Document kDm54rDZw7mbEbvqroaz89JyO

VINYL CHLORIDE MONOMER PROBLEM IN JAPAN July, 1974 JAPANESE PVC ASSOCIATION BFG29924 Contents A. Vinyl Chloride Monomer Problems -- ------ _____ i Attached : List of Members - ---------- _____ 3 VCH/PVC Situation in Japan ------ _________ -4 Annex : 1. VCM/pVC Manufacturers in Japan - - 8 2. Production and Shipment of PVC -- --11 3. Guide to Vinyl Chlbride Operation Manual for Safe Handling and Use Contents and two Clauses --------- 12 4. Emergency Temporary Standard - -.-17 5.. Press Release - -- -- -- -- - 19 6. Samitation of PVC Pood Containers 21 7. Japan Hygienic PVC Association -- its Organization --------22 8. VCM Migration from PVC Bottles - -23 9. Determination of Vinyl Chloride in the Working Environment(:Draft)-------------- 27 10. Method for the Determination of Vinyl Chloride in PVC Resin and/or in Food - -- - 33 C. Health! Service -------- ----------------------------------------------------------- 36 Reference : I An Autopsy Case of Primary Haenioangioma J ^ of the Liver-------- - - - - - 39 II Primary Liver Sarcoma ------ 41 III Statestecs on the Number of Autopsy , in Japan -- ----- - ------ ---42 IV Temporary Standard for Medical Surveillance -- ------ -- -- - - 43 D. Questionnaire 45 BFG29925 CABLE ADDRESS PVCASSN TOKYO JAPANESE PVC ASSOCIATION 1-1, 2-CHOME, UCHISAIWAI-CHO, CHIYODA-KU, TOKYO, JAPAN tbjephcm TOKYO (30> 3481 VINYL CHLORIDE MONOMER PROBLEM rWe thank you for meeting with our mission today, and also express our deep gratitude for arranging us a chance for exchanging information on VCM and for ) hearing your valuable advices on the problem. In Japan the VCM/PVC industry commenced the commercial production in 1949 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 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 improving the people's daily livings. 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/PVC manufactur ing employees, and occupational health and safety for exposures to VCM has caused a worldwide discussion. Further on 5 April, 1974 and Emergency Temporary Standard for Exposure to VCM wa3 published on your Federal Register, and continually within the 6 months a Proposed Standard was published on 10 May, 1974 on your Federal Register. The Japanese VCM/PVC manufacturers understood the suspected proplem that not only the health and safety of the employees, but the trend of the problem is critical which may threaten the Japanese PVC industry and will greatly affect the national economy. In April 1974 the Labor and Health Committee was organized inside the Japanese PVC Association, and started taking positive actions. / BFG29926 24332003 JAPANESE PVC ASSOCIATION As a result of the action the following three points were decided as an emergency temporary action, and were recomended to the manufacturers. Each company started improving the enviroment and are making medical surveillance in accordance to the decision. 1) Work environment concentration : VCM below 50 ppm 2) In any work environment where exposure exceeds 50 ppm, employees shall be provided, and shall use, protective devices. 3) Temporary Standard for Medical Surveillance was prepared and medical ) screening is under way in accordance to this Standard. Surveillance is con ducted parallel to this on the death cause of the employees including the retired workers. The Japanese government agencies concerned are actively considering for enforcing national standards, the domestic labor unions under the influence of ICF and other international labor unions are taking actions. The news are frequently published on newspapers and released on televison. The general people are now showing interest on the problem. We consider that the VCM problem should be handled from global standpoint. Under this consideration, we wish to learn the actual situation here and the j sophisticated practical measures taken in your country. We also wish to exchange opinions for deep mutual understandings. We hope to establish a tight connection with your industry, and hope your good assistance for the settlement of this VCM problem. fojozzepz --2 BFG29927 JAPANESE PVC ASSOCIATION Leader LIST OP MEMBERS Mr. Kyohei Kawai General Manager, Environmental Protection & Safety Toa-Gosei Chemical Industry Co., Ltd. Dr. Kameo Hasegawa Medical Director Mitsui-Toatsu Chemicals, Inc. Dr. Mitsuru Suzumura Medical Director Toa-Gosei Chemical Industry Co., Ltd. Mr. Keiji Kano Manager, Techenical Division-Plastics & Chemicals Kanegafuchi Chemical Industry Co., Ltd. Mr. Osamu Egawa Manager, Manufacturing Dept., Kikumoto Works Sumitomo Chemical Co., Ltd. Mr. Hideo Iijima Manager, Environment & Safety Dept. Nippon Zeon Co., Ltd. Dr. H. Matsuo Technical Manager Nippon Zeon of America Mr. M. Kono Technical Advisor Kaneka. America Corp. Mr. N Kagawa Sumitomo Chemical Co.,Ltd. New York Representative Mr. H. Ochi Representa tive of Ne->v York Office Mitsui-Toatsu Chemicals, Inc. 3 BFG29928 cable address PVCASSN TOKYO JAPANESE PVC ASSOCIATION 1-1, 2-CHOME, UCHISAIWAI-CHO, CHIYODA-KU, TOKYO, JAPAN telephones TOKYO (SOS) S4SI VCM/PVC SITUATION IN JAPAN I. VCM/PVC Industry In Japan the VCM/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 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 VCM 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. s n iO o 4 BFG29929 JAPANESE PYC ASSOCIATION In reply to proposal by the workforce, the Japanese PYC Association took immediate actions by conducting a medical survey putting emphasis on cleaning . work in the polymerization reactors, and prepared a Guide to Vinyl Chloride Operation Manual for Safe Handling and Use. Subsequently, each member company of the Association ha3 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/PVC manufactur ing employees, and occupational health and safety for exposures to YCM ha3 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 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 may threaten the existence of the Japanese PVC industry, and will greatly affect the national economy. 3 Actions The actions tohk to date by the Association are as followss 3-l) The Labor Health Committee was organized inside the Japanese PVC Association as for discussing thi3 VCM problem, and also Medical Group and Technical Group were established a3 the sub-committees. 3--2) Through discussion by the Labor Health Committee an Emergency Temporary 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. 5 BFG29930 LQQZZVbz JAPANESE PVC ASSOCIATION 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 VCM/PVC. b) In any work environment where exposure exceeds the 50 ppm, employees shall be provided, and shall U3e, 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 maximum " " " " 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 i3 suspected, there are very few workers appointed specially for such cleaning heretofore. In Japan high-presure watersjet clean ing system i3 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 was water-jet cleaned, and then hand scraping was made by the poOLy-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. 34S22C08 6-- BFG29931 JAPANESE PVC ASSOCIATION III. Problem of VCM Migration In May 1973 VCM 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 3uch 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. ) s 7 BFG29932 JAPANESE PVC ASSOCIATION VCM/PVC Manufacturers i Tanan Annex 1 ! manufacturer and plant Asahi Glass Co.,Ltd. Chiba (VCM/PVC) Kashima Vinyl Chloride Monomer Co.,Ltd. Kashima (VCM) Kanegafuchi Chemical Industry Co.,Ltd. Osaka (PVC) Takasago (VCM/PVC) ) Kashima (PVC) Kureha Chemical Industry Co.,Ltd. Nishiki (VCM/PVC) San Arrow Chemical Co.,Ltd. Tokuyama (VCM/PVC) Sanyo Monomer Co.,Ltd. Mizushima (VCM) Shin-Etsu Chemical Industry Co.,Ltd. Naoetsu (VCM/PVC) Nanyo (PVC) Kashima (PVC) Sumitomo Chemical Co.,Ltd. Kifeunoto (VCM/PVC) Chiba (PVC) Central Chemical Co,Ltd. Kawasaki (VCM/PVC) site Chiyoda-ku, Tokyo Ichihara-shi, Chiba Kashima-gun, Ibaragi Kita-ku, Osaka Settsu-shi, Osaka Takasago-shi, Hyogo Kashima-gun, Ibaragi Chuo-ku, Tokyo Iwaki-shi, Pukushima Tokuyama-shi, Yamaguchi Chiyoda-ku, Tokyo Kuras hiki-shi, Okayama Chiyoda-ku, Tokyo Naka--Kubiki-gun, Niigata Shin-Nanyo--shi, Yamaguchi Kashima-gun, Ibaragi Kita-ku, Osaka Niihama-shi, Ehime I chiratar-shi , Chiba Kawasaki-shi, Kanagawa 24323010 8 BFG29933 JAPANESE FVC ASSOCIATION Chisso Corporation Minamata (VCM/PVC) Mizushima (PVC) Goi (PVC) Chiba VCM Co.,Ltd. Chiba (VCM) Tekkosha Co.,Ltd. Yokkaichi (PVC) Denki Kagakil Kogyo Kabushiki Kaisha Omi (VCM/PVC) Shibukawa (PVC) Chiba (PVC) Toagosei Chemical Industry Co.,Ltd. Tokushima (VCM/PVC) Kawasaki (PVC) Toyo Soda Manufacturing Co.,Ltd. Nanyo (VCM) Yokkaichi (VCM/PVC) Tokuyama Sekisui Industry Co.,Ltd. Nanyo (VCM) Nissan Chemical Industry Co.,Ltd. Chiba (VCM/PVC) Nissin Chemical Industry Co.,Ltd. Takefu (PVC) Nippon Zeon Co.,Ltd. Takaoka (VCM/PVC) Mizushima (PVC) 9 Chiyoda--ku, Tokyo Minamata-shi, Kumamoto Kurashiki-ahi, Okayama Ichihara-shi, Chiba Ichihara-shi, Chiba Chuo-ku, Tokyo Yokkaichi-shi, Mie Chiyoda-ku, Tokyo Omi-machi, Niigata Shibukawa--shi. Gumma 'Ichihara-shi, Chiba Minato--ku, Tokyo Tokushima--shi, Tokushima Kawasaki-shi, Kanagawa i Shin-Nanyo-shi, Yamaguchi Yokkaichi-shi, Mie Kita-ku, Osaka Shin-Nanyo-shi, Yamaguchi Chiyoda-ku, Tokyo 1 Ichihara-shi, Chiba Chiyoda-ku, Tokyo Takefu-shi, Fukui Chiyoda-ku, Tokyo Takaoka-shi, Toyama Kurashiki--shi, Okayama BFG29934 JAPANESE PVC ASSOCIATION Mitsui Toatsu Chemicals,Inc Nagoya (VCM/PVC) Sempoku (VCM/PVC) Mitsubishi Monsanto Chemical Company Yokkaichi (VCM/PVC) Ryo-Nichi Co.,Ltd. Mizushima (VCM/PVC) Hayatsuki (PVC) ) Chiyoda-ku, Tokyo Minami--ku, Nagoya Takaishi-shi, Osaka Chiyoda-ku, Tokyo Yokkaichi-shi, Mie Chiyoda-ku, Tokyo Kurashiki-shi, Okayama Namerikawa-shi, Toyama ) -- ro BFG29935 JAPANESE PVC ASSOCIATION CM <Xx> c c < ) \ i \ I o p* M VO CM p*> O irv '-i ov o CM CM P>y- o\ tt-t* CM O *" x- xc-- 00 VO vo Tfr O irvrn cm rox-- vo r- or* r**-' r- f~ civ Pr-'S Cr~M CO t ; bD Co 0U) cu I 05 : ca ;P C o p to o -H c 00 (* *H *H -p S ^ s o5 o <y a o *3 H M ^ ji} H&*. C aj t5 0 o - CO ^ ao ^ Sh * cu i: *C3 I a P r\ *ao 2 s! u cu y- CM oO k*T" T" xT c~- On x- tC^V XT XT xj" -XT X-- x-- x-- t-- r-- O ITS O CM t- CM y- X" X-- X-- X-- X-- O '-nc-'* Y- PS CM CM CM vo OV CO O OS OS O PS CM MD so O PS OS O CO ITS t- x-- ITS O 'j-wco c~m its co oo ^ 'f rO PS PS PS PS O OS PS CO Y^J- CO VO Yvroovr'^ vo VO vo PS PS CM CM CM CM CM CM p> ps NO LT\ y-- O cvo-- vrOo coont"PS PS PS y3* ro irv 1-0 ^ oo ro Nf O vr 'T T "3- "3- O vrv r- i-v co OsOO CM ov- ov oo vf M' L,v m- vr croj- oLTS mLTS Il i \il Wc po GP 0 So G P P^ iI | Xj +> CO s \ CM y-- t-- lT\ vo VO os ps PS OV IT) O >- no irsr- its co cm PS os ^vo y-- OS P) O CO CM P> y- CM PS VO tfs V- rO O ^ 20 OV <~n rx VO lOffvOcO lO CJV O lfvp~ VO Y- Y-- CVJ CM PS PS covom irvco CO CM IT) co o nt-in OVO >trs rnco t-- r-- y- O Os -- CM ITVVO C-- r-i ixmtv O PS ^3" PS VO CM yicv r-- ovo - O PS x-- r" co c0 *OH 00O a> a. 00a3> c ccu ctf "5 0) o u o3 CO P r o d u c tio n and S h ip m e n t o f PVC to i i c GO OP po OP 3^ TJ p o S . NoO orOS CM t- CM cm ps CVI lT\ O C-- t- NO X-- NO CM os co co oo Ov oo oo ITS o vo TJ-VO CM Y^fNO r-- OS vo ov t-- r- lt vo xj* os ooo\t-wm tAx--onos vo o r-O O CM CM O ITS CO y- OS C-- C-- PS CO p> CM Os y-- x- CM OS OS PS ITS O OS C-- U"S O O vj-h-CO CO Y-- X^J- NO Y- Y~ CM PS PS PS 'vj* YvJ- vr r-OvO v Y-- f-- To o <-o u VO C-- 00 Ov O CM PS LTS VO- C--CQ OS O y- CM PS ITS its irv cfv ic\ irvvo vo vo vo vo vo NO NO vo VO c^~ r~~ c-- >* os os OS 0\ OS 0S OS Os Os CTs Os Os OS OS os CTS C7S Os OS CTs T-- T~ -- // BFG29936 05 IS) *0 a w JAPANESE PVC ASSOCIATION Annex 3 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 such 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 24322034 !Z -- BFG29937 JAPANESE PVC ASSOCIATION Jm 3-4 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". (4) 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. V&ZZ2VZ !3 BFG29938 i JAPANESE PVC ASSOCIATION VCM c o n c e n tr a tio n Start of ventilation 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) Protective glasses (b) Protective gloves (c) Protective clothing suitable to prevent skin contact such as long sleeve clothes f4- -- BFG29939 Co w to o 0 JAPANESE PVC ASSOCIATION (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. ) 24322617 /5-------------- BFG29940 JAPANESE PVC ASSOCIATION 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. /6 BFG29941 JAPANESE PVC ASSOCIATION Annex 4 To All Members 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. --n BFG29942 JAPANESE PVC ASSOCIATION (1) 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. (2) Technical improvement to decrease monomer concentration under work environments and emission to the atmosphere and also technical improvement of monitoring system. Sincerely, JAPANESE PVC ASSOCIATION M. Shimamura, President *' -- /Q BFG29943 JAPANESE PVC ASSOCIATION Press Release Brief history of occupational health and safety for exposures to vinyl chloride monomer Annex 5 June 12, 1974 j 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 Association has adopted up unxil 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. JFollowing 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. | jI j ! ! ! I i Lsozzg& z /9 -- BFG29944 JAPANESE PVC ASSOCIATION (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 liv"er 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 jof 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. 2432202a -- 20 BFG29945 Annex 6 June loth, 1974 Sanitation of PVC food containers In the United States some VCM was detected in whisky packed in PVC containers sometime ago. Subsequently PDA announced a ban against PVC containers used for alcoholic beverages us a provisional measure in May, 1973. We, Japan Hygienic PVC Association, followed to the PDA announcement without frilling 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 on production process and by improvement of producion equipment suspectable VCM migration into food can be minimized to non-detection. As tho 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 be remaining in food thereafter. Japan Hygienic PVC Association BFG29946 21 24322023 Japan Hygienic PYC Association. -------- its organization -- Annex 7 CHAIRMAN BOARD OP DIRECTORS PROPAGATION OP RECOMMENDATION COMMITTEE Propagation of the recommended standard. Checking of the products in market . PTTBT.TC 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 *Tid arrangement of technical report at home and abroad. COMMITTEE ON BUSINESS AFFAIRS Negotiation and liaison vith the related official Agencies and referenced Associations. Management of General affairs 24322024 22 BFG29947 Annex VCM Migration from PVC Bottles \ June 1, 1974 j Japan Hygienic PVC Association Experiment l jl * VCM migration into alcoholic solvents with use bf PVC resins containing different levels of residual VCM, PVC bottles containing various levels of residual VCM ( l^ca. 20 ppm ) were moulded. \ Pilled with 20 ? and 50 i* 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 5Calcoholic 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 No. 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 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 . BFG29948 24322025 Table 2 bottle weigth bottle volume VCM in bottle VCM in solution VCM migration ( gram ) ( ml ) ( PPn ) rate from solution\^ bottle ( # ) 20# alcohol * n sake II II 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 # ) From Table 1 and 2, in thinking of Japanese spirits, as the tested condition ( at 50c, 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 PTC 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 an&lized 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. ti 2432202$ 24-------------- BFG29949 i Table 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 15^5 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 bottles 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 : ratio of weight of contents / weight of bottle k : VCM residue ( `ft ) from compounding process to bottle blowing process. f : VCM migration rate from PVC bottle into bottled food. 24322027 25 BFG29950 Residual VCM amount in PVC compound = XxA k 10O f 100 Accordingly, to keep x - value below 0.05 onm ; In case of spirits, supposing A=10, k=80?5, f=30?6 are fixed ; 0.05|xl --- --------------------- 0.8 x 0.3 1 == 2 |pPm * ( maximum VCM amount in confound ) In this supposition, A--10 is rather particular case. It is thought in general A=20 should be more common. 8Z9ZZSPZ -- 26 BFG29951 JAPANESE PVC ASSOCIATION Annex 9 Determination of Vinyl Chloride in the WotMy Environment ( twapt ) 1. Scope The following procedure describes a method for the quantitative determination of vinyl chloride ( VCM ) in the working environment. 2. Outline of Method Air sample is drawn into a gastight syringe and injected into the gas chromatograph and the area of the 701 peak measured. This area is compared to that of the calibration staudard3. 3. . Apparatus Gas sampler 11.-. Class bottle 201. Gastight syringe Syringe 200ml. Vacuum Pump Mercury manometer Gas chromatograph, equipped with flame ionization detector. 4. Reagents (l ) Liquified high purity 7(31 in bomb (2) Na in bomb 5. Gas Chromatograph Operating Conditions Column Stainless steel tubing 3 am ID X 5 I* Stationary liquid 20 Tricresyl phosphate on stationary solid ( weight percent ) Stationary Detector Injector temperature Chromosorb AW 60 ~ 80 mesh Hydrogen flame ionization detector 150 C Column temperature 70 C Carrier gas Na at 60ml./ mirt Sample size Chart speed 5 ml . 20 mm / min BFG29952 27 24322029 6. Standardization A. VCM Gas Sampling ' \ (1) The assembly of apparatus for sampling of VCM gas in the gas sampler ( A ) is shown in Fig. t. (2) Turn the three -- way cock ( F ) to the vacuum pump and evacuate the gas sampler ( A ). (3) Turn the three -- way cock ( F ) to the VCM bomb ( G ). (4) Open the valve of the VCM bomb ( G ) gradually and introduce slowly VCM gas into the gas sampler ( A ). (5) Wien the mercury manometer shows one atomospheric pressure, close the v value of the VCM bomb ( G ). (6) Turn the three - way cock ( F ) to the vacuum pump and evacuate the gas sampler ( A ) again. (7) Bepeat steps (3) - (6) three times. (8) Finally, introduce VCM gas into the gas sampler ( A )alightly higher ( Ca. 30 mmHg ) than 1 atomospheric pressure. (9) Close the valve ( B ) and remove the three - way cock ( F ) and the stainless needle ( D ). B. Preparation of Calibration Standards (1) The assembly of apparatus for preparing calibration stanmC.ards.5 is shown in Fig. 2. (2) Open the cock ( L ) and ( K ), and evacuate the 201 glass bottle ( H ). (3) Close the cock ( L ) and ( K ). (4) Draw the VCM gas into the gastight syringe through the silicon rubber septum ( P ) of the glass sampler( a ) , and inject the VCM gas to he measured into the ^iol glass bottle ( H ). O S0Z2&2 BFG29953 Volume of VCM to be drawn into gastight syringe 2 ml. 1 ml. 200 J*1* 100 jaI. 20 VCM concentration of calibration standards 100 ppm 50 ppm 10 ppm 5 ppm 1 ppm (5) Open the cock ( J ), then introduce slowly the lfa gas into the 201, glass bottle ( H ) to 1 atomospheric pressure and close the cock ( J ). (6) Stab the needle of the 200ml.syringe through the silicon rubber septum ( 0 ), and mix thoroughly the VCM gas by repeating suction and injection. (7) Calculate the concentration of 7(3! in the standard by following formula. ppm VCM Volume of VCM gas injected (^1.) Volume of 201. glass bottle ( 1.) C. Preparation of the calibration curve. Inject exactly 5ml .of the calibration standard into the gas chromatograph and run at the above conditions. Determine the VCM peak area of the concentration of each of the calibration standards and prepare a calibration curve. J2QZZZ&Z BFG29954 29 7. Procedure (1) Set instrument parameters at the values listed in 5. (2) Inject exactly 5 ml. of the sample gas into the gas chromatograph and run at the above conditions. (3) Measure the area of the VCM peak and read out the VCM concentration in air from the calibration curve. 30 -- BFG29955 Sifartl&s MAtdh CP9 Tij.i Assz7*.bly jon. 1/ C.tf &txc 3/ BFG29956 24322033 A-If,1C 3 BFG29957 Annex 10 j Method for the determination of vinyl chloride in PVC resin* and/or in food I Vinyl chloride entrapped in PVC resins and/or migrated into foods such ns alcoholic beverages and edible oil packaged in PVC containers can be determined by dissolving the PVC resins in tetrahydrofuran (XrlF) and subsequent analysis of the solution by gas chromatograph in the former and in the latter by injecting directly;the foods into gas chromatograph, using suitable standard solutions as reference. 1 Determination of vinyl chloride in PVC resin V.'eigh accurately about 1 gram of the PVC resin into a 25 ml volume of test tube and add 20 ml of tetrahydrofuran* (THF) and close the tube tightly with a ground glass stopper or silicon rubber stopper. V/hen PVC resins are completely dissolved, 5~10/tl aliquots of the solution is injected into gas chromatograph equipped with flame ionization detector under conditions shown in Table 1. * THF showing no peak on gas chromatogram at a retention time of vinyl chloride must be used. 2 Determination of vinyl chloride in food Vinyl chloride migrating from PVC containers into foods, such as alcoholic beverages and edible oil, can be determined by injecting directly 5--10pX aliquots of thfcse foods into gas chromatograph. 4 24322035 33 BFG29958 3 .Preparation of standard solutions of vinyl chloride * (i) Stock solution. About 1000 PPM Vinyl Chloride About 195 ml of ethanol are taken in a 200 ml volumetric flask and close with a silicon rubber stopper, and then it is weighed. Dissolve about 200 mg of vinyl chloride through the silicon rubber stopper using a syringe and mix to get complete solution. The flask is reweighed to determine the vinyl chloride dissolved, in the ethanol. Add ethanol through the silicon rubber stopper up to the mark. The stock solution thus obtained is cooled to -50"C with methanol-dry ice. (ii) Working standards a) About 10 PPM Vinyl Chloride Transfer 1 ml aliquots of standard stock solution to a 100 ml volumetric flask and dilute to volume with ethanol. When the concentration of vinyl chloride is accurately determined, fcjia l ml of stock solution kept at -50"C should be reduced to that at room temperature. The reduced volume can be obtained by the following equation : V : reduced volume (ml) : 'Weight of 1 ml ethanol at room temperature . * Weight of 1 ml stock solution cooled at -50"C 9ES>ZbZ 34 BFG29959 b) About 0.05--0.2 PPM Vinyl Chloride Transfer aliquot v; of about 10 PPM standard solution prepared as above to 100 ml volumetric flask to prepare about 0.05 0.07, r0.10, 0.15 and 0.2 PPM solutions, and dilute to volume with ethanol. * Table 1 Gas Chromatography Conditions Column Carrier H^Air (i) A 3 x 5m/m (i.d) coiled glass column packed with 25 wt5a PEG-20M on 6o~ 80 mesh Chromosorb (ii) W-AW ei ' A 3TM x ya/m (i.d) coil glass column packed with 10 wt?> Ucon oil LB-550X on 60~80 mesh Anakrom SD (iii) A Jm x Jm/m (i.d) coiled glass column packed with 10 \vt% Silicon DC-550 on 60~80 mesh Gasport A Any of these columns may be used. N2 20~60 ml/min Optimized # Temp. Column ; 60~<70VC, Sample size 5~10 pX Injector ; 150~200*'C LSQZZSVZ 35 -- BPG29960 JAPANESE PVC ASSOCIATION Health Service We have come into contact with informations concerning the VCM problems. We were strongly shocked at the case report, "angiosarcoma of Liver in the manu facture of PVC", which was published in the Journal of Occupational Medicine, Vol. 16, No.3. As a physician, who works at a PVC plaint, I am 1 very interested in the Health Service Program that in cludes proposal from your government. Similar to your country, "angiosarcoma of Liver" is a very rare disease in our country. We have found out few reports, as will be seen in the attached references I, II and III. And up to now, our investigations have failed to find a PVC worker who died from this disease though the investigation is being carried on for the remaining factories. On the other hand, a general AOL investigation ) under governmental instruction has found only two slightly abnormal persons. However, we are strongly conscious of the fact that our country come3 more than 10 years behind yours in the PVC-manufacturing industry and are very much worrying about the safety of the workers of whom we are taking care. 24322(538 36 -- BFG29961 JAPANESE PVC ASSOCIATION Therefore, we are starting a health service under the standards as the attached reference IV and, are calling on you and at some related facilities in your country in order to collect some correct opinions.as much as possible. The followings are some of our questions that look forward to your kind cooperation and reply. (1) We hope that we can have some papers con- cerning the clinical picture of haemoangiosarcoma from you. We believe that the appearance of splenomegaly is an important aetiological index. But, how do you think of this? (2) How do you assume the aetiologie of VCM- diseases, such as AOL, haemoangiosarcoma, liver disfunc- tion, etc? (3) Do you agree with the conception of "Allge- meine Sklerotische Krankheit" as proposed by the German Scholars? (4) Is there any other malignant tumor in addi- tion to "haemoangiosarcoma of liver" that has been found in the human suffering from VCM? (5) Are there some determinants based on which a conclusion of "normal" can be drawn from a result of ' I [ | ! j j i t S i ! i ! i j j 24322039 37-- -- BFG29962 JAPANESE PVC ASSOCIATION serum liver function test? If any, please send us the related lists. (6) How do you conduct the investigation on Mead persons"? We would highly appreciate it if you could give us some of the investigation forms. (7) The number of international classification about malignant neoplasm (for example, 155.0 Liver Carci noma) seems to be unsuitable for computation tape. But, which system of classification do you follow in your coun try? KAMEO HASEGAWA M.D. MITSURU SUZUMURA M.D. I --38 BFG29963 JAPANESE PVC ASSOCIATION Reference I An autopsy case of primary haemoangioma of the liver H. Kumano, T. Kainuma, H. Shoyama & K. Kojima ) Ganno Rinsho Vol. 17* No.7* 1971 A quite rare autopsic case of primary haemoangioma of the liver was reported. A farmer aged 66, violent epigastral pain and vomitation occurred in March of 1969, hut lightened, after about 1 month's treatment. In July of 1969, anaemia, swiftness of blood sedimentation occurred. Later, jaundice and oedema came into appearance despite of various cli nical examinations and treatments, and be entered to hospi tal owing to suspicion of liver cancer. The primary symptoms were slight disturbance of liver function, bloody ascites, serious anaemia, and high blood sedimentation reaction, but marasm proceeded gradually and died on Decem ber 28, 1969. 39 BFG29964 XfQZZEVZ JAPANESE PVC ASSOCIATION Primary haemoangiosarcoma and metastasis towards spleen, kidney, suprarenal body, jejunum and lymphatic system were demonstrated by the cLutopsy. 40 BFG29965 JAPANESE PVC ASSOCIATION Reference II Primary Liver Sarcoma Haemoangioendothelioma Malignant mesenchymoma Fibrosarcoma Rhabdomyosarcoma Leiomyosarcoma Liversarcoma Reticulosarcoma Reticuloendothelioma Primary lymphosarcoma Chondrosarcoma + Hepatoma Mixosarcoma Liposarcoma Kupffer cell sarcoma Total 11 (2) 2 3 1 3 (2) 4 1 2 1 1 (1) (1) 1 30 + (6) (false) The Annual of the Pathological Autopsy Cases in Japan (1966 - 1971). 24322043 BFG29966 4/ JAPANESE PVC ASSOCIATION Reference III Statistics on the Number of Autopsy in Japan Year 1966 1967 1968 1969 1970 1971 Population 99,056,000 99,657,000 100,704,000 102,022,000 105,119,000 104,345,000 The Dead (A) 670,342 675,006 686,555 693,787 712,962 684,521 Autopsy (B) 17,830 20,902 25,224 23,904 22,003 21,725 B/A 0.028 0.031 0.037 0.034 0.031 0.032 BFG29967 JAPANESE PVC ASSOCIATION Reference IV Temporary Standard for Medical Surveillance The 1st medical screening Once every 6 months (once every 3 years as for Item No. 7) lo Screening of past work history 2. An employee shall be checked concerning (l) alcohol intake, (2) past exposure to potential hapatotoxic agent, (3) past history of blood transfusions and (4) past history of serious illness. 3. Physical examination shall be performed regarding the following subjective and objective past symptom: 1) Enervation, fatigability syncopal dizziness, poor appetite, upper abdominal pain and indis position which might be caused by exposures to VCM. 2) Paralysis of fingers, paleness, pain, paresthesia, scleroderma which might be caused by exposures to VCM. 3) Liver disease and melanorrhagia 4. Physical examination shall be performed to find ) whether the following subjective and objective symptom is detected or not at present: Enervation, fatigability, poor appetite, upper abdominal pain and indisposition, anemia, jaundice, melanorrhagia, paralysis of fingers, paleness, pain, disorder of perception and scleroderma. 5- Physical examination shall be performed to detect enlargement of liver or spleen., 6. Screening shall be made with regard to serum biliru bin, transaminases (GOT and GPT), LDH and alkaline phosphatase to test liver function and also shall be 43 -- BFG29968 JAPANESE PVC ASSOCIATION 2 made concerning total blood density and hemoglobin. 7. X-ray examination of fingers The 2nd medical screening 1. Examination of work environments 2. In case a doctor finds them necessary, tests shall be conducted with respect to platelet count, GOTP ", BSP or ICD retention rate and fractions of plasma protein. 3,, If hemorrhage or hepatic or splenic tijmor is detected and a doctor finds it necessary, medical test shall be applied. BFG29969 CABLE ADDRESS PVCAS6N TOKYO JAPANESE PYC ASSOCIATION 1-1, 2-CHOME, UCHISAIWAI-CHO, CH1YODA-KU. TOKYO, JAPAN Questionnaire 1. Operation environment 1-1 'i How much VCM concentration would be seen to become to the final standard by US government ? Will there be any time-weighted idea included in the law-making ? If there is, how much will it be ? 1-2 In case of irregular operations such as emergency case in production, repairs of production equipments, maintainance, etc.; From where does VCM come out ? And, how much volume is it at present ? what is the counter-action to it ? 1-3 In the production lines of VCM and PVCJ form what part of the production line does VCM come out in regular operation ? And, how much volume is it at present ( exhaust from drier, reactor, etc. ) ? And, what is the counter-action to it ? -----45- ------- BFG29970 1-4 What cleaning procedure had been taken to clean the polymerization reactors in past ? And, what is today ( how changed ) ? 1-5 What is the working condition and working hour of operators for polycleaner so on who will be frequently exposed in high VCM atmosphere ? 1-6 How is the situation of using safety respirator in working operation ? Is there any inconveniece to use it in working behaviour ? Is there any quantitative data on effectiveness to use safety respirator ? 1--7 If VCM concentration in PVC processing factories has been measured, we would like to know the data. 1-8 and PVC resin maker What kind of counteraction does government*take against PVC converting factories.? 1--9 How active is the labour union against the VCM problem ? ) 2. Healtli cbh'trol 2-1 What are the working history, years of service, degree of VCM exposure of the death people ? 2-2 Are VCM exposed people clearly differentiated from general citizen in epidemic or statistic view point ? 2-3 How many factories and workers are engaged in VCM production, PVC production, PVC processing respectively ? '' --4 6----- ---- --................ ..... ....... --------- ___ BFG29971 24322048 1 2-4 Ve would like to hear what had happened until the origin of angiosarcoma being determined to be VCM. If so, what is the reason why ? How do you think of relation with ACRO ? 2--5 Ve would like to know of the progress on the animal experiments as to respiration and skin breath. And, if there is any new plan in mind, we would like to hear. 2-6 Ve would like to hear of the detail of each of critical pictures. Food packaging, and others 3-1 Vhen and how will residual VCM in food packaging materials be legally regulated ? 3--2 3--3 How do PVC processing manufacturers feel on VCM problems ? 3 How do food product manufacturers feel on VCM problems ? 3-4 Vhat are the applications of FVC as food packaging material ? And, how big is the total volume of FVC for food packaging use ? 4-1------- BFG29972 3-5 PVC liquor bottles are prohibited now. But, will PVC liquor bottles be permitted with similar restriction to other food packaging uses of PVC after all uses of PVC food packaging being appraised ? 3-6 How will cosmetic/pharmaceutical applications of PVC go ? 3-7 And, how will PVC potable water pipes be ? ( method of water extraction ) 3-8 What are the present residual VCM contents in suspension PVC, emulsion PVC, and copolymer resins ? 3-9 Is there any claim from PVC processors to reduce residual VCM in resin ? If any, how much is it ? How does PVC resin manufacturer think of it ? 3 -10 How do consumer groups behave ? And, what action is taken to cope with ? 3 -11 How^is the progress of animal feeding test ? ( methods of breeding_and feeding ) 24322050 4. General environment 4-1 How is the movement toward making regulations for general environment ? If some regulations are considered, when and how vill they come out ? 4-2 How is the general environment in USA ? ... -46 -- BFG29973 ( For example : VCM concentration in air at boundary of the factory ) Analysis methods 5-1 What is the best way fixed place measuring system, monitoring or personal monitoring ? ( being practiced ? ) 5 -- 2 Analysis method for FVC moulded products ? 5.-3 Analysis method for migrated VCM into foods ? 5--4 Standard measuring procedure for labouring atmosphere ? 5--5 Simplified analysis method ? 7 BFG29974 6. Others 6-1 How is it presently considered of VCM material balance from VCM of PVC to moulding ? Hov much is the unit eonsumotion of VCM ? If the unif .gf VCM is reduced, how much is it as a target ? 6--2 How is it considered of closed system ( regulation for total volume ) ? 6--3 Is it considered to make cooperative works with each other on research and engineering development ? How is the present situation of treatment of rerefied VCM gases ? And, how is it deemed on developing some means for solving the problem ? 6-4 How will the VCM problem affect to other products than FVC such as EDC, VDC, TRICLENE, AN, etc. 2 3 -j ZZSVZ BFG29975