Document 15JnKXynnVDkLjO2J1oMGVm0X

VINYL CHLORIDE MONOMER PROBLEM IN JAPAN July, 1974 JAPANESE PVC ASSOCIATION COPIED BY MCA VVC 000006089 CABLE ADDRESS FVCASSN TOKYO JAPANESE PVC ASSOCIATION 1-1, 2-CHOME, UCH15AIWAI-CHO, CHIYODA-KU, TOKYO, JAPAN TELEPHONES TOKYO (BOB) 5AS1 VCM/PVC SITUATION IK JAPAN I. VCM/PVC Industry In Japan the YCil/WC 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 yearn. The production of PVC in Japan has become the second largest in the world coming after your production. PVC has 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 VCM/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 VVC 000006090 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. .fANESE VC AALOCIATION In reply to Drorosnl by the workforce, the Japanese PVC Aasocia'jicn took immediate actions by conducting a medical survey putting emphasis <tm cleaning work in the polymerization reactors, and prepared a luide to Vinyl Chloride bncraoion Manual for Safe handling and Use* Cubseauently, each member company of the Association has adopted up until todav 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 acroosteolvsis at the 2nd medical survey in 1972, we have not found so far the above specific disease. p. At the end of January 1974, a report from USA of a possible ccnnection between angiosarcoma of liver a rare form of cancer, -- of VCM/pVC manufac lur ing employees, and occupational health and safety for exposures to VOM has cause:' 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 has 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 raay threaten the existence of the Japanese PVC industry, and will greatly affect the national economy. p. 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. 0-2) Through uiscussion xyj the Labor Health domnictee an Emergency Tamporar: Standard on Occupational Health and Safety for Exposures to VCM was published, and the following items were recommended to the member ccnoanies by the President of the Association. 000006091 vve a) VCM concentration, shall be maintained not more than ^0 ppm under work environments where employees will possibly be exposed to in pro duction of VCM/PVC. b) In any work environment where exposure exceeds the 5Q 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 - 1973 at present maximum ti n it ti 1000 ppm 100 - 500 ppm 50 - 200 ppm 50 - 100 ppm 50 ppm In connection with the cleaning work in a polymerization 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 }965 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 was water-jet cleaned., and than hand scraping w-3 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. VVC 000006092 III. Problem of VCM Migration In May 1973 7CK migration problem of PVC liquor bottle spread I into Japan from the United States. The Japan Hygienic PVC Association -- composed of ;C0 companies vrho are from PVC resin manufacturers to the food producers -- performed analysis on Honor 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. 00000*0" 7 P ro d u c tio n and S h ip m e n t o f PVC S o u rce : Ja p a n e se PVC A s s o c ia tio n w Vl G G <C - . i! 1 c c_ X W i vO CM O U\T- ON O Cu O <- O U N ro CM f-- c*~ On J ."N CM CM T T^-- ON r-- co vo vo T5-J-- oT" vo r- o-r-- i---O CM CO c ii o c tj O i iH -_> G G 02 ! T-- CM -^r c-- on T-" r-- O "!fr UN o r- O t-nc- T-- 'O On CO r-f "H -*-= o M .'--3 ' rO r-- *T5--3" N-- -M- T3- T--*rt* ***-=-T M- CM T-- CM - ocj <m CM r-- t--* ir- o ON ON OJ (D o +c->rt uJ w IG. .TJ ( G o T5 0) 1 1 oN 1 G H Oo o., H 1 i o <-o O ""I J\0 CO H>r- <- UN O CO ON ro CO vr co vo <-- ' OT aj a <--1 CL. G PH : CM VO *3- cm co r-- UN UN CC CO VO -53- '-ct- ^ rO rO i-O ) ^OC\r" c*-- vo vo vo <o 1-0 r--1 Oi CM CM OJ CM CM Hw cS ^0 G Oh I i CO +> OS3 c + so C- 'H H -G + co a> I j r^i VO UN i *. . CX2 VO CO O r-', o~ V- ro 'O *sT N 'O l -o `AOnJ- co -o <^r t^- O nT 53- O u"n >-- co U*N <3\ T-- on CO vr -.r un --r ON CO CM CO O UN s3- UN UN 1 I l CM r-- un VO VO ON rn t- m v.*- G\ UN O li , r-- un co c\j ON r-1 o CO CM UNUN -- /--l o 3- unon o co CM 'O -t -O ON -53-VO -- <"-> t-- CM `O 'O cn o\ 0\0 clAo r--ovvoo 04 Nf CO VO r~N UN CO co CM LTV coOrnc^m lTn ,--; ro C-- t-- av O t<-00% -- ''} iTNvC C-- O -- <-- SJccn qn o -- ro UN UN ^3 t\l rO *- /-n ) w Go +oj -*-> *aooGhG, o 1--1 fj VOC' o1** ON CM CM CM CUCOMN OOUNN MOt-O EC^--M VU"ON* UUNN3O0 Ot-N ot----n rUC~MN* VO NUMN n--^Tr '-- vOo vp^--on OOCMNn IO<N-o- 1On-0 COcf <~N P5--r OJ c-5oT vMVoO OOoNN Ccc----O CrOO-- cUonN Xon) t-- T3-* r*- VCOM ^ f^ONOs vOComN X-C5M3- cOooN Oo--N Oro--N rO M r ^3" UN 'O C-- CO ON O UN U\ UN UN UN UN VO -- cm <-o rr UN vo vo vo vo vo vo f-- cO On O vo vo vo vo r-- CM 1-0 c-- r-- c- U ON C3N ON ON ON ON 0 On On ON on ON C7\ On On ON ON On ON ON VVC 000006094 (".aide to Vinyl Chloride Operation Manual for Safe Handling and lr3e September 1970 Japanese PVC Association Contents: 1. Properties 1.1 Important physical and chemical properties 1.2 Toxicity 2c Engineering Control of VCM and PVC Manufacturing System 2.1 Production 2.2 2.3 Facilities Instalation of cleaning system for polymerisation 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 3.8 First aid Education and training 4. Medical Screaning 5. Other Protection Procedures /2 -- 0^ oooob 3Cleaning 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". (li) 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. ; 1 ooooo*096 f -) VCM c o n c e n tra tio n \ \ 500 ppm Start of ventilation Start of kettle entry Ventilation Relation between degassing time and VCM concentration in the reactor Measure VCM concentration bv one of.' the following methods, (a) Kitagawa type detector (b) Interference refractometry (c) Gaschromatography (5) (6) 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. 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) Protective glasses (b) Protective gloves (c) Protective clothing suitable to prevent skin contact such as long sleeve clothes f4 VVC 000006097 jrif/XitliOC* i >V nJJuwrtnuii (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. VVC 000006098 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) Semiluraan 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. /6 VVC 000006099 niiritJJw To All Members June 1 , 1974 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, 1974. This is based upon the outline of the captioned Standard agreed at the 30th Board of Directors Meeting on May 21, 1974 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, pro t ec tive 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 pptn. Reflecting such circumstances, our Labor Health Committee is planning to take the follow ing measures in the next stage. VVC 000006100 /7 Revision of work practice standard, especially the perraitt ed level, taking account of results of cnntinui ng research as v/ell as study result by the Medi cal Subcommittee. Technical i mprovement to decrease monomer cone entrati on under work environments and emission to the atmosphere and also technical improvernent of monitoring system. Sine er ely, JAPANESE PVC ASSOCIATION M. Shimamura , President /a VVC 000006101 Release Brief history of occupational health and safety for exposures to vinyl chloride monomer June 12, 1574 In the autumn of 19&9 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 wore suspected of acroosteolysis at the 2nd medical survey in 19711 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 1974, 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. WC 000006102 (1) The temporary emergency standard requires that no employee exposure is permitted to levels of VCM coneentration 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. Shiraamurn , oresider. t, 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. VVC 000006103 20 Annex Juno loth, 1974 Sanitation of PVC food containers In the United States some YCM was detected in whisky packed in PVC containers some time ago. Subsequently FDA announced a ban against PVC containers used for alcoholic boveragos as a provisional measure in May, 1973. We, Japan Hygienic PVC Association, followed to the FDA announcement without fTUling 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 tho VCM migration to its origin, it has appeared that by severly control cn production process and by improvement of producion equipment suspoctable 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 VVC 000006104 Japan Hygienic ^VC Association its organization CHAIRMAN BOARD OF DIRECTORS PROPAGATION OP 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 VVC 000006105 22 VCM Migration from PVC Bottles June 1, 1974 Japan Hygienic PVC Association Experiment 1 1. VCM migration into alcoholic solvents with use hf PVC i resins containing different levels of residual VCM, PVC bottles containing various levels of residual VCM ( l*--ca. 20 ppm ) were moulded. \ Filled with 20 fa and 50 fa 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 veigth bottle volume VCM in bottle VCM in solution VCM migration ( gram ) ( ml ) ( Ppm ) ( ppm ) rate from bottle (f) 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 ( Average 26fo ) Table 2 describes the VCM migration rates into 2Qf> alcoholic solution and sake from PVC bottles containing various levels of residual VCM by the same manner as in Table 1 . VVC 000006106 23 Table s olutionN, bottle veigth bottle volume VCM in bottle VCM in solution VCM migration { gram ) ( ml ) ( PPm ) rate from bottle ( 'r ) i sake it it 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 50ac, 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 vas 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 cotaiaing 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 0oo6 Ttabx 3 VCM in PVC compound ( ppm ) VCM in PVC bottle ( ppm ) Residue percent (*) 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 15V5 2.4 8.8 17 77 86 80 74 86 70 74 average- 78 fo 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 battles at the end. Prom 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: k: f: ratio of weight of contents / weight of bottle VCM residue ( ) from compounding process to bottle blowing process. VCM migration rate from PVC bottle into bottled food. 25 ooooo108 VMC Residual YCM amount in PVC 'pound = X :: ... k 100 x A f 100 Accordingly, to keep x -- value below 0.05 ncm ; In case of spirits, supposing A=:10, k=80?&T f--30?S are fixed ; O.05 x 10 -------------------------------------=== 2 ppm 0.8 x 0.3 ' ( maximum VCM amount in compound ) In this supposition, A=10 is rather particular case. It is thought in general A=20 should be more common. VVC 000006109 26