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Allergic contact dermatitis  the most common allergens

Allergic contact dermatitis  the most common allergens. Riitta Jolanki, D.Tech. (Chem.Eng.), Docent Senior Research Scientist, Dermatotoxicologist Finnish Institute of Occupational Health (FIOH) Department of Occupational Medicine Section of Dermatology riitta.jolanki@ttl.fi.

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Allergic contact dermatitis  the most common allergens

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  1. Allergic contact dermatitis the most common allergens Riitta Jolanki, D.Tech. (Chem.Eng.), Docent Senior Research Scientist, Dermatotoxicologist Finnish Institute of Occupational Health (FIOH) Department of Occupational Medicine Section of Dermatology riitta.jolanki@ttl.fi

  2. Most common causes of allergic contact dermatitis • rubber chemicals, e.g. accelerators and antioxidants • plastic chemicals • epoxy and acrylic compounds, phenol-formaldehyde resins • metals and their compounds • nickel, cobalt, chromium compounds • gold, mercury • formaldehyde and other antimicrobials • formaldehyde, formaldehyde releasers • isothiazolinones, dibromo dicyanobutane • glutaraldehyde • colophony

  3. Rubber and rubber chemicals

  4. Occupational allergic contact dermatitis by cause in 1990-96 (N = 2 647 cases) Rubber chemicals 26% Plastic chemicals 21% Metals (Ni, Cr, Co, Hg, Au) 15% Antimicrobials 10% Others 28%

  5. natural rubber latex isoprene synthetic rubber isoprene nitrile neoprene or chloroprene butyl styrenebutadiene accelerators thiuram mix and mercapto mix component thioureas, dithiocarbamates antioxidants PPD-mix components (IPPD, CPPD, DPPD) vulcanizers retarders plasticizers filling agents, dyes Rubber + RUBBER POLYMER RUBBER CHEMICALS

  6. Exposure to rubber chemicals • Occupational • rubber manufacture • rubber gloves (> 80% of cases) • rubber boots, rubber grips of tools, cable materials, tires, etc. • Clothing • shoes, boots, socks, stockings, waistbands, etc. • Health care • tubes, bandages, catheters, etc. • Condoms

  7. Allergic rubber dermatitis • 12% of all occupational dermatoses are caused by rubber and rubber chemicals • Allergic contact dermatitis (70% of occupational rubber dermatoses) • due to delayed allergic reaction • rubber chemicals in natural rubber and in synthetic rubber (nitrile, neoprene, etc.) • Contact urticaria / protein contact dermatitis (30% of occupational rubber dermatoses) • due to immediate allergic reaction • proteins in natural rubber latex (NRL)

  8. Incidence rates of occupational contact urticaria caused by natural rubber latex (1991-1996, cases/100,000 worker years) • Dental assistants 118 • Dentists 60 • Physicians 39 • Nurses 22 • Laboratory assistants 10 • Cleaners 5 • ALL OCCUPATIONS 2

  9. Occupational contact urticaria caused by natural rubber latex (NRL) proteins • An occupational skin disease caused mostly by protective gloves used by health care workers • Dental assistants and dentists are at highest risk • The risk of cleaners is not very high despite frequent use of protective NRL gloves

  10. Plastic chemicals

  11. Occupational allergic contactdermatitisby cause in 1990-96 (N = 2 647 cases) rubber chemicals 26% plastic chemicals 21% metals (Ni, Cr, Co, Hg, Au) 15% antimicrobials 10% others 28%

  12. Finished plastic materials are mixtures • Polymer molecules (e.g. PVC) • may contain remnants of raw material (e.g., monomers) and additives used in polymerization process • Additives (e.g., phthalates)

  13. Sensitizing plastic chemicals • Uncured plastic materials, and handling of resins or resin-based products, such as two-component paints and glues • raw materials (monomers) • synthetic resins (prepolymers), e.g., epoxy resins • hardeners • rective diluents • accelerators, catalysts, etc. • Finished plastic products • remnants of monomers, synthetic resins, hardeners, etc. • inert additives (plastisizers, dyes, etc.) • chemicals released during working the plastic material • chemicals released during decomposition by high temperature, moisture, etc.

  14. Contact allergy caused by finished plastic products • Uncommon • May develop after prolonged or repeated skin contact (e.g., using of plastic gloves)

  15. Occupational allergic contact dermatitis from plastic chemicalsin 1990-96 (N = 557 cases) Epoxy resin compounds 250 cases Acrylates and methacrylates 135 cases Formaldehyde-based resins 109 cases Other plastic chemicals 63 cases

  16. Epoxy resin system • Epoxy resin • Hardener • Reactive diluents • Other additives epoxy resin compounds

  17. Two-component epoxy resin products • Epoxy resin • Hardener  (e.g. polyamines) • Reactive diluents • Additives • Additives

  18. One-component epoxy resin products • Epoxy resin • Latent hardener + heat (e.g. phthalic anhydrides) • Reactive diluent • Additives

  19. DGEBA epoxy resin • About 75 % of the epoxy resins used worldwide are of DGEBA type • Reaction product of bisphenol-A and epichlorohydrin  DGEBA (MW 340) and larger molecules (up to over MW 8000) • DGEBA (MW 340) is the strongest allergen O C H C H 2 Epoxy group

  20. Liquid epoxy resin • Contains mostly sensitizing DGEBA molecules (MW 340) Solid epoxy resin • Contains low amounts of sensitizing DGEBA molecules (MW 340)

  21. Properties possessed by epoxy resins • Easy cure • High adhesive strength • High electrical insulation • Good resistance against water, chemicals, corrosion, heat and abrasion • Low shrinkage • Expensive

  22. Use of epoxy resins • Two-component paints and other coatings • Two-component glues • Electrical insulation materials • Manufacture of glass-fiber (sizing) • Manufacture of sporting goods, e.g. skis • Concrete injection resin (repairing) • Lamination work and prepreg-laminates • Powder paints • Microscopy immersion oil • Nail cosmetics • Medical devices

  23. Occupational allergic contact dermatitis from epoxy resin compounds at FIOHin 1974-95 (N = 182) DGEBA epoxy resins 80% non-DGEBA epoxy resins 9% polyamine hardeners (PA) 23% reactive diluents (RD) 16% simultaneous contact allergy 30%

  24. Epoxy resin compounds • Roughly 1% of the exposed workers in Finland annually develop allergic contact dermatitis

  25. Patch testing • No single chemical alone (i.e. standard DGEBA epoxy resin) can screen for epoxy sensitization • Isolated or simultaneous contact allergies to other epoxy resin compound • polyamine hardeners • reactive diluents • non-DGEBA epoxy resins • New allergens in patients’ own materials

  26. Occupational allergic contact dermatitis from plastic chemicalsin 1990-96 (N = 557 cases) Epoxy resin compounds 250 cases Acrylates and methacrylates 135 cases Formaldehyde-based resins 109 cases Other plastic chemicals 63 cases

  27. Sensitizing acrylic compounds • Methacrylates, e.g., • 2-HEMA (2-hydroxyethyl methacrylate) • TEGDMA (triethylenegkycol dimethacrylate) • MMA (methyl methacrylate) • BIS-GMA (epoxy dimethacrylate) • Acrylates, e.g., • EA (ethyl acrylate) • BIS-GA (epoxy diacrylate) • Cyanoacrylates • ethylcyanoacrylate

  28. Use of (meth)acrylates and cyanoacrylates • Dental composite restorative materials, dental sealants and dental coatings • Manufacture of dentures, bone cements, hearing aids • Anaerobic sealants (Loctite, screw-thread locking) • Instant glues (cyanoacrylates) • UV-reactive inks, printing plates of photoprepolymer type and coatings • Manufacture of circuit board • Nail cosmetics, etc.

  29. Occupations at risk - acrylic compound • Dental nurses • Dentists • Dental technicians • Plumbers • Machinists • Machine and metal product assemblers • Electrical and teletechnical equipment assemblers • Printers • Beauticians

  30. Occupational allergic contact dermatitis from plastic chemicalsin 1990-96 (N = 557 cases) Epoxy resin compounds 250 cases Acrylates and methacrylates 135 cases Formaldehyde-based resins 109 cases Other plastic chemicals 63 cases

  31. Formaldehyde-based resins • Phenol-formaldehyde resins (CA to resin or formaldehyde) • plywood adhesives and glue films • mineral wool resin • mold core resins (metal industry) • neoprene contact adhesives (e.g., leather adhesives) • Urea-formaldehyde resins (CA to formaldehyde) • textile finishing resin • chipboard glues • wood glue industry

  32. Non-occupational exposure to allergenic plastic materials • Two-component paints, lacquers and glues (epoxy compounds), and two-component cements (polyesters) • Contact adhesives (phenol-formaldehyde resin) and instat glues (cyanoacrylate) • Anaerobic acrylic sealants (methacrylates) • Dental fillings and prosthesis (methacrylates) • Clothing (textile resins; formaldehyde) • Nail cosmetics (lacquers, sculptured nail materials and artificial-tip glues; acrylic compounds) • Plastic gloves and spectacle frames (plastisizers)

  33. Metals and metal compounds

  34. Occupational allergic contact dermatitis by cause in 1990-96 (N = 2 647 cases) Rubber chemicals 26% Plastic chemicals 21% Metals (Ni, Cr, Co, Hg, Au) 15% Antimicrobials 10% Others 28%

  35. Metals and metal compounds • Most common sensitizers • nickel • cobalt • chromium compounds • Uncommon sensitizers • gold • mercury

  36. Statistics of the Finnish Institute of Occupational Health (FIOH) • 10–15% of all occupational skin diseases diagnosed in Finland

  37. Skin diseases(FIOH, 1991-1999) • 1893 patients examined • 558 patients diagnosed as having occupational ACD • 78 cases (14.0%) from chromium, nickel and cobalt and their compounds • 2 cases from gold • 2 cases from mercury

  38. Occupational ACD caused by other metals (FIOH) • Gold (2 cases) • dental nurse (gold sanding dust) • metal worker (gold-plating solutions and metallic gold) • Mercury (2 cases) • chemistry student (laboratory chemicals) • dentist (metallic mercury from amalgam)

  39. Chromium compounds • Chromium metal itself does not cause sensitizing • Chrome-tanned leather (water-soluble chromium III compounds) • tanning work; leather gloves; shoes etc. • Cement-based products • in Finland since 1987 the amount of sensitizing hexavalent chromium compounds has been reduced by adding ferrous sulfate to the cement  insoluble non-sensitizing trivalent chromiumI compounds • Chromate-coating solutions • Wood material preserved with chrome salts • Metal-working fluids being in use • Printing inks, paints

  40. Cobalt • Cobalt metal itself and its salts may cause sensitizing • Minor element in nickel compounds • Hard metal (2–39% Co), stellite (60% Co) and metal dusts • Metal salts of electroplating • Metal-working fluids • Accelerator or catalyst of polyester or acrylate resin systems • Dryers in oil-based paints, lacquers, printing inks • Cement and pottery clay • Cobalt dyes • Animal feed enriched with cobalt salts

  41. Nickel • Nickel metal itself and its salts may cause sensitizing • Nickel-containing metals (nickel-silver, copper-nickel, nickel-brass, some white gold alloys), and nickel-plated items • tools, scissors, keys, coins, pens, needles, musical instruments, etc. • Stainless steels such as 18/8 (18% Ni) are generally safe at skin contact • Electrical equipment • Machines • Metal-working fluids

  42. Nickel Directive • From 2001, the EU Nickel Directive limits nickel in items intended for direct and prolonged contact with skin (e.g., jewelry, watches, buttons, and spectacle frames) • The limit value for nickel release is 0.5 µg/cm² per week • Nickel is not restricted in other type of items

  43. Dimethylglyoxime (DMG) test Simple to use Release of nickel ions is indicated by red or pink color (positive DMG test) after rubbing the surface with cotton wool-tipped stick soaked with drop of DMG and ammonia Nickel test

  44. Occupational ACD from metals - concluding remarks • chromium • chrome-tanned leather  • cement-based products  • nickel • contact allergy from non-occupational exposure, and then dermatitis from occupational exposure • cobalt • hard metals, stellite • polyester resin accelerators • occupational ACD from other metals • uncommon

  45. Occupations at risk - nickel, cobalt and chromium • Nickel • platers • electronic industry asseblers • metalworkers • hairdressers • cashiers • Cobalt • metal smelting workers • machinists • Chromium • construction workers • leather tanners • metal workers (chromate-plating)

  46. Formaldehyde and other antimicrobials

  47. Occupational allergic contact dermatitis by cause in 1990-96 (N = 2 647 cases) Rubber chemicals 26% Plastic chemicals 21% Metals (Ni, Cr, Co, Hg, Au) 15% Antimicrobials 10% Others 28%

  48. Most common sensitizing antimicrobials • Formaldehyde • Formaldehyde releasers • Methyl(chloro)isothiazolinones • Methylchloroisothiazolinone (and) Methylisothiazolinone* • Kathon CG • Euxyl K 100 • Dibromo dicyanobutane • Methyldibromo Glutaronitrile* • Euxyl K 400 • Tektamer 38) • Glutaraldehyde *INCI = International Nomenclature of Cosmetic Ingredients

  49. Formaldehyde releasers in cosmetics • Chemical itself and released formaldehyde can cause sensitization • Imidazolidinyl urea* (Germall 115) • Diazolidinyl urea* (Germall II) • 2-Bromo-2-nitropropane-1,3-diol* (Bronopol) • Chloroallylhexaminium chloride (Quaternium-15*, Dowicil 200) • DMDM hydantoin* • Benzylhemiformal* (Akyposept B) • Methenamine* • Tris(hydroxymethyl)nitromethane* *INCI = International Nomenclature of Cosmetic Ingredients

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