ARTICLE
Auteur(s) : Christian
Geraut1, Dominique Tripodi1, Béatrice
Brunet-Courtois1, Fabrice Leray2, Laurent
Geraut1
1Service des maladies professionnelles CHU Nantes,
Hôtel Dieu, 44093 Nantes cedex 1, France
2Laboratoire interrégional de chimie de l’ouest,
Département Prévention Risques Professionnels, CRAM Nantes
accepté le 21 Janvier 2009
Occupational contact dermatoses are the most frequent forms of
contact dermatitis and their occurrence raises concerns of
diagnosis, prevention and prognosis [1, 2]. Plastics in the form of
epoxydic and phenolic resins are handled in very many trades and
sometimes involve epidemic dermatitis in certain companies.
Dermato-allergists are sometimes at a loss faced with the
multiplicity of suspected products and the complexity of the
chemical formulas of the products handled. The allergic dermatoses
to epoxydic and phenolic resins are often the most serious of the
dermatoses to plastics and they remain common, although their
compensation by law in the tables for occupational diseases has
been envisaged for a long time in France.
Occupational and other exposure
Epoxydic and phenoplast resins have excellent mechanical and
chemical qualities and are very commonly used; more than
500,000 tons of epoxy resins are used per annum in the world
(including 45% in coatings) [3].
These resins have exceptional properties of hardness and impact
resistance to heat, water and many chemicals. They also have
important properties of adhesiveness on many materials (metals,
plastic, rubber, wood, glass, ceramics, concrete) and of electric
insulation [4]. Their implementation requires the use of two
components: the hardener is added to the resin just before the
application, reticulation is carried out at ambient or hot
temperatures and the reaction is exothermic. Some of them have more
particular characteristics: fireproofing properties of the
brominated epoxy resins, good electrical insulation of the
epoxy-hydantoin resins, better chemical resistance and performance
with the high temperatures of the epoxy-novolaque resins.
Epoxy resins are mainly used for:
- – adhesives and coatings for the car, electronics and
aeronautics industries, articles of sport (skis, bicycles…), but
also do-it-yourself [5];
- – run resins for the manufacture of models and moulds
(foundry, manufacture of various objects, prostheses, mountings for
glasses, manufacture of resin utensils and capsules;
- – composite materials, very much used in aeronautical
engineering [4, 7, 8] (in a pre-impregnated form with glass fibers,
plastic fabrics in plates, carbon fiber), being used for
manufacture of articles of sport and leisure (tennis rackets, skis,
fishing rods) [6]. Certain epoxydic resins are used for competitive
boats or prototypes, but are becoming more and more widely used
(for example for sailboards) [4];
- – coatings: paintings and varnish, frontage coatings,
road coatings, anti-corrosive protection of metal tanks, cisterns
and swimming pool coatings, manufacture of electronic components
(credit cards, printed circuits), coil insulation and wires,
impermeable concrete for pipes or tanks, protection of the ground
and walls against chemicals, printing inks… [9-11].
Epoxy resins are also used as histological fixers in electronic
microscopy and in immersion oils for optical microscopy
[12-14].
Epidemiology
The majority of epidemiological studies give rates of 1% positivity
to patch tests to epoxy resins in a consulting population for
suspicion of allergic contact eczema [15]. A rate of 0.9% was
found in the study of Schnuch et al. on 40,000 patients [16]. In
Italy, the prevalence of cutaneous allergy to epoxy resins in the
general population (percentage of positive tests to epoxy resins in
593 Italian subjects in good health) was evaluated by Seidenari et
al. [17] at 0.2%.
Epoxy resins are primarily allergens of professional origin.
Studies on populations consulting for suspicion of occupational
dermatitis in general find higher rates of positivity. In a study
carried out on 1559 patients tested for suspicion of allergic
contact eczema, Holness and Nethercott [15] highlighted that 3.7%
had positive tests with epoxy resins. In the group of patients with
occupational contact eczema, 11.7% had positive tests with the
epoxy resins.
Thus, epoxy resins represent the third most frequently
responsible allergen for occupational allergic contact eczemas,
after chromates and the rubber allergens. These allergies to
epoxydic resins are thus by far the first cause of dermatitis among
workers with plastics. The allergies sometimes occur in epidemics
where one finds 40 to 60% of workmen affected [4].
The responsibility of the various types of plastics can be
evaluated through the statistics from the center of occupational
dermatology in Nantes: in 186 cases of occupational dermatitis to
plastics, 108 were due to epoxydic resins, 30 to glass fibres, 21
to acrylates and methacrylates, 15 to phenol-formol resins, 6 to
urea-formol resins, 6 to polyester resins, 2 to polyurethanes and
finally 2 to poly chloroprenes (neoprenes). The epoxy resins thus
represent the first cause of cutaneous allergy to coating materials
[4]. They are also the principal allergen in the electronics
industry [11]. The construction industry is also at risk of allergy
to epoxy resins [9]. In the interpretation of these results, it is
important to note that the positivity of the studied patch test
corresponds only to the epoxy resin of DGEBA type used in the
standard battery.
One can also refer to 62 cases seen in the same department
between 2001 and 2008. The professional gestures, the products
handled and the clinical aspects of the lesions were analyzed with
precision. Results: the building and public works professions lead
with 18 cases, including 13 allergic eczemas to epoxydic resins,
mainly in painters, users of concrete treated with epoxy resin and
construction workers, the remainder corresponding to tank or
plaster manufacturers, with an allergy to a melamine formol resin
in this activity. Nautical construction suffers equally from these
cases, with 18 observations in plastic workers, including 8 cases
of airborne dermatitis from epoxy resins in users of adhesives. The
aircraft industry arrives in 3rd position with 14 cases, including
6 workmen manufacturing special pipes, 4 painters, 2 fitters, 1
caster and 1 aeronautical carpenter allergic to phenol-formol
resins. The other various cases are 3 coil winders manufacturing
electric motors, 2 foundry workmen (with allergy to a resin
melamine-formol), 1 caster, 2 carriage-builder painters, 2 workmen
manufacturing printed circuits, 1 woman allergic to a phenol-formol
resin used to stick shoes and 1 artist allergic to epoxy.
Contact urticarias
The number of cases is considerably lower than that of allergic
contact eczemas. The Finnish statistics of 1990 to 1994 recorded 3
cases of urticaria to anhydrides of acids and 2 cases to epoxy
resins [18].
Clinical demonstrations
Contact dermatoses to these resins do not usually pass unperceived
because of their intensity.
Airborne dermatitis
Clinically, these allergies appear as a contact dermatitis,
evocative by their localization. Indeed, there is a predilection
for: the dorsal face of the fingers and hands, the upper face of
the wrists and forearms, and also the face, with frequent oedema of
the eyelids. This eyelid oedema can be isolated. The lesions are
often very intense and recur with even very fleeting contact with
the allergen (simple passage in a workshop where the epoxy is
used). [4, 19, 20] This is why one speaks about “airborne
dermatitis”, due to dust or resin vapors. The pattern of this
eczema on the uncovered parts of the body is very evocative [21,
22].
These airborne dermatoses are often very acute, pruriginous and
oozing [21, 22]. Jolanski [23] found facial involvement in 60% of
patients having a contact dermatitis to epoxy resins. An isolated
attack on the face is rare but possible. In a sensitized subject,
lesions can appear at the time of only a slight and fleeting
contact with the allergen, such as a passage through a workshop
where epoxy resins are handled [19, 20]; the contact can be
cutaneous, (hands, gloves) or airborne, some compounds being
volatile (reactive thinners, hardeners) [42].
Eczema with localised allergic contact
This aspect is more traditional and the professional forecast is
better. Sometimes, it occurs with only lesions of the hands and
forearms or the forearms alone, at the top of the gloves when there
is an effective wearing of gloves: it should be noted that
molecules of the epoxydic resins can cross react with the rubber
gloves.
Prognosis
Few studies have evaluated the prognosis of cutaneous allergy to
epoxy resins. It is generally favorable after removal of the
allergen, because it is not ubiquitous like chromates or nickel
[24]. Rosen and Freeman [25] showed a cure and/or improvement for
more than 60% of patients having allergic contact eczema to epoxy
resins. Nevertheless, the majority of allergic patients with a form
of airborne dermatitis must change occupation because of the
reappearance of lesions with even tiny quantities of allergens [4,
19, 20].
Irritation dermatitis
Contact with some epoxy resin compounds can give rise to burns, to
ocular reactions with conjunctivitis, and to cutaneous irritations
(erythemato-squamous lesions, more or less cracked) [26]. Glass
fiber dermatitis among plastic workers and the personnel cutting
out printed circuits can be added to the list [4, 11]. Burns have
been described with epichlorhydrine, the aliphatic polyamines (very
alkaline pH) and heated acids. Dicyanodiamide, organic solvents and
TGIC can also be irritating.
The epoxy resins of DGEBA type have an irritating capacity which
decreases with the increase in the molecular weight of the
oligomer. In 843 cases of irritation contact dermatitis at work,
Jolanski [23] reports 5 cases (0.6%) secondary to composite epoxy
resins.
Contact urticaria [23, 27]
There are very acute forms of contact urticarias with certain very
sensitizing modern resins (TGPAP, TGMDA).
Other contact urticarias have been blamed on the following
substances:
- – epoxy resins based on DGEBA;
- – reactive thinners (PGE and CGE);
- – anhydrides of acids (MHHPA, MTHPA, Pa);
- – aliphatic polyamine hardeners (DETA, TEIA).
Other rarer occupational dermatoses
- – Sclerodermatous lesions with erythema, cutaneous
sclerosis and muscular weakness in 6 subjects working with epoxy
resin polymerization. The responsibility for an amine was evoked
[28];
- – Polymorphic erythema [29];
- – Lichenoid dermatitis [30];
Practical tests with the European
or International Standard Battery
Initially, faced with an apparent eczema of allergic nature, there
is recourse in our services to the standard battery of allergens,
including a test entitled “epoxydic resin”. The epoxydic resin in
the standard battery test of allergens which is entitled “epoxydic
resin” corresponds to the diglycidyl ether of bisphenol A [31]
(available at a concentration of 1%).
The chemical formula of this resin: it belongs to the group of
thermohardening plastics i.e. plastics which harden by reticulation
during the reaction of a resin precomposed with a hardener or
catalyst, with an exothermic reaction. The basic component is
epichlorhydrine, having the epoxydic function of binding to
bisphenol A to produce a diglycidylether bisphenol
A [31].
The epoxy resins thus contain at least 2 strongly reactive epoxy
groups, brought by the two epichlorhydrine molecules [32].
For this reason, their chemical name will always include the
“epoxy” term or “glycidyl”. More than 75% of the epoxy resins are
manufactured starting from the polycondensation of epichlorhydrine
with bisphenol A, forming a mixture of monomers of diglycidyl ether
of bisphenol A (DGEBA) with a molecular weight of 340 Dalton
(Da) and oligomers of a higher molecular weight [33].
Value of patch tests included in the standard
battery
Experimental studies in animals highlight that, for the epoxy
resins based on DGEBA, the monomer of 340 Da of molecular weight is
more sensitizing, and that the capacity for sensitizing decreases
with an increase in the molecular weight of oligomers.
Nevertheless, the epoxy resins of high molecular weight contain
sufficient monomers (340 Da) to also involve a risk of sensitizing.
In man, multiple studies show cases of contact allergy to
composites of epoxy resins. Epoxy resins of type DGEBA with a low
molecular weight (< 500) are more sensitizing, mainly the
monomer of 340 Da, which can sensitize accidental contacts, even
afterwards.
Nevertheless, epoxy resins based on DGEBA with a raised
molecular weight are sensitizing because they contain from 0.2 to
15% of monomer 340 Da [33]. Epoxy resins of DGEBA type having a low
molecular weight (350-400 Da) are liquid, with sometimes very high
rates (approximately 90%) of DGEBA monomers, whereas those of
higher molecular weights (> 900 Da) are solid, with lower rates
of DGEBA monomers (up to 15% and more) [31]. Kanerva et al. [34]
investigated 182 patients with an allergic contact eczema to the
epoxy resins over a period of 22 years. 146 patients out of 182
(80%) were allergic to epoxy resins of the DGEBA type; 35/182
patients (approximately 20%) had negative tests with the DGEBA
standard resin epoxy used in the standard battery, but positive
results with other composites of epoxy resins.
It appears obvious that this simple test of the standard battery
is not sufficient in the event of negativity and that the practice
of specialized complementary batteries is essential [35].
Use of specialized batteries
If a patient confirms handling a resin that he qualifies as “epoxy”
(which is already rather precise, most patients are completely
unaware of the composition of the adhesives, varnishes, painting
materials or resins handled, and certain safety information cards,
obtained with great difficulty, being only marked as “epoxydic
resins”), there can be a great number of different substances with
new compounds which appear without decreasing their allergenic
capacity, quite the contrary in fact.
They form glycidylic ethers of a general formula [31-33].
The more the molecular weight is raised, the less the resin is
allergenic. The molecular weight of bisphenol
A diglycidylether is 340, whereas that of the polymer obtained
is at least 624 [36].
Resins available in specialized commercial batteries
Traces of bisphenol A or epichlorhydrine, themselves
potentially sensitizing, [45-47], can persist from where used to
testing with precursors of the diglycidylethers like bisphenol A,
available at a concentration of 1%, bisphenol F, available at a
concentration of 0.25% or epichlorhydrine, available at a
concentration of 0.1%. There does not seem to be a risk of
sensitizing to bisphenol A. In animals, on the other hand,
epichlorhydrine is sensitizing [46]. Epichlorhydrine; 11% of these
products penetrate the dermis after 10 hours in the pig [48].
DGEBF
It is proven that many resins used in industry at the present time
also contain DGEBF (bisphenol F diglycidylether, molecular mass
312) or are made up of only DGEBF, which appears to us another
argument for the epoxy battery “mix” also to contain this
component.
The resin Epikote 862 is an epoxy resin of low viscosity
obtained starting from Bisphenol F and epichlorohydrine. It is used
in construction and various industries like the production of
adhesives, mortars... Ponten and Bruze [37] report a frequency of
allergy to DGEBF slightly higher than that to DGEBA (study of 23
cases of allergy to epoxy resins among 299 patients tested for
suspicion of eczema of allergic contact); Jargot underlines the
increase in the use of the DGEBF in many epoxydic resins [38]. In a
German multicentric study, reactions crossed with DGEBA and DGEBF
were frequently observed [39]. This is available at a concentration
of 0.25%.
Cycloaliphatic epoxy
Among the epoxy resins not based on DGEBA, most frequently positive
are the cycloaliphatic epoxy resins. This epoxydic resin resists
ultraviolet rays well [38]. Its principal use is in the manufacture
of electrical insulators (sleeves, mechanisms, insulators). It is
at the origin of a certain number of cases of allergies [42]. It is
available at a concentration of 0.5%.
Triglycidylisocyanurate
This is sometimes mixed with other resins, in particular in
painting materials or coatings with polyesters where it plays more
the part of hardener than of resin [41]. Allergies crossed with
diaminodiphenylmethane and hydroxyethylmethacrylate are seen [42],
the frequency of these allergies is weak: 3% (6/182) cases of
allergy to TGIC [34]. It is available at a concentration of 0.5%.
Epoxyacrylates
These contain bisphenol A and acrylates, but do not contain
epoxydic groupings. However, they are nevertheless sensitizing,
with the possibility of sensitizing crossed with bisphenol
diglycidylether A (DGEBA) [42]). The most well known resin is
BisGMA (Bisphenol A Glycidyl Methacrylate), used in dentistry.
In a recent study, 85% of subjects allergic to bisGMA also reacted
to DGEBA [43] (available at a concentration of 2%).
Thinners of resins
Jolanki et al. [33] investigated 182 patients with an allergic
contact eczema to epoxy resins over a 22 year period. Allergic
reactions to the thinners represented 29 cases out of 182 (16%).
Half of epoxy resins have added reactive thinners in order to
reduce the viscosity of the resin during use [40].
The reactive thinners contain strong sensitizing chemicals,
mainly phenyl glycidylic ether, cresyle glycidylic ether or
butanediol diglycidylic ether [49-51]. There is no cross reaction
between reactive DGEBA and thinners. On the other hand, cross
reactions are possible between the reactive thinners and the
cycloaliphatic epoxy resins [52].
Allyl- and butyl- glycidyl ether is available at a concentration
of 0.25%. Cresyl glycidyl ether is available at a concentration of
0.25%; isopropylglycidyl ether is not available to our knowledge
[53].
2-Phenyl glycidyl ether (C9H10O2) dilutes reactive epoxy resin.
It forms chemical bonds with the resin during treatment and
accelerates the process. It is available at a concentration of
0.25%.
Trimethylolpropane triglycidylether (C15H25O6). Use: Thinner
used to reduce the viscosity of epoxy resins. Available at a
concentration of 0.25%.
1,6-Hexanediol diglycidylether (C12H22O4). Use: in the
production of epoxy resin-like thinners to decrease viscosity.
Available at a concentration of 0.25%.
1,4-Butanediol diglycidylether (C10H18O4). Available at a
concentration of 0.25%.
Finally it is advisable to indicate that the epoxydic resins are
often mixed with other sensitizing resins which should be tested:
urea-formol or phenol-formol.
Resins not currently available in commercial
batteries
Brominated epoxy
Novolaque glycidylic ethers (which resist heat well) [40].
Dimethylhydantoine epoxies (very effective in their adhesion to
fibres, in particular the new fibres, Kevlar polyparaaramides, and
their resistance to electric arcs) [40].
Other epoxy resins not derived from DGEBA which are also
sensitizing do not appear in the commercial batteries.
Polyfonctional epoxy
These epoxies concern triglycidylic ether derived from
p-amino-phenol (TGPAP) (very resistant to high temperatures) and
from tetraglycidylmethylenedianiline (TGMDA), which has excellent
mechanical and adhesive properties, making it a product very much
used in the aircraft industry.
To be tested, these two products must be preserved in the
freezer and tested in acetone at 20%.
Their formulas are as follows:
In the presence of new resins of unknown or vague composition,
chromatography can be used to highlight the presence of particular
compounds which could be tested.
Hardeners
The hardener, generally an amino, acts on the liquid or paste-like
resin to give the finished plastic. In taking its final form,
passing from a liquid or paste-like state to a solid state, the
molecule becomes more complex with a three-dimensional structure.
The passage of the linear form epoxy resins to their
three-dimensional final structure is carried out thanks to the use
of these hardeners, which allow the formation of bridges between
the linear chains. Hardeners are usually classified into two
principal groups: polyamines and acid anhydrides [31-33, 55-58].
Resin hardeners are often responsible for dermatitis because of
their caustic character, in particular certain amino hardeners,
which then secondarily support a sensitization with the resin epoxy
itself (irritation “prepares the ground” for the allergy).
Polyamine hardeners of low molecular weight are strong
sensitizing agents:
- – Jolanki et al. [44] explored 182 patients with an
allergic contact eczema to epoxy resins over a 22 year period:
42/182 (23%) were allergic to polyamine hardeners.
- – The most commonly used hardeners are the basic
hardeners like triethylenetetramine, (C6H18N4) Available at a
concentration of 0.5%.
- – Diethylenetriamine (C4H13N3). Solvent for the
intermediaries of the organic synthesis of resins and a hardener
for epoxy resins. Available at a concentration of 1%.
- – Triethanolamine, (C6H15NO3). Available at a
concentration of 2%.
- – Hexamethylene tetramine (C6H12N4). Used in the
production of phenolformaldehyde resins. Available at a
concentration of 2%.
- – Ethylenediamine, (C2H10Cl2N2). Available at a
concentration of 1%.
- – Isophoronediamine, (C10H22N2). A common hardener
of epoxy resins [54]. Available at a concentration of 0.1%.
- – Diaminodiphenylmethane, an agent binding in resins
Available at a concentration of 0.5%.
- – Aminophenols, (3 and 4 aminophenols).
m-Xylylenediamine (C6H12N2). Synonym: 1,3-(a) (aminomethyl)
benzene. Use: Intermediary used in the production of epoxy resins
as a hardener. Taking into account the manufacturing process, this
intermediary is not found in the finished product. The handling of
these intermediate agents is carried out only in the professional
environment. Available at a concentration of 0.1%.
- – 3 (Dimethylamino) propylamine. Available at a
concentration of 1%.
The polyamine hardeners most frequently positive are the MDA,
the DETA and IPDA [55, 56].
The positivity of certain tests does not necessarily mean an
allergy to composites of the epoxy resins. Thus, sensitizing with
ethylenediamine can be due to an exposure to cutting fluids,
cosmetics or rubber, which contain it. In the same way, sensitizing
to diaminodiphenylmethane can correspond to an allergy to an amine
as a para (for example: para-phenylenediamine) [58].
The other non-polyamine hardeners are much more rarely
implicated in allergic contact eczema: some rare cases with
anhydride dodecenyisuccinic, anhydride methylhexahydrophtalic and
dicyanodiamide have occurred [56].
Allergic reactions to the other components are rarer:
- – In the study by Jolanski; 1 case in 182 was of allergy
to hardeners containing phtalic anhydride [55, 56], available at a
concentration of 0.5%.
Other additivies [57]
Plasticizing: potentially sensitizing, but seldom observed as such:
- – Dimethyl phthalate; available at a concentration of
5%;
- – Di-n-butylphtalate; available at a concentration of
5%, classified as toxic for reproduction, category 2;
- – Dietthylphthalate; available at a concentration of
5%;
- – Ethylhexylphthalate; available at a concentration of
5%, classified as toxic for reproduction, category 2;
- – Triphenylphosphate; available at a concentration of
5%;
- – Tricresylphosphate; available at a concentration of
5%.
Solvents: there is often irritation dermititis to resin solvents
which precede or accompany allergic reactions. Indeed, resins are
frequently diluted in solvents where the solubilizing action of the
coating lipoacide of the skin is more or less marked [59]. Toluene
is frequently found, (classified toxic for reproduction, category
3) and xylene, ethylglycol, isopropanol, carbinol, ethyl or methyl
acetates, acetonitrile, tetrahydrofuranne, methylisobutylketone, or
methylethylketone, not forgetting acetone, which is caustic unless
frequent hand washing is performed [60].
The manufacture of these plastics involves using extenders (pine
oils, tar), products to render it more flexible, and additives. The
additives can be mineral (silica, carbon fibers, classified by the
International Cancer Research Center as cancerogenic category 1, in
the forms of silica crystalline, quartz, talc, graphite, glass
fibers, pulverulent metals…) or others (wood powders, tar, pitch,
bituminizers…).
Prepared tests with the products handled
Many examples could be reported in which one can note that the
tests are negative with the standard batteries but positive with
the resins handled, these last tests proving completely relevant
since suppression of contact with the resins implicated results in
a total cure.
The practice of tests carried out with products
brought by the patients
This seems to remain the only satisfactory technique in the most
difficult cases. JM Lachappelle rightly proposes the technique of
half-open tests, which consist in applying products brought by the
patient directly to the skin, after preparation and dilution to a
non-irritating concentration, letting them dry out and then
covering them only when dry, with the adhesive support of the patch
test.
Can solid plastic be tested?
Certain solid materials can, although rarely, contain monomers or
oligomers of non-polymerized epoxy resins and involve an allergic
contact eczema. Jolanki et al. [42] recommend testing them after
extraction with acetone. This type of test is usually useless.
Nevertheless, it should be known that in the polymer obtained, 5 to
25% of the monomer can persist for several hours in a free state
after polymerization, just like the basic components such as
epichlorhydrine (less than 1 ppm in general and always less than 10
ppm) or bisphenol A. Before testing the professional products to
which the patient is exposed, it is necessary to know their
composition, in particular to avoid caustic burns [8]. These tests
can expose the patient to the risk of sensitizing, induced by the
epoxy resins which are powerful allergens [61].
In rare cases there is no reaction to the various types of
resins used and the hardener tested separately: however the subject
is certain that the lesions appear only with work; then the two
mixed products (resin + hardener) should be tested. An allergic
reaction then sometimes appears, probably related to the presence
of intermediate amines which are formed at the time of the
reaction. This test must be made with prudence to avoid any caustic
effect. In the same way, one should not test the pure hardener, as
is too often seen, with the risk of very strong caustic reactions
[62].
Must one consider an “epoxy-mix” test?
The tests carried out with the products handled and which prove to
be positive, are not undertaken with a pure chemical but with a
mixture of various ingredients, each potentially able to induce the
allergic reaction.
Dermatitis due to glass fibers
Many epoxydic or phenolic resins are created on a support which
ensures their solidity, namely a kind of lattice of glass fibers.
The dermatoses due to glass fibers are due to a phenomenon of
mechanical irritation by fibers of a diameter greater than 5
micrometers, which penetrate by friction through the skin and the
dermis and cause a histamine release by mast cells. The lesions,
with a type of tiny red papules, prevail on the exposed parts of
the body (hands, wrists and forearms). Cases of diffuse erythemas
of the trunk have been observed, often worsened by scratching, and
having a slightly purpuric aspect, and others, less classically
described, on the face. There can be lesions with a type of
conjunctivitis [59].
The aspect can, more rarely, be that of an eczema nummulaire, an
appearance of folliculitis, a worsening of telangiectases,
urticaria or linear cuttings [59].
The open-test is an examination carried out on the upper
internal face of the forearm. It consists of lightly rubbing the
skin with glass fiber. When it is positive, this test causes the
appearance of papules either immediately (in 15 minutes, the time
of histamine release), or with delayed-action (approximately an
hour after the test). When clinical symptomatology appears, the
professional gestures are a sufficiently evocative diagnosis, the
open-test is not essential. In fact, generally, the cutaneous
phenomenon disappears in 2 to 3 days, and only 5 to 10% of subjects
continue to be troubled. These often have impressive scratching
lesions [63, 64].
Advice for individual preventive measures includes wearing
gloves, fully covering clothing, (closed at the wrists, the ankles
and neck, quite distinct from their town clothes), and taking of
showers without friction following exposure. However, the main
effort needs to be to design workplaces provided with effective
aspiration systems and with a water curtain making it possible to
avoid the dissemination of dust in the processing atmosphere.
Dermatitis to phenolic resins
Still called “phenol-formol resins” or more generally “phenoplast
resins”, these are obtained by polycondensation of phenols (but
also of cresol, resorcin), with formaldehyde (or furfuraldehyde).
They can be used as adhesives or to form certain laminates with
carbon fibers (masts). These resins are very sensitizing and the
allergy can be related to the presence of formaldehyde (formol),
furfuraldehyde (produced for testing respectively at 1% and 3% in
water), or which had a corrosive and sometimes sensitizing phenolic
monomer, in particular paratertiaire butylphenol resin (PTBP),
which is very sensitizing and at the origin of depigmentations [59,
65].
The “plastics” battery includes the following allergens:
- – Similar phenoplast resins and their components;
- – Phenol formaldehyde resin 1%, Resorcin formaldehyde
resin 5%, Paratertiaire butylphenol formaldehyde1%, Paratertiaire
butylcatechol 1%;
- – Resins. Toluene sulphonamide formaldehyde resin
10%;
- – Components: 2-4-dinitrophenol 1%, Hydroquinone 1%,
N-dimethyl-p-toluidine 2%, Resorcinol monobenzoate 1%.
The powder resins polymerize thanks to basic catalyst actions
(hexamethylene tetramine, irritating and sensitizing) and the
adhesive or resin liquids are polymerized by the addition of acids
and hardeners irritating for the skin, like the hydrochloric acid
or paratoluenesulfonic acid.
In this reaction amines intervene, which are able to sensitize
(triethylamine, ethylamine, methylamine, triethylene diamine,
etc.). One also frequently adds pigments (cobalt or chromium salts
or oxides) which are able to sensitize.
Very often, the dermato-allergist does not know the precise
chemical composition of these secondary reagents, whose secrecy is
kept by the manufacturer, and requires the help of a chemistry
laboratory. In all cases, it is advisable to carry out the patch
tests with a very diluted product (0.5 to 2% in water).
As for other plastics, various solvents and thinners can have an
irritating effect on the skin (toluene, xylenes, chlorinated
solvents…).
Prevention in plastic workers
The company doctor must be informed so that he can, as far as
possible, make the necessary prevention provisions, (collective
prevention, in particular, better dust and vapor extraction,
protection against aerosols, choices among caustic hardeners, work
surfaces covered with disposable paper, automation, humidification
to avoid glass fiber dust…) [66, 67]. The wearing of protective
gloves does not protect from resin or hardener vapors and thus does
not prevent recurrence on exposed parts of the body, which it is
necessary to protect with a cream. Rubber gloves do not protect
effectively from the components of resin, which end up penetrating
through the gloves. One thus needs gloves made out of plastic and
adapted to the resin, or special gloves [68].
It is necessary to insist on the gestures to be avoided or
abandoned: not applying resins and their hardeners to naked hands,
not washing the hands with solvents or to rubbing skin covered with
glass fiber. Emollient creams make it possible for the skin to
recover the water lost at the time of the chemical aggressions.
Medical Prevention [3] relies on early treatment with
dermocorticoides, applied in effective amounts (i.e. weak), on
emollient creams for the symptomatic treatment of irritative
contact dermatitis, and associated with the suppression of the
allergen and irritating factors. It is essential to inform the
patient of all the sources (professional and other) of contact with
the epoxy resin compounds, in order to avoid the repetition or the
perpetuation of the problem, which risks evolving to a persisting
autonomous eczema.
The study of Castelain et al. [7] clearly shows the
effectiveness of prevention measurements (at the same time
technical and medical) in the aviation sector. The evaluation of
cases of allergy to epoxy resins over two periods (1955-1965 and
1981-1990) after the installation of a prevention scheme, shows a
fall from 19 to 3 cases of allergy to epoxy resins.
Compensation
In order to benefit from recognition as an occupational disease,
contact dermatitis can be declared in France [3]:
- – in the general list of occupational diseases, Social
security n° 51 “Occupational diseases caused by epoxydic resins and
their components”, for epoxy resins and their components;
- – under article n° 15 (a) “Allergic mechanisms affected
by the aromatic amines, their salts…” for the amino aromatic
ones;
- – under article n° 49 “Affections caused by aliphatic
and alicyclique amines” for the aliphatic amines. Irritative
dermatitis with aromatic amines can be also declared under article
n°15.
Conclusion
These plastic dermatoses are dominated by allergies to epoxydic
resins whose chemical formulas change regularly with progress of
research, and which do not take into account their allergenic
capacity, which is certainly not the principal reason for this
research. On the contrary, it seems that the allergenic capacity of
certain new compounds is worse than that of traditional epoxy with
appearance of previously unknown urticarias of contact.
The dermato-allergist sometimes has difficulty finding the
composition of the various plastics handled by a user, who often
has very little idea of the exact nature of products which he uses.
The commercial batteries are often behind on technical progress and
must thus be supplemented by tests developed by the
dermato-allergist himself, with the assistance of chemists and
while taking care to avoid caustic effects by using suitable
dilutions.
Acknowledgements
Financial support: none. Conflict of interest: none.
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