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ia Dermatitis from Synthetic Resins and Waxes* LOUIS SCHWARTZ. M.D., F.A.P.H.A. Set.tor Surgeon, U. S. Public Health Service, New York, N. Y. DERMATITIS ir. the manufacture For -.aking plastics, such a telephone re- of natural resins and from their ceivers, pipe stems, push buttons, ear phones' use has been reported by numerous obcigar holders, bottle caps, butiuns, inks' servers,1 but dermatitis in the manu artificial teeth plates, ornaments, bracelets' earrings. ' facture of synthetic resins and from For making varnishes, flexible coatings I I 1 ' I their use has not been frequently re floor finishes. . 'j ported 2 or studied. The iprincipal synthetic resins manu factured in the United States are: For making cements, wall boards, gears dishes, watir containers, insulators rubber compounds, and numerous other objects and for electrical insulations on condensers and * j I 1. Phenol-formaldehyde resins, sold under wires. various trade name:, such as Bakehte, Durite, Durez, Resinox, Indur, etc. 2. Urea-formaldehyde resins, sold under The most important of the resins, from a standpoint of volume used and trade names such as Beetle, Plaskon, Unite skin hazards, are the phenol-formalde 3. Coumaron resin, made from coal tar hyde, the urea-formaldehyde and the residue coumaron resins. 4. Ester gums, which are natural resins, such as Rosin, Dammar and Copal, in which the acid of the resin has been combined and PHENOL-FORMAIDEHYDE RESINS neutralized with glycerol These are made in two principal S. The glyptal resins, which are a com bination of glycerol and an organic acid, such as phthalic and malleic adds 6. The vinyl resins, which are vinyl esters, ethers or halides combined with phenol, formaldehyde and hexamethylenetetramine 7. Furfural resins, obtained from combining varieties: 1. The cast resin, which is finished in the factory 2. The molding resin, which is sold to molding companies and completed in the molding process furfural with phenol (furfural obtained from corn cobs by treating with H2SO^ and frac tional distillation) Phenol or cresol, formaldehyde and ammonia are mixed in proper propor 8. Chlorinated resins, obtained by chlo tions in a kettle and heated a sufficient rinating various oils and balsams length of time and to the proper 9. Chlorinated waxes, obtained by chlo rinating mineral oils, paraffin, naphthalene, di-phenyl, etc. temperature.3 They combine and are_. ___ drawn out of the kettle in the form of a syrup. This is run into pans and These resins are used for many allowed to cool, when it sohdifies. purposes: This is known as " first stage resin," or " alpha resin." The pans are then Read before the Industrial Hygiene Section of the American Public Health Association at the Sixty*fourth Annual Meeting in Milwaukee, Wis., October S, 1933. heated, the resin re-melted and poured into suitable molds. These a-e placed in large, mineral oil filled carriers and j [586] UOUOii HARTOLDMON0021578 ?J6 Vol. 26 Dermatitis 587 placed into curing ovens, where they it may contain, but if this is not care are heated and go through the so-called fully done, dermatitis may result from beta and gamma stages into the com too much alkali. pleted cast resin. The skin hazards to the users of After being taken out of the oven, these cast resins are practically nil, be the resin is taken out of the molds and cause when they are finished no phenol oil, and washed with soap and water or formaldehyde are given off from and dried, and it is then ready to be them. carved or lathed or bored into whatever The molding resin is made up in object is desired. numerous qualities, containing different During the course of these opera proportions of phenol and formalde reones, inks, lets, i tions, formaldehyde is given off and the air of the room is strong with the odor of it, unless adequate forced ventilation is emploved. Workers in the rooms who are sensitive to formaldehyde may hyde and ammonia. It is carried to tire alpha stage or beta stage, and then is ground, heated, and mixed with ground wood, zinc stearate, soap, dyes, and hexamethylenetetramine in a mix ungs, develop dermatitis of the face, neck, mill. From this mill it is discharged and arms, as well as of the covered on to conveyors, where it is air cooled. ars, parts where there is friction, such as While cooling, it forms lumps which >ber the belt line, the ankle at the shoe top, are ground in mills to proper sizes fit and and and the wrist at the cuff line. for molding. The workers engaged in The oil used in the curing process mixing, grinding, and packing the mold :ns, and tldethe | dissolves out of the resin some of the phenol and formaldehyde and, if used over and over again, it can contain considerable quantities of these sub stances. One sample which was' ing resin are all exposed to the dust of the irritating chemicals it contains, as well as to the formaldehyde which it gives off, the odor of which permeates the rooms. Dermatitis is a frequent analyzed after it came out of the ovens occurrence in this occupation, especially contained 2 per cent each of phenol if the rooms are not properly ventilated and formaldehyde. The men handling to draw off dust, and if the machines pal this oil have their clothes splashed with and jobs where there is dust are not it and at times suffer not only from oil properly protected by suction hoods. the acne and dermatitis of the legs, thighs, In a factory employing about 400 and other parts touched by the oil- workers, where no great care was taken to the soaked clothing, but also from derma to allay and prevent dust, 27 cases of titis due to the irritating action of the dermatitis occurred in 8 months. Patch phenol and the formaldehyde contained tests performed on 10 cases with various nd jn the oil. The eruption in these cases resins, hexa, 4 per cent solution of .or is usually a diffuse erythematous base formaldehyde, and 2 per cent solution ient on which there are scattered the papules of phenol, showed that hypersensitivity pet- and pustules of an oil folliculitis. to hexamethylenetetramine and to are Jhe girls washing the oil off the formaldehyde was the cause of 80 per n of fesin, with soap and water, may also cent of the occupational dermatitis in and develop dermatitis of the hands and this plant. Hypersensitivity to phenol ,es. n, i) arms from the oil and also from the was also found, but in lesser degree than strong soap solution with which their to formaldehyde and hexa. hen -ed ;ed ,tnd ands are constantly wet. In many actories, the oil is treated with sodium -'Irate after, each baking in order to neutralize the phenol and formaldehyde The actual cause of dermatitis from exposure to hexa and formaldehyde is the same. They both finally decompose in the presence of warmth and moisture _v r <*' -W-Vr r-jsse-y .'*> "Aeiu* 588 American Journal of Public Health June,1936 into formic acid, which is the real skin irritant. Dermatitis from the dust of the mold ing resins usually occurs at the points of friction with the clothing--the wrist, the belt line, the shoe tops and the collar line. It may, however, occur on the covered parts when the dust penetrates the clothing. The skin around the eyelids may also be af fected. The eruption consist?, usually, of scattered papules and vesicles on an erythematous base. Jt gets well if the worker stays away from work, and returns again if he re sumes work. In this factory, the dermatitis was more prevalent in the winter because the workers did not take showers in cold weather after their shift, whereas in the summer they were more likely to do so. UREA-FORMALDEHYDE RESINS These are made by mixing urea and formaldehyde in a kettle. No heat is required, the reaction generating its own heat. A syrupy liquid results. This is mixed with bleached sulphite pulp, under heat and pressure, and dried in tray dryers. It is then mixed in a ball mill with pigments, zinc stearate, and a small amount of hexamethylenetetramine, about per cent. It is then screened, and is ready for shipment. Minute amounts (frac tions of 1 per cent) of other ingredients are added to different brands. The manufacture of the ureaformaldehyde resins on a commercial scale is more recent than that of the phenol-formaldehyde resins, hence the two factories studied had more modern machinery and safety appliances than the phenol-formaldehyde resin fac tories. There were adequate ventila tion facilities and good facilities for dust prevention. As a result, among 190 employees over a period of over 2 years, there had occurred only 4 cases of dermatitis. They were all due to hypersensitivity to formaldehyd Two chemists in the experimental laboratory of these plants were hyper sensitive to formaldehyde and suffered with dermatitis when exposed to jt One of them exposed his forearm jn my presence to the mouth of an open bottle of formalin and almost jm. mediately an erythema developed 0n the exposed skin. In a molding plant in Ohio empl0yjn,, about 300 workers, where phenol- formaldehyde and urea-formaldehvde resins are used, 26 cases of dermatitis occurred in the first 10 months of 1934 and in a molding plant in Pennsyl vania half of the workers developed dermatitis in the hot months of 1935, The process of molding is practically the same for all the resins. The powder is placed in a " pill machine " and pressed into proper shapes for the molds. The pills are then placed into the molds where they are subjected to heat and pressure which shapes and hardens them. During the molding process gases are given off from the molds and the odor of formaldehyde is strong in the room and irritates the nose and throat and eyes of those unaccustomed to it. There is an excess of powder in the molds which flows out during the mold ing process and is only partially " cured." This is called the " flash." When the molds are opened the flash is cleaned off the molds and filed off the molded object. Patch tests with the resins with which they worked were performed in the winter on 2 active cases of derma titis, and 10 workers who had recovered from dermatitis, gave only 2 positive reactions, 1 to the phenol-formaldehyde and 1 to the urea-formaldehyde resin. The examination and history of the 10 cases who had dermatitis but were free of it when the patch tests were made, showed that 2 had dermatephytosis and 1 probably had ptyriasis rosea. It ' 1 GOOD- HARTOLDMON0021580 V June, 1936 aldehyde. 'vperinierual > "pre hvpeN d suffered -ed to it, forearm in f an open most im. veloped on employing e phenolrmaldehvde f dermatitis hs of 1934, n Pennsyls developed of 1935. practically The powde'r chine " and es for the ' placed into subjected to shapes and .he molding iff from the formaldehyde irritates the es of those owder in the mg the mo!ddy partially the "flash!" led the flash and filed off resins with performed in ses of dermahad recovered ly 2 positive -formaldehyde dehyde resin, ory of the 10 but were free .s were made, rmatophytosis asis rosea. It 'ol. 26 Dermatitis 589 js probable that a considerable number In the urea-formaldehyde resin, hexa of the 26 cases reported in 1934 were acts as a stabilizer to prevent the resin not of industrial origin. from hardening before it is molded. The same plant was visited in The ventilating and dust prevention August, 1935. Twelve cases of derma conditions in the molding plants were titis had occurred since the first visit poor. There were no suction hoods 9 months before. This time 9 workers over the mending machines. The suc who had dermatitis during this period tion hood over the " pill machine " was were patched with suspected samples out of order. There was only window of urea-formaldehyde and phenol- ventilation in the workrooms, and formaldehyde resins, as well as with wash-ups or showers after work were hexamethylenetetramine. Four showed not compulsory. With proper dust no reactions after 24 hours to any of allaying facilities, such as forced venti the 7 patches applied. Five showed lation, suction hoods, wet sweeping of positive reactions to one or more of floors after each shift, compulsory the resins, and of these 5, 3 showed showers, protective clothing and oint positive reactions to hexamethylene ments, the incidence of dermatitis in tetramine. this plant could be decreased. Two of the 4 cases who showed no Dermatitis may occur in users of reaction had eruptions at the time the molded phenol-formaldehyde and urea- patches were applied. One was a case formaldehyde resin wares if the hexa of dermatophytosis and the other an is not all combined. Theoretically, it eczema which dated back to childhood. is all combined in the completed resin, The weather was cold (less than 70) but practically (as in some imperfectly during the period the patches were on. cured pieces or pieces in which there and this may have a bearing on the was too much hexa in the molding reactions, because, of the 26 cases re compound to be completely taken up), ported in 1934, 18 had occurred during there may be a sufficient amount re periods of hot weather in May, June, maining to cause dermatitis in hyper July, and August. sensitive people. The same thing may There can be little doubt that a be true of the phenol, if not com considerable percentage of the derma pletely combined. titis in this plant was of occupational Dermatitis has been reported as due origin. to contact with finished resin products, That hexamethylenetetramine is a such as dermatitis of the ear from major causative factor, is shown by the telephone receivers, and of the hands fact that most of the cases occurred in from varnishes. workers handling the phenol-formalde In order to show that a dermatitis hyde resin, which contains more of it may have been caused by contact with than does the urea-formaldehyde resin. a resin, it must be established that: Hexa, which was extensively used in the rubber industry as an accelerator and caused dermatitis, has now been 1. The dermatitis followed contact with the resin 2. That portion of the skin which came almost entirely displaced by other accelerators. It is necessary in certain phenol-formaldehyde molding resins in order to furnish the necessary amount of formaldehyde and ammonia required in contact with the resin was first affected 3. A powdered portion of the suspected resin placed on the clear skin near the eruption in the form of a patch test, pives a positive reaction if left on 24-96 hours to go through the gamma stage--or to To determine the actual chemical in completion. the resin which caused the dermatitis, fl $ iBaj -*Uf /* -Vfjr HARTOLDMON0021581 590 American Journal of Public Health June, ioj6 the nature and chemical composition of the resin must be determined, and patch tests performed on the patient with each of the chemicals composing the resin in order to determine to which of them the patient is hypersensitive. The patches of the chemicals should be in such dilutions as will not cause reaction on the normal skin if allowed to remain on for 24 hours. A 2 per cent aqueous solution of phenol can remain on the normal skin in the form of a patch test, for 24 hours without causing a reaction. A 4 per cent solution of formalde hyde can remain on the normal skin, in the form of a patch test, for 24 hours without causing a reaction. Powdered hexamethylenetetramine may remain on the normal skin, in the form of a patch test, for 24 hours without causing a reaction. Powdered coumaron resin may re main on the normal skin, in the form of a patch test, for 24 hours without causing a reaction. Coumaron resin is used in varnishes, adhesives, rubber, paint, chewing gum, lacquers, paper and fabric sizing, print ing inks, and waterproofing. It is made from the crude coal tar distillate, which comes off between 150 and 200 C. This distillate is re-distilled to re move impurities such as benzol, toluol, zylol, naphthalene and tar acids--and a sharply fractionated naphtha is obtained. The naphtha is dried in lead-lined or stone-ware receptacles by treatment with Hi-SO*, in the propor tion of 3 to 5 parts per 1,000. After standing a while, the acid is drawn off and fresh H2SO< is added slowly and agitated until 3 to 5 per cent of acid is added. The kettle is kept cold during the reaction with brine-cooled refrigeration. After the reaction takes place, the mixture is allowed to stand until the tar and sludge settle. They are then removed and the remaining oil js pumped to a neutralizing tank and treated with caustic soda to destroy the remaining acid. The oil is tjje^ washed with water to remove the soluble matter, and it is allowed again to settle and the water is removed. The oil is now distilled and the solvent naphtha is distilled off and the naphthalene is removed by live steam. After this, there remains a heavy 0j| boiling at 320-330 C., which is re moved from the resin. COUMARON RESiNS There are no skin hazards, outside of acid and alkali burns, in these opera tions, because they are totally en closed. No skin lesions were found in a large plant and the medical records for a number of years showed no cases of dermatitis. Dermatitis has occurred from cou maron resin in vanish which was used on heddle frames in a cotton mill. The skin on the forearms of the weavers was struck continuously by the moving heddle frames and some developed dermatitis. Patch tests showed that they were sensitive to chlorinated ceresin and coumaron resin in the varnish. The varnish grades of cou maron resin, especially the darker resins, may contain sulphuric acids re sulting from the sulphuric acid treat ments, if they are not carefully pre pared, and it is these acids that cause dermatitis. SYNTHETIC WAXES The principal synthetic waxes manu factured in this country are chloro naphthalenes and the chlero diphenyls. They are both used for practically the same purposes--as electric insulators on condensers, as insulators on electric wires, in paints, varnishes, and lacquers, and as oil in transformers. The chlorinated naphthalenes are made by passing chlorine through UOUOb i`l______ Jj J_. HART OLDMON0021582 rv?` TH Junc, 1936 ye! 26 Dermatitis 591 remaining oil . Kmhzing tank and hthalene and replacing of the parts, the shoulders, and the belt-line, n"jj ,,en atoms with chlorine. One and even on the penis. The lesions on c sda to d 7,, K"' m . ,to remove tij u ls aHowed again more of the hydrogen atoms can replaced, forming mono, di, tri, up oer chloro naphthalene, in which 8 *f the hydrogen atoms are replaced with the skin resemble acne. They begin as small, pale, elevated papules, many having no openings in them. They develop into hard cyst-like elevations Uef is removed ^hlorinej the formula being C10Clt,. under the skin, some of which go distilled and 'the -yhe more chlorine, the more solid is on to suppuration, forming boils. Some ^l^d off and the die material. of the lesions also occur at the mouth ved b}' llve steam. jn making chlorinated diphenyls, it of the follicles and resemble the mains a heavy oil j jj first necessary to manufacture comedones and pustules of acne vul- Which is re. in. i diphenyl, CaoH1(. This is manufac- garis. tured bv passing benzol, CcH0, through Jn addition to these skin lesions, RESINS molten lead, at a temperature of about symptoms of systemic poisoning have 800 F., where 2 molecules of benzol occurred among workers inhaling these n hazards, outside combine to form 1 molecule of diphenyl, fumes. Those working with the chloro rns, in these opera- 1 hydrogen being set free. diphenyls have complained of digestive are totally en- I Diphenvl is a solid, crystalline-like disturbances, burning of the eyc-s, im- sions were 'found substance. This is melted in closed potence and hematuria. The latter and the medical f cylinders and chlorine is bubbled symptom developed among a number - of years showed s. ' through, replacing the hydrogen. One of men making amino diphenyl, which | or more of the hydrogen atoms can be is used in the manufacture of a rubber curred from couh which was used cotton mill. The replaced, forming mono chloro diphenyl, antioxidant. Cases of death from yellow di chloro diphenyl, up lo deca chloro atrophy of the liver have been rediphenvl, C^CIjo. Hydrochloric acid ported among workers exposed to the s the weavers Iy by the moving is a by-product of this reaction. The fumes of the chloro naphthalenes. chloro diphenyls are liquid or semi- Patch tests performed with Halowax some developed -sts showed that to chlorinated solid, up to the hexa chloro diphenyl, and with the chloro diphenyls have Nonochloro diphenyl, CjoHCiu, sold yielded negative results. The skin I under the trade name of Arachlor, is lesions probably result from the ,n resin in the i grades of coudly the darker dphuric acids rehuric acid treatU carefully preacids that cause j used as an insulator for automobile mechanical plugging up of the follicles 1 electric wires and in condensers, and of the skin with the waxes as the fumes * also as a de-lusterer of rayon. solidify on the skin.* The chlorine j In the manufacture of the chloro present in the waxes may have an ! diphenyls, the workers-are exposed to irritating effect on the plugged follicles j a benzol hazard when the diphenyl is and cause suppuration. made, as well as to a hazard from the inhalation of the fumes of diphenyl. prevention The workers engaged in chlorinating i. The protection of the workers from the WAXES tic waxes manua try are chloro :hlero diphenyls, r practically the the diphenvl, especially that part ofirritating chemicals that compose the resins and j the ope1 ration where the crudje Aa rachlori_i Twoaxdeos f^rom ththce prreosciensss asnhdouwldaxebes tothtaeUmvseelvne.s. j is being re-distilled to remove impun- closcd If this is not p05Sibie, hoods'with ties, are affected with an acne-like con- suction exhaust should be so placed over I dition of the skin. This also occurs open processes that dust and fumes are pulled ?ctric insulators 1 tors on electric es, and lacquers, lers. phthalenes are lorine through / in workers exposed to the fumes of the awa>' from lhe worker and out of thc room- 1 chloro naphthalenes, or Halowax. The i have recently seen the wife and fumes of these compounds cause acne child of a worker who had developed on the face and neck and may comedones and pustules from contact with 1 . . ,, , , , 'bis work clothes which were saturated with penetrate the clothes and cause acne- haIowax and which he was accuslomed to like lesions to develop on the covered wear at home. . L. S. ' ' ' ,1 i } j i | | | s | r|i |j Is || S '1 .{ ;| .S >| ; . . _____ J . 0000V 1 twf:/........... ' ... HARTOLDMON0021583 5^2 American Journal of Public Health Jnc,i936 2. Thv workrooms themselves should be ventilated by intake and exhaust fans to remove dust and fumes. 3. The floors, walls, and ceilings should be washed down at frequent intervals to keep them free of dust. 4. Two lockers should be furnished to each worker. One for his street clothes and one for his work clothes. The lockers for street clothes and work clothes should be in sepa rate rooms, with the shower baths between the locker rooms. The worker coming to work enters the locker room for the street clothes, takes them off, and puts them in the locker and goes into the locker room where his clothes are kept and dons them. From this room he goes to the workrooms through a connecting door. At the end of hi? shift, he goes through this door to the work clothes locker room, takes off his work clothes and leaves them on the floor or bench to be washed and then goes to the shower baths and bathes and dries. Then he goes to the street clothes locker room, puts on his clothes and goes out of the door leading to the street. It has been estimated at one plant where such a system was insti tuted that 6 cents a day per worker will take care of furnishing clean work clothes each day. 5. New workers who are hypersensitive, but have only mild eruptions, should be given protective ointments and clothing and kept at work for about 3 or 4 weeks with the hope that they will develop an immunity 0, become " hardened." If this does not occur they should be taken off the job. * 6. New applicants for jobs should be care, fully examined for skin diseases and those found to have them should not be employed 7. There should be periodic medical ex. amination of workers to detect cases of dermatitis and workers in chlorinated naphthalenes and diphenyls should he periodically examined tor symptoms 01 systemic poisoning. 8. Laws should be passed making it corn- pulsory for factories where there are skin hazards to adopt these measures. REFERENCES 1. Siemens, H. \V. Dermatitis Caused by Ad. hesives. Munchen. mcd. Wchnschr., Aug. 7, 192j p. 1333. ' Unna, J\, Jr, Waster Dermatitis. Arch. Dermal. Sr Svph., Sept. 2S, 1926. C.L.I. Congress Number p. 85. ' Reinhauer, L. S. Resin Dermatitis. Report of Case. J.A.M.A.* July 7, 1923. p. 13. Manouvrier, A. Cancer from Resin. Ann. i'hyi. pubtniuc ct mcd. legate, XLV, 1856. Stein, Emii. Professional Dermatosis in GLm Makers. ft'ien. hlin. Wchr.schr., 16:447, 1904. 2. Biumenthal, F., and JaSe, K. Eczema Caused by Bakeiile Varnish. l.AM.A.,94:375(Feb. 1), 1930. Eller, J. J. Ear Photie Dermatitis. Arch. Dermal. & Syph., 22:268 (Aug.), 1930. 3. Eliis, Carieton. Synthetic Resins and Their Plastics. The Chemical Catalog Co., Inc., N'en York, 1923. . A.I.C.P. Guide for Public Health Nurses A GUIDE jor Public Health Nurses of Educational Nursing and has been published by the New York City subjected to the criticism of outstand Association for Improving the Condiing cardiologists. tion of the Poor, is a unique publica Similar guides covering syphilis, tion. A systematic description of child development, and tuberculosis cardiac conditions, for the benefit of have recently been revised and, although public health nurses and a guide to the intended for the nursing staff of the care which they can give patients has A.I.C.P,, they will readily be of in recently been prepared by the Bureau terest to a wider circle. OOOOtl yd- 2* PiCri unnecess; death am personal the nece brought manner direction financial, program is essent to make technics guide m provide with an and ser of the public h tunities insure public 1: There " set-up educatic in diffe Certain veloped periodic or new The im of hea' * Read tioo of t the Sixty* October $ iffiW HARTOLDMON0021584