically in the case of these 2 patients. We have not been able to use DEGM in any routine testing. The present study population includes 4 patients (nos.1 4) who reacted to both their own polyester cements and to the routine polyester cement test substance in the resin patch test series. ne of these (no. 3) was also sensitized to 4-tert-butyl catechol, which is a possible component of polyester resins. In addition, one of the cobalt-allergic cases (no. 5) reacted to the routine test substance Viapal putty resin. The literature includes a case report of two plasterers who reacted to a Polykit polyester product (Sikkens, Sassenheim, The Netherlands) (20). Dooms-Goossens and de Jonge also investigated an automobile body repairman who reacted to two unsaturated polyester resins. The product types were not described in detail, but they were possibly car putties (21). We were not able to find any other case reports deriving from polyester putties/cements in the literature. Since the year 2000, we have not come across any other types of polyester Contact Dermatitis, 75,

5 ALLERGYTPLYESTERRESINSYSTEMS AALT-KRTE & SUURNEN Table 2. Recommended patch test concentrations for different polyester products Polyester product Recommended concentration in pet. (%) Polyester putty, resin part 5 Polyester putty, hardener 1 Cured polyester putty, e.g. putty dust 20 Polyester powder paint 10 Polyester lamination resin, resin part 5 Polyester lamination resin, hardener 1 product that provoke allergic reactions in patch testing at the FIH, apart from cobalt-containing laminating resin in a cobalt-sensitized patient (no. 6 in Table 1). In the literature, a boat builder in Sweden had allergic patch test reactions to lamination polyester resins, but no sensitization to cobalt or to any other polyester-related allergen (22). ther compounds Two of our patients (nos. 3 and 7) reacted to 4 -tert-butyl catechol. These 2 patients had used car putties from the same manufacturer (Vosschemie, Uetersen, Germany). 4-tert-Butyl catechol is used as an inhibitor of unsaturated polyester resins. Unfortunately, we did not try to analyse the substance in the polyester resins used by our sensitized patients. A Japanese series of 29 workers exposed to unsaturated polyester resins in the manufacture of fibreglass-reinforced plastics included 2 patients sensitized to 4-tert-butyl catechol, although exposure to 4-tert-butyl catechol was not shown directly (14). 4-tert-Butyl catechol seems to be a possible allergen in polyester resins, but, as long as exposure to it is not shown by chemical analyses, the relevance of the allergic reactions remains uncertain. Carboxylic acid anhydrides are used in the production of polyester resins. These chemicals very rarely cause delayed-type contact sensitization, but they may induce immediate contact allergy. A relatively recent series of 21 acid anhydride contact urticaria cases at the FIH included 1 case caused by maleic acid anhydride in the production of polyester resins (23). There are other possible allergens in polyester resin systems (2), but we have not tried to review all of them in this case series. Conclusions Contact allergy to polyester resin products is rare. At the FIH, the product type that most often induced allergic contact dermatitis was unsaturated polyester resin car putty. Car putties are used not only in repair car painting but also in some industrial trades to smoothen surfaces before painting. In order to confirm the diagnosis, patients own putties need to be tested, as commercial test substances are lacking. The uncured resin part of a putty can be tested at a concentration of 5% pet. Cobalt is used in several types of unsaturated polyester resin product (also putties) as accelerators, and these must be considered as a possible cause of cobalt sensitization. In addition, TGIC is used as a curing agent in polyester powder paints, and poses a considerable risk of sensitization in these products. ur recommendations for test concentrations of polyester products are shown in Table 2. Contact allergy to polyester products seems to have a poor prognosis, as all of our patients changed tasks or left their jobs. References 1 Funke W, Hoppe L, Hasselkus J et al. Paints and Coatings, 2. Types. In: Ullmann s Encyclopedia of Industrial Chemistry: B Elvers (ed), Wiley nline Library, Hoboken, New Jersey, USA, John Wiley & Sons, Inc., 2010: pp Nixon R, Cahill J, Jolanki R. Polyester resins. In: Kanerva s ccupational Dermatology, T Rustemayer, P Elsner, S M John and H I Maibach (eds): Berlin, Heidelberg, Springer-Verlag, 2012: Tarvainen K, Jolanki R, Estlander T. ccupational contact allergy to unsaturated polyester resin cements. Contact Dermatitis 1993: 28: Kanerva L, Estlander T, Alanko K et al. ccupational allergic contact dermatitis from unsaturated polyester resin in a car repair putty. Int J Dermatol 1999: 38: Munro C S, Lawrence C M. ccupational contact dermatitis from triglycidyl isocyanurate in a powder paint factory. Contact Dermatitis 1992: 26: Foulds I S, Koh D. Allergic contact dermatitis from resin hardeners during the manufacture of thermosetting coating paints. Contact Dermatitis 1992: 26: Erikstam U, Bruze M, Goossens A. Degradation of triglycidyl isocyanurate as a cause of false-negative patch test reaction. Contact Dermatitis 2001: 44: McFadden J P, Rycroft R J. ccupational contact dermatitis from triglycidyl isocyanurate in a powder paint sprayer. Contact Dermatitis 1993: 28: Dooms-Goossens A, Bedert R, Vandaele M, Degreef H. Airborne contact dermatitis due to triglycidylisocyanurate. Contact Dermatitis 1989: 21: Anavekar N S, Nixon R. ccupational allergic contact dermatitis to cobalt octoate included as an accelerator in a polyester resin. Australas J Dermatol 2006: 47: Cahill J L, Andersen K E. ccupational cobalt-allergic contact dermatitis resulting from polyester resin. Contact Dermatitis 2010: 63: Contact Dermatitis, 75, 14 19

6 ALLERGYTPLYESTERRESINSYSTEMS AALT-KRTE & SUURNEN 12 NISH. Manual of analytical methods, 1994, method 7027: cobalt and compounds Available at: niosh/docs/ / (last accessed 17 December 2015). 13 Jolanki R, Tarvainen K, Tatar T et al. ccupational dermatoses from exposure to epoxy resin compounds in a ski factory. Contact Dermatitis 1996: 34: Minamoto K, Nagano M, Inaoka T, Futatsuka M. ccupational dermatoses among fibreglass-reinforced plastics factory workers. Contact Dermatitis 2002: 46: Tarvainen K, Jolanki R, Forsman-Gronholm L et al. Exposure, skin protection and occupational skin diseases in the glass-fibre-reinforced plastics industry. Contact Dermatitis 1993: 29: Nishioka K, gasawara M, Asagami C. ccupational contact allergy to triglycidyl isocyanurate (TGIC, Tepic). Contact Dermatitis 1988: 19: Jolanki R, Kanerva L, Estlander T, Tarvainen K. Concomitant sensitization to triglycidyl isocyanurate, diaminodiphenylmethane and 2-hydroxyethyl methacrylate from silk-screen printing coatings in the manufacture of circuit boards. Contact Dermatitis 1994: 30: Craven N M, Bhushan M, Beck M H. Sensitization to triglycidyl isocyanurate, epoxy resins and acrylates in a developmental chemist. Contact Dermatitis 1999: 40: Pfaffli P, Jolanki R, Estlander T et al. Identification of sensitizing diethyleneglycol maleate in a two-component polyester cement. Contact Dermatitis 2002: 46: Dooms-Goossens A, de Jonge G. Contact allergy to unsaturated polyester in a boat builder. Contact Dermatitis 1985: 12: Dooms-Goossens A, de Jonge G. Letter to the Editor. Contact Dermatitis 1985: 12: Lidén C, Löfström A, Storgårds-Hatam K. Contact allergy to unsaturated polyester in a boatbuilder. Contact Dermatitis 1984: 11: Helaskoski E, Kuuliala, Aalto-Korte K. ccupational contact urticaria caused by cyclic acid anhydrides. Contact Dermatitis 2009: 60: Contact Dermatitis, 75,