Document rpwJMLGy20mbq6aVJkdNEqvQ0

VINYL CHLORIDE MONOMER PROBLEM IN JAPAN July, 1974 JAPANESE PVC ASSOCIATION COPIED BY MCA CMA 016297 CA9UE ADDHSSS FVCASSN TOKYO JAPANESE PVC ASSOCIATION 1-1, 2-CHOME, UCHISAIWAI-CHO, CHIYODA-KU, TOKYO, JAPAN TELEPHOHeS TOKYO (208) SAfl VCM/PVC SITUATION IN JAPAll I. VCM/PVC Industry In Japan the VCH/PVC industry commenced the commercial production in 1949 -- although small production has been made during the Second World 'War -- and since then the industry developed smoothly and especially very fast of late years. The production of PVC in Japan has become the second largest in the world coming after your production. PVC ha3 superior properties and is sold at reasonable price. Thus it is used for producing containers, wrapping film, electric insulation, pipes and a wide range of products. It has become an indispensable material for improv ing the people's daily livings. The manufactures of VCM/PVC are all members of the Japanese PVC Associa tion listed as on annex. The production and shipment to date are as shown on annex table. The workers employed for the production of VCJt/PVC is roughly numbered at 2,200, and those engaged in the molding and processing business counts to about 500,000. II. Problem of 7CM Exposure 1. At the occasion of the 16th International Congress on Occupational Health, held at Tokyo in the autumn of 1969, reports were made by the American and Italian doctors on acroosteolysis of employees at VCM/PVC plants. And the cause of the disease was named as VCM. CMA 01^298 In reply to proposal by ths workforce, the Japanese PVC Association took immediate actions by conducting a radical survey putting emphasis on cleaning work in the polymerization reactors, and prepared a Guide to Vinyl Chloride Crernsion Manual for Safe Handling and Use, Subsequently, each member company of the Association has adopted up until today prevention measures respectively in accordance with this handling manual and has been executing a special medical examination of employees. Except 2 workers who were suspected of acroosteolysis at the 2nd medical survey in 1972, we have not found so far the above specific disease. 2. At the end of January 1974, a report from USA of a possible connection between angiosarcoma of liver -- a rare form of cancer, -- of VCM/FVC manufactur ing employees, and occupational health and safety for exposures to VCM has caused a worldwide discussion. As soon as obtained such information, the Association discussed on what action the industry should take. As a conclusion, though liver angiosarcoma ha3 not been found so far in Japan, the Association decided to cope with the suspected problem positively understanding that not only the health and safety of the employees, but the trend of the question is a critical problem which may threaten the existence of the Japanese PVC industry, and will greatly affect the national economy. 3. Actions The actions took to date by the Association are as follows* 3-l) The Labor Health Committee was organized inside the Japanese PVC Association as for discussing this VCM problem, and also Medical Group and Technical Group were established as the sub-committees. 5-2) Through uiscussion by the Labor Haalth Committee an Emergency Temporarv Standard on Occupational Health and Safety for Exposures to VCM was published, and the following items were recommended to the member companies by the President of the Association. CMA 016 a) VCM concentration shall be maintained not more than 50 ppm under work environments where employees will possibly be exposed to in pro duction of VOl/PVC. b) In any work environment where exposure exceeds the 50 ppm, employees shall be provided, and shall use, protective devices. The members are enforcing the measures in their plant as soon as possible. Further, a Temporary Standard for Medical Surveillance was prepared and medical screening is under way in accordance to this Standard. Surveillance is conducted parallel to this on the death cause of the employees including the retired workers. 4. The historical VCM concentration in atmosphere of the Japanese VCM/PVC plants are estimated as follows: - 1955 1955 - 1965 1965 - 1970 1970 - 1975 at present maximum " 1000 ppm 100 - 500 ppm 50 - 200 ppm 50 - 100 ppm 50 ppm In connection with the cleaning work in a polymerisation reactor where a high level exposure to VCM is suspected, there are very few workers appointed specially for such cleaning heretofore. In Japan high-presure water-jet clean ing system is applied, and the time required for staying in the kettle for poly cleaning is now extremely short. The water-jet cleaning system has been adopted in Japan from 1965 and in 1970 -- the year after an information was introduced into Japan that acroosteolysis patient existed amoung poly-cleaners -- every plant applied the system. In the early period each time the polymerization is terminated the kettle wa3 water-jet cleaned, and then hand 3crapir.g wa3 made by the poly-cleaner. At present due to development on the system, one hand scraping for a very short time is required only once for several batches of polymerization. CMA 016300 III. Problem of VCM Migration In May 1973 7CM migration problem of PVC liquor bottle spread into Japan from the United States. The Japan hygienic PVC Association -- composed of 300 companies who are from PVC resin manufacturers to the food producers -- performed analysis on liquor from the same bottle and detected no such migration. Further investigations were made on food wrappings beside PVC bottle. It was made clear that such problem will not occur by correct molding and by improved production process. At present such actions are taken by all the manufacturers- --r CMA 016301 CMA 0 1 6 3 0 2 7ear 1954 1955 1956 1957 1953 1959 I960 1961 1962 1963 1964 1965 19 66 1967 1968 1969 1970 1971 1972 1973 Production and Shipment of PVC Annex 2 Production (motrie tons) 21,960 32,210 55,852 108,905 91,160 179,247 257,561 307,526 303,144 348,061 473,376 482,992 489,664 711,099 941,778 1,047,078 1,162,058 1,019,269 1,079,248 1,313,098 Shipment (metric tons) 19,672 33,651 55,954 91,379 103,055 180,880 254,221 293,336 309,191 353,244 473,363 466,614 501,588 752,306 935,833 1,046,775 1, 137,758 1,063,198 1,125,002 1,315,915 End- Use Percentage ('/) Rigid Products Plasticised Electric Products Induration Flooring, and wise. 18.3 36.3 38.6 40. 5 33. 1 37-0 41. 1 43.3 41. 5 44.3 47.4 40.8 45-0 49-5 51.1 49-3 48.8 48.9 50.8 55.2 62.0 46.3 44.0 42.3 38.5 37.0 3 5-8 35-5 38.1 38. 1 , 34. 5 34-0 34.0 30.9 29.3 27-8 27-4 26.8 26. 6 26.1 18.1 14.2 15-4 14.7 14.9 14. 1 14. 1 14.0 12.4 11-5 12.0 11.1 11.0 13.1 12.3 12. 7 12. 1 10. 6 9.9 9-8 Export 1.6 3.2 2.0 2.5 M. 1 11-9 9.0 7-2 8.0 6* 1 6.1 14.1 10.0 6.5 {* 3 10. 2 11.7 13.7 12.7 8.9 Source : Japanese PVC Association Guide to Vinyl Chloride Operation Manual for Safe Handling and Use September 1970 Japanese PVC Association Contents: 1. Properties 1.1 Important physical and chemical properties 1.2 Toxicity 2. Engineering Control of VCM and PVC Manufacturing System 2.1 Production 2.2 Facilities 2.3 Instalation of cleaning system for polymerization reactor 3uch as high-pressure water jet cleaner 2.4 Ventilating in polymerization reactor 2.5 Ventilation of VCM handling area 3. Control for Handling and Use 3.1 Transportation 3.2 Storage 3.3 Application 3.4 Cleaning operation of polymerization kettle 3.5 Leak and procedures 3.6 Other operation notifications 3.7 First aid 3.8 Education and training 4. Medical Screaning 5. Other Protection Procedures fZ -- CM* 016303 3.k Cleaning procedure in a polymerization kettle (1) Whenever the manhole of a polymerization kettle is opened, make sure not to inhale residual vinyl chloride monomer (VCM) gas since it flows out. For example, transfer slurry simultaneously when the manhole is opened or start exhauster immediately- after opening of the manhole. (2) Before entering the reactor, wash the inside by high pressure water. (3) Turn off pipe lines of the reactor and disconnect motors without fail and lock switch ' board in the presence of a responsible person. Put up a sign of "Operator in the reactor". (lk) Remove completely residual VCM gas in the reactor by water substitution or exhauster etc. to decrease gas concentration in the bottom part of the inside reactor below the permitted concentra tion. In case exhauster is used, since the relation between residual VCM gas concentration in the reactor and degassing time is shown in the following figure, set up a degassing time 1.5 times as long as the required time for decreasing sufficiently the VCM concentra tion to arrive at equilibrium condition. 13-- -- CMA 016304 Start of ventilation --J Start of kettle entry Ventilation Relation between degassing time and VCM concentration in the reactor Measure VCM concentration by one of the following methods . (a) Kitagawa type detector (b) Interference refractometry (c) Gaschromatography (5) While cleaning of the reactor, always introduce large quantity of fresh air into the reactor to maintain VCM concentration below the permitted level. Also observe carefully to maintain it. (6) Use the following protective devices. Store the protective devices in a specified storing place where a clear sign is put on to that effect. Check them periodically, at least once a week. (a ) Pro t ec tive glasses (b) Protective gloves (c) Prot ec tive clothing suitable to pr event skin contact such as long sleeve clothe f4 C"A 016305 (7) Employees engaged in reactor cleaning should wash face and hands after cleaning work and take bath or shower at the end of the shift. CMA 016306 k. Medical screening The following points shall be checked up as to employees engaged in polymerization or other operation which may expose them to VCM. (1) At time of initial employment and once every year or more often (as for X-ray examination, once every two years) Periodical examination shall be made to find whether the below mentioned items are detected or not. (a) Headache, head heaviness, tiredness, gastroenteric disorder, skin alteration, paralysis of fingers, pain and indisposition, arthritis, Raynaud syndrome and deformity or shortening of fingers. (b) Urobilinogen and bilirubin in urine (c) Semiluman marginal irregularity, transverse deformation, color-button phalanx detected by X-ray examination. (2) As a result of the above check-up, if subjective or objective abnormality is detected and a doctor finds them necessary, the following tests shall be applied. (a) Liver function test (serum test on GOT and GPT) (b) physical examination Note: Results of screening will be classified and health care will be followed accordingly. In the meantime, plant doctors shall take care of them. -- /e CMA 01630 Table 3 VCM in PVC compound ( ppm ) VCM in PVC battle ( ppm ) Residue percent ( fa ) No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 1.7 2.8 15 21 2.8 12.5 23 1.3 2.4 12 15a'5 2.4 8.8 17 77 86 80 74 86 70 74 average 78 fa Control method for VCM migration into PVC bottled food at compounding process PVC blow bottles are made by PVC bottle manufacturers with PVC powder compound supplied by PVC compounders. And, food is filled into the PVC bottles at the end. From the experiment results shown in the previous sections, if the ratio A ( weight of contents versus weight of PVC bottle ) is fixed, in compounding process, we will be able to predict and control the VCM migration amount into food from PVC bottle. In the following equation. : A : ratio of weight of contents / weight of bottle k : VCM residue ( fa ) from compounding process to bottle blowing process. f : VCM migration rate from PVC bottle into bottled food. 25 ~~~ CMA 016308 Residual VCM amount in PVC compound = XxA k. 100 x 100 Accordingly, to keep x - value below O.OJ ppm ; In case of spirits, supposing A=10, k=80?5r f=30$ are fixed ; O.Op x 10 -d--==' 2 ppm 0.8 x 0.3 * ( maximum VCM amount in compound ) In this supposition, A=1Q is rather particular case. It is thought in general A=20 should be more common. 26 -- CMA 016309 VCM Migration from PVC Bottles June 1, 1974 Japan Hygienic PVC Association Experiment \ 1* VCM migration into alcoholic solvents with use of PYC resins containing different levels of zesidual )cM, PVC bottles containing various levels of residual VCM ( l"*ca. 20 ppm ) were moulded. \ Filled with 20 $ and 50 $ alcoholic solutions intoythe PVC bottles, and the filled bottels were kept at 50*c for 4 weeks. \\ And then, the quantity of migrated VCM into the alcoholic solutions and the migration rate of VCM were estimated from the following VCM analysis data : Table 1 describes the data of 50$ alcoholic solution, at 50*c, for 4 weeks. Table 1 bottle weigth bottle volume VCM in bottle VCM in solution VCM migration ( gram ) ( ml ) ( ppm ) ( ppm ) rate from bottle ($) No. 1 .2 No. 3 No. 4 No. 5 No. 6 No. 7 20 20 27.6 20 13.3 13.3 20 200 200 400 200 100 100 200 1.1 1.6 2.8 3.5 8.8 19.0 23.0 0.02 0.03 0.07 0.07 0.40 0.82 0.56 20 19 37 20 32 30 24 ( Averag 26$ ) Table 2 describes the VCM migration rates into 20$ alcoholic solution and sake from PVC bottles containing various levels of residual VCM by the same manner as in Table 1 . 23-- -- CM/l 016310 Tania solution's. bottle weigth bottle volume VCM in bottle VCM in solution VCM migration ( gram ) ( ml ) ( Ppm ) rate from bottle ( $ ) 20$ alcohol n \\ sake 13.3 13.3 13.3 13.3 13.3 13.3 100 100 100 100 100 100 2.4 8.8 19.0 2.4 8.8 19.0 0.05 0.21 0.48 0.05 0.19 0.48 15 18 19 16 16 19 ( Average 17 $ ) Prom Table 1 and 2, in thinking of Japanese spirits, as the tested condition ( at 50*c, for 4 weeks ) is thought to have equivalent extraction effect to one year storage at room temperature, picking up the data of 50$ alcohol solution in Table 1 out of the above data for the sake of more safe, and it was thought the average 26$ migration rate should be reasonable for the time being. 2. Residual VCM content in PVC compound and bottle It can be estimated the VCM migration amount into spirits from PVC bottles in referring Table 1. In addition, to know of VCM befaviour on the line from PVC compounding process to bottle production, we analized VCM content in bottles made from PVC compounds cotaining various levels of residual VCM ranging from 1.7 to 23 ppm. Table 3 shows the VCM analysis results, and the VCM transferrance into bottles was found average 78 $. Accordingly, residual VCM in PVC bottles appeared to be predominantly determined at the stage of compounding process. 24 CMA 016311 n:i nX 1 Juno loth, 1974 Sanitation of PVC food containers In thu United States some VCM wus dotocted in whisky packed in PVC containers some Lime' ago. Subsequently PDA announced a ban against l'VC containers used for ulcoholic beverages as a provisional measure in May, 1973. We, Japan Hygienic PVC Association, followed to the PDA announcement wi Lliou t fTUi ing behind. As the results of our VCM analysis in SAKE, ardent spirits, and other relating foods, VCM was not detected in any case. On .the other hand, as the results of our research on tracing the VCM migration to its origin, it has appeared that by severly control on production process and by improvement of producion equipment suspectable VCM migration into food can be minimized to non-detection. As the consequence, it was consented to observe voluntarily its production method in the industries. And, it is being proceeded to form a system that no detectable VCM bo remaining in food thereafter. Japan Hygienic PVC Association zt-- -- CMA 016312 Japan Hygienic PYC Association. its organization ------- CHAIRMAN BOARD OF DIRECTORS PROPAGATION OF RECOMMENDATION COMMITTEE Propagation of the recommended standard. Checking of the products in market . PUBLIC RELATION COMMITTEE Propagation of the Safety of PVC products standardized in accordance with positive list. Issuing of the Associations report and technical service report, etc. RESEARCH COMMITTEE Research of shipping statics as plastic food packaging materials. TECHNICAL COMMITTEE Reseaching of the regulation related to the recommended P.L. Collection and arrangement of technical report at home and abroad. COMMITTEE ON BUSINESS AFFAIRS Negotiation and liaison with the related official Agencies and referenced Associations. Management of General affairs ' 3 ------22 -- CMA 01631 Prsas Release Brief history of occupational health and safety for exposures to vinyl chloride monomer June 12, 1574 In the autumn of 1969 at the l6th International Congress on Occupational Health held in Tokyo, doctors from the U.S. and Italy reported acroosteolysis of workers of PVC manufacture. The Association immediately conducted a medical survey putting emphasis on cleaning work in a polymeri zation reactor and prepared a handling manual of vinyl chloride monomer under instruction from and the guidance of the Japanese Ministry of Labor. Subsequently, each member company of the Associa tion has adopted up until today prevention measures respectively in accordance with this handling manual and has been executing a special medical examination of employees. Except 2 workers who were suspected of acroosteolysis at the 2nd medical survey in 1971, we have not found so far the above specific desease. Following to a report in the end of January by | the B.F. Goodrich Chemical Co. in the U.S. of a possible connection between angiosarcoma of liver, a rare form of liver cancer, of PVC manufacturing employees and VCM exposures, occupational health and safety for exposures to VCM was caused worldwide discussion. In the U.S. Federal Resister dated April 5, 197^, Department of Labor billed a notice as an emergency temporary standard for exposures to VCM arising in process of VCM production, polymer production and molding. CMA 016314 \ (1) The temporary emergency standard requires that no employee exposure is permitted to levels of VCM concentration under work environments above a 50 ppm ceiling limit and (2) requires personal protective measures and equipment where exposure is greater than the 50 ppm level. As soon as obtained such information, the Association discussed what action the industry should take. As a con clusion, though liver angiosarcoma has not been found so far by a medical examination in Japan, we organized Labor Health Committee in this April to cope with the suspected problem positively understanding that the trend of the question is not only a critical problem which may threaten the existence of the Japanese PVC industry, but also will affect greatly upon national economy. The letter by Mr. Shimamura, president of the Japanese PVC association, shows activities so far and schedule for the future. There has been no such precedent before in Japan. Since there are many uncertain points, including relation between work environments and medical matters, the Association plans to dispatch a survey mission consisting of doctors and technical people. * 20 CMA 014315 f * To All Members 4anriv a June 1 , 197^ Subject: Emergency Temporary Standard on occupational health and safety for exposures to vinyl chloride monomer Gentlemen: We are pleased to inform you the following Emergency Temporary Standard which has been deliberated and decided at the 3rd Labor Health Committee on May 28, 197^. This is based upon the outline of the captioned Standard agreed at the 30th Board of Directors Meeting on May 21, 197^ to be adopted by the Japanese PVC industry Since institution of the Labor Health Committee we have been discussing the contents of this Emergency Temporary Standard. You may have already taken concrete measures along with the discussion. If not, we earnestly urge you to adopt the Standard to make perfection more perfect. Emergency Temporary Standard 1. Vinyl chloride monomer (VCM) concentration must be maintained not more than 50 ppm under work environments where employees will possibly be exposed to in production of VCM and PVC. 2. In any work environment where exposure exceeds the 50 ppm, employees must be provided, and must use, protective devices. With respect to the above 1 and 2, you are requested to enforce them as soon as possible. 3- Medical surveillance This shall be decided by the Medical Subcommittee which is organized by plant physicians. ' Incidentally, in the U.S. Proposed Rule was submitted to change labor environment standard from not more than 50 ppm of the temporary standard to a permanent level, no detectable level, virtually under 1 ppm. Reflecting such circumstances, our Labor Health Committee is planning to take the follow ing measures in the next stage. -- /7 CMA 016316 Revision of work practice standard, especially the permitted level, taking account of results of continuing research as well as study results by the Medical Subcommittee. Technical improvement to decrease monomer coneentration under work environments and emission to the atmosphere and also technical improvement of monitoring system. Sine erely, JAPANESE PVC ASSOCIATION M. Shimamura, President /& ------ CMrt 01631