Polyurethane Resins

  • Kristiina Aalto-KorteEmail author
  • Malin EngfeldtEmail author
  • Tuula Estlander
  • Riita Jolanki
Reference work entry


Polyurethane (PU) products are formed by reacting a di- or polyfunctional isocyanate with a polyol in the presence of suitable catalysts and additives. The most feared PU-associated occupational disease is isocyanate-induced asthma, and preventive measures in work places have been focused to decrease respiratory exposure to isocyanates. Isocyanates in PU hardeners are also a relatively important cause of occupational allergic contact dermatitis, at least in some countries. The typical location is hands and face. Occupational allergic contact dermatitis is most commonly induced by diphenylmethane diisocyanate (MDI)-based products. Chemicals in PU resins are also skin irritants. Isocyanate-induced contact urticaria is a very rare disease.

When patch testing workers exposed to polyurethane chemicals, it is advisable to test with their own work material in addition to the commercially available patch-test preparations of diisocyanates. A second reading on day seven is advisable since positive reactions may appear late. Positive reactions to methylenedianiline (MDA) (also known as diaminodiphenylmethane) should be taken into account as it is an important marker for MDI sensitivity.


Isocyanates Diphenylmethane diisocyanate (MDI) Diaminodiphenylmethane (MDA) Paints Surface coatings Glues Adhesives Foams Contact urticaria Toluene diisocyanate (TDI) Isophorone diisocyanate (IPDI) Hexamethylene diisocyanate (HDI) Polymeric MDI (PMDI) Dicyclohexylmethane diisocyanate (DMDI) Car painters Paint industry Casts 


  1. Aalto-Korte K, Pesonen M, Kuuliala O, Alanko K, Jolanki R (2010) Contact allergy to aliphatic polyisocyanates based on hexamethylene-1,6-diisocyanate (HDI). Contact Dermatitis 63(6):357–363PubMedCrossRefGoogle Scholar
  2. Aalto-Korte K, Suuronen K, Kuuliala O, Henriks-Eckerman ML, Jolanki R (2012) Occupational contact allergy to monomeric isocyanates. Contact Dermatitis 67(2):78–88PubMedCrossRefGoogle Scholar
  3. Anonymous (1996) Thermosetting plastics. Statue Book of the Swedish National Board of Occupational Safety and Health. AFS 1996:4Google Scholar
  4. Anonymous (2001) TA: concise international chemical assessment document (CICAD) PG:25 p YR:2001 IP: VI:27Google Scholar
  5. Baur X, Marek W, Ammon J et al (1994) Respiratory and other hazards of isocyanates. Int Arch Occup Environ Health 66(3):141–152PubMedCrossRefGoogle Scholar
  6. Bello D, Herrick CA, Smith TJ et al (2007) Skin exposure to isocyanates: reasons for concern. Environ Health Perspect 115(3):328–335PubMedCrossRefGoogle Scholar
  7. Bello D, Redlich CA, Stowe MH et al (2008) Skin exposure to aliphatic polyisocyanates in the auto body repair and refinishing industry: II. A quantitative assessment. Ann Occup Hyg 52(2):117–124PubMedGoogle Scholar
  8. Belsito DV (2003) Common shoe allergens undetected by commercial patch-testing kits: dithiodimorpholine and isocyanates. Am J Contact Dermat 14(2):95–96PubMedCrossRefGoogle Scholar
  9. Bertrand JP, Wantz JM, Heintz P et al (1984) Pathologic lies e l'utilisation des isocyanates dans les mines de charles. Arch Mal Prof Med Travail Sécur Soc 45:3–9Google Scholar
  10. Crespo J, Galan J (1999) Exposure to MDI during the process of insulating buildings with sprayed polyurethane foam. Ann Occup Hyg 43(6):415–419PubMedCrossRefGoogle Scholar
  11. Donovan JC, Kudla I, DeKoven JG (2009) Rapid development of allergic contact dermatitis from dicyclohexylmethane-4,4′-diisocyanate. Dermatitis 20(4):214–217PubMedCrossRefGoogle Scholar
  12. Emmett EA (1976) Allergic contact dermatitis in polyurethane plastic moulders. J Occup Med 18(12):802–804PubMedCrossRefGoogle Scholar
  13. Engfeldt M, Pontén A (2013) Contact allergy to isocyanates after accidental spillage. Contact Dermatitis 69(2):122–124PubMedCrossRefGoogle Scholar
  14. Engfeldt M, Isaksson M, Zimerson E, Bruze M (2013a) Several cases of work-related allergic contact dermatitis caused by isocyanates at a company manufacturing heat exchangers. Contact Dermatitis 68(3):175–180PubMedCrossRefGoogle Scholar
  15. Engfeldt M, Goossens A, Isaksson M, Zimerson E, Bruze M (2013b) The outcome of 9 years of consecutive patch testing with 4,4′-diaminodiphenylmethane and 4,4′-diphenylmethane diisocyanate. Contact Dermatitis 68(2):98–102PubMedCrossRefGoogle Scholar
  16. Estlander T, Keskinen H, Jolanki R et al (1992) Occupational dermatitis from exposure to polyurethane chemicals. Contact Dermatitis 27(3):161–165PubMedCrossRefGoogle Scholar
  17. Fisher AA (1986) Contact dermatitis. Lea and Febiger, PhiladelphiaGoogle Scholar
  18. Forsberg K, Mansdorf SZ (2007) Quick selection guide to chemical protective clothing. Wiley, HobokenGoogle Scholar
  19. Fregert S (1967) Allergic contact reaction to diphenyl-4,4′-diisocyanate. Contact Dermatitis Newslett 2:17Google Scholar
  20. Frick M, Bjorkner B, Hamnerius N et al (2003a) Allergic contact dermatitis from dicyclohexylmethane-4,4′-diisocyanate. Contact Dermatitis 48(6):305–309PubMedCrossRefGoogle Scholar
  21. Frick M, Isaksson M, Bjorkner B et al (2003b) Occupational allergic contact dermatitis in a company manufacturing boards coated with isocyanate lacquer. Contact Dermatitis 48(5):255–260PubMedCrossRefGoogle Scholar
  22. Frick M, Zimerson E, Karlsson D et al (2004) Poor correlation between stated and found concentrations of diphenylmethane-4,4′-diisocyanate (4,4'-MDI) in petrolatum patch-test preparations. Contact Dermatitis 51(2):73–78PubMedCrossRefGoogle Scholar
  23. Frick-Engfeldt M, Zimerson E, Karlsson D et al (2005) Chemical analysis of 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate and isophorone diisocyanate in petrolatum patch-test preparations. Dermatitis 16(3):130–135PubMedGoogle Scholar
  24. Frick-Engfeldt M, Zimerson E, Karlsson D et al (2007) Is it possible to improve the patch-test diagnostics for isocyanates? A stability study of petrolatum preparations of diphenylmethane-4,4′-diisocyanate and polymeric diphenylmethane diisocyanate. Contact Dermatitis 56(1):27–34PubMedCrossRefGoogle Scholar
  25. Goossens A, Detienne T, Bruze M (2002) Occupational allergic contact dermatitis caused by isocyanates. Contact Dermatitis 47(5):304–308PubMedCrossRefGoogle Scholar
  26. Hamada H, Bruze M, Zimerson E, Isaksson M, Engfeldt M (2017a) Sensitization and cross-reactivity patterns of contact allergy to diisocyanates and corresponding amines: investigation of diphenylmethane-4,4′-diisocyanate, diphenylmethane-4,4′-diamine, dicyclohexylmethane-4,4′-diisocyanate, and dicylohexylmethane-4,4′-diamine. Contact Dermatitis 77(4):231–241PubMedPubMedCentralCrossRefGoogle Scholar
  27. Hamada H, Zimerson E, Bruze M, Isaksson M, Engfeldt M (2017b) Sensitizing capacities and cross-reactivity patterns of some diisocyanates and amines using the guinea-pig maximization test. Can p-phenylenediamine be used as a marker for diisocyanate contact allergy? Open Derm J 11:87–97CrossRefGoogle Scholar
  28. Helaskoski E, Suojalehto H, Kuuliala O, Aalto-Korte K (2015) Prick testing with chemicals in the diagnosis of occupational contact urticaria and respiratory diseases. Contact Dermatitis 72(1):20–32PubMedCrossRefGoogle Scholar
  29. Henriks-Eckerman ML, Mäkelä E (2015) A new penetration test method: protection efficiency of glove and clothing materials against diphenylmethane diisocyanate (MDI). Ann Occup Hyg 59(2):221–231PubMedGoogle Scholar
  30. Isaksson M, Engfeldt M, Zimerson E, Bruze M (2013) Contact allergy to two synthetic plastics in an orthopaedic engineer. Contact Dermatitis 69(4):257–259PubMedCrossRefGoogle Scholar
  31. Israeli R, Smirnov V, Sculsky M (1981) Intoxication due to dicyclohexyl-methane-4-4′ diisocyanate exposure (author’s transl). Int Arch Occup Environ Health 48(2):179–184PubMedCrossRefGoogle Scholar
  32. Kanerva L, Lähteenmäki MT, Estlander T et al (1989) Allergic contact dermatitis from isocyanates. In: Frosch PJ, Dooms-Goossens A, Lachapelle J-M, Rycroft RJG, Scheper RJ (eds) Current topics in contact dermatitis. Springer, Berlin/Heidelberg/New York, pp 368–373CrossRefGoogle Scholar
  33. Kanerva L, Jolanki R, Estlander T (1997) 10 years of patch testing with the (meth)acrylate series. Contact Dermatitis 37(6):255–258PubMedCrossRefGoogle Scholar
  34. Kanerva L, Grenquist-Norden B, Piirila P (1999) Occupational IgE-mediated contact urticaria from diphenylmethane-4,4-diisocyanate (MDI). Contact Dermatitis 41(1):50–51CrossRefGoogle Scholar
  35. Karlsson D, Dalene M, Skarping G et al (2001) Determination of isocyanic acid in air. J Environ Monit 3(4):432–436PubMedCrossRefGoogle Scholar
  36. Karol MH, Kramarik JA (1996) Phenyl isocyanate is a potent chemical sensitizer. Toxicol Lett 89(2):139–146PubMedCrossRefGoogle Scholar
  37. Kerre S (2008) Allergic contact dermatitis to DMDI in an office application. Contact Dermatitis 58(5):313–314PubMedCrossRefGoogle Scholar
  38. Kieć-Świerczyńska M, Swierczyńska-Machura D, Chomiczewska-Skóra D, Nowakowska-Świrta E, Kręcisz B (2014) Occupational allergic and irritant contact dermatitis in workers exposed to polyurethane foam. Int J Occup Med Environ Health 27(2):196–205PubMedCrossRefGoogle Scholar
  39. Klees JE, Ott MG (1999) Diisocyanates in polyurethane plastics applications. Occup Med 14(4):759–776PubMedGoogle Scholar
  40. Larsen TH, Gregersen P, Jemec GB (2001) Skin irritation and exposure to diisocyanates in orthopedic nurses working with soft casts. Am J Contact Dermat 12(4):211–214PubMedGoogle Scholar
  41. Liippo J, Lammintausta K (2008) Contact sensitization to 4,4′-diaminodiphenylmethane and to isocyanates among general dermatology patients. Contact Dermatitis 59(2):109–114PubMedCrossRefGoogle Scholar
  42. Lodi A, Mancini LL, Pozzi M et al (1993) Occupational airborne allergic contact dermatitis in parquet layers. Contact Dermatitis 29(5):281–282PubMedCrossRefGoogle Scholar
  43. Malten KE (1984) Dermatological problems with synthetic resins and plastics in glues. Part I. Derm Beruf Umwelt 32(3):81–86PubMedGoogle Scholar
  44. Mancuso G, Reggiani M, Berdondini RM (1996) Occupational dermatitis in shoemakers. Contact Dermatitis 34(1):17–22PubMedPubMedCentralCrossRefGoogle Scholar
  45. Marand A, Dahlin J, Karlsson D et al (2004) Determination of technical grade isocyanates used in the production of polyurethane plastics. J Environ Monit 6(7):606–614PubMedCrossRefGoogle Scholar
  46. Militello G, Sasseville D, Ditre C et al (2004) Allergic contact dermatitis from isocyanates among sculptors. Dermatitis 15(3):150–153PubMedCrossRefGoogle Scholar
  47. Morgan CJ, Haworth AE (2003) Allergic contact dermatitis from 1,6-hexamethylene diisocyanate in a domestic setting. Contact Dermatitis 48(4):224PubMedCrossRefGoogle Scholar
  48. Rattray NJ, Botham PA, Hext PM et al (1994) Induction of respiratory hypersensitivity to diphenylmethane-4,4′-diisocyanate (MDI) in guinea pigs. Influence of route of exposure. Toxicology 88(1–3):15–30PubMedCrossRefGoogle Scholar
  49. Rothe A (1976) Occupational dermatoses due to polyurethane drugs. Berufsdermatosen 24:7–24PubMedGoogle Scholar
  50. Rothe A (1995) Gefahren bei der Injektion von Rissen in Betonbauwerk. Bauhinia 2:72–75Google Scholar
  51. Schroder C, Uter W, Schwanitz HJ (1999) Occupational allergic contact dermatitis, partly airborne, due to isocyanates and epoxy resin. Contact Dermatitis 41(2):117–118PubMedCrossRefGoogle Scholar
  52. Stingeni L, Bellini V, Lisi P (2008) Occupational airborne contact urticaria and asthma: simultaneous immediate and delayed allergy to diphenylmethane-4,4′-diisocyanate. Contact Dermatitis 58(2):112–113CrossRefGoogle Scholar
  53. Tait CP, Delaney TA (1999) Reactions causing reactions: allergic contact dermatitis to an isocyanate metabolite but not to the parent compound. Australas J Dermatol 40(2):116–117PubMedCrossRefGoogle Scholar
  54. Tanaka K, Takeoka A, Nishimura F et al (1987) Contact sensitivity induced in mice by methylene bisphenyl diisocyanate. Contact Dermatitis 17(4):199–204PubMedCrossRefGoogle Scholar
  55. Thompson T, Belsito DV (1997) Allergic contact dermatitis from a diisocyanate in wool processing. Contact Dermatitis 37(5):239PubMedCrossRefGoogle Scholar
  56. Thorne PS, Hillebrand JA, Lewis GR et al (1987) Contact sensitivity by diisocyanates: potencies and cross-reactivities. Toxicol Appl Pharmacol 87(1):155–165PubMedCrossRefGoogle Scholar
  57. Thorpe D (2002) Isocyanates. In: Lee S (ed) The huntsman polyurethanes book, 1st edn. Wiley, New York, pp 63–88Google Scholar
  58. Ulrich H (2001) Diisocyanates. In: Ulrich H (ed) Chemistry and technology of isocyanates. Wiley, Chichester/NewYork/Brisbane/Toronto/Singapore, pp 315–467Google Scholar
  59. Uter W, Lessmann H, Geier J et al (2002) The spectrum of allergic (cross-)sensitivity in clinical patch testing with ‘para amino’ compounds. Allergy 57(4):319–322PubMedCrossRefGoogle Scholar
  60. Vaichere E, Lefevre A, Choudat D et al (1986) Allergies cutanées et respiratoires liées a la confection de “platres” orthopédiques à base de résines synthétique. Arch Mal Prof Méd Travail Sécur Soc 47:35–36Google Scholar
  61. Valks R, Conde-Salazar L, Barrantes OL (2003) Occupational allergic contact urticaria and asthma from diphenylmethane-4,4′-diisocyanatae. Contact Dermatitis 49(3):166–167CrossRefGoogle Scholar
  62. White IR, Stewart JR, Rycroft RJ (1983) Allergic contact dermatitis from an organic di-isocyanate. Contact Dermatitis 9(4):300–303PubMedCrossRefGoogle Scholar
  63. Wilkinson SM, Cartwright PH, Armitage J et al (1991) Allergic contact dermatitis from 1,6-diisocyanatohexane in an anti-pill finish. Contact Dermatitis 25(2):94–96PubMedCrossRefGoogle Scholar
  64. Zimmerman R (2002) Catalysts. In: Lee S (ed) The huntsman polyurethanes book, 1st edn. Wiley, New York, pp 137–150Google Scholar
  65. Zissu D, Binet S, Limasset JC (1998) Cutaneous sensitization to some polyisocyanate prepolymers in guinea pigs. Contact Dermatitis 39(5):248–251PubMedCrossRefGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2020

Authors and Affiliations

  1. 1.Occupational MedicineFinnish Institute of Occupational HealthHelsinkiFinland
  2. 2.Department of Occupational and Environmental DermatologySkåne University Hospital (SUS), Lund UniversityMalmöSweden
  3. 3.Terveystalo Healthcare OyjHelsinkiFinland
  4. 4.Section of Dermatology/Control of Hypersensitivity DiseasesFinnish Institute of Occupational Health (FIOH)HelsinkiFinland

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