Document 6wJG7jjkDqbnRmXB1G1KOnVnE

.ttnafe* VINYL C5L0HIDE MONOMER PROBLEM IN JAPAN J July, 1974 1 JAPANESE PVC ASSOCIATION T Contents A. Vinyl Chloride Monomer Problems ----- -------- -- 1 Attached : List of Members --------- 3 3. VCH/PVC Situation in Japan ---------- --------4 Annex : 1. VCM/pVC Manufacturers in Japan - -- 8 2. Production and Shipment of PVC - -11j 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 Pood -- -- - 33 - Z\j'3ZZ2VZ C. Healthl Service ----------______------------------______36 Reference : I An Autopsy Case of Primary Haemoangioma 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 s JAPANESE PVC ASSOCIATION CABLE address PVCASSN TOKYO 1-1, 2-CHOME, UCHISAIWAI-CHO, CHIYODA-KU, TOKYO, JAPAN telephones TOKYO (SOS) 94SI VINYL CHLORIDE MONOMER PROBLEM ?We 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 i3 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/FVC 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. 0) / 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 assistince for the settlement of this VCM problem. S & 2 r JAPANESE PVC ASSOCIATION LIST OP MEMBERS Leader s Mr. Kyohei Kawai General Manager, Environmental Protection & Safety Toa-Gosei Chemical Industry Co., Ltd. Br. 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 4 Safety Dept. Nippon Zeon Co., Ltd. Dr. M. Matsuo Technical Manager Nippon Zeon of America ) Mr. M. Kono Technical Advisor Kaneka. America Corp. Mr. K- Kagawa Sumitomo Chemical Co.,Ltd. New York Representative 2r. H. Ochi Representative of New York Office Mitsui-Toatsu Chemicals, Inc. --3 24322005 CABLE ADDRESS PVCASSN TOKYO JAPANESE PVC ASSOCIATION 1-1, 2-CHOME, UCHISAIWAJ-CHO, CHIYODA-KU, TOKYO, JAPAN telephonr* TOKYO Csoe) S4M vcm/pvc situation in japam 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 500,0Cf* 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. *5 4 as JAPANESE PVC ASSOCIATION t \ . *. In reply to proposal by the workforce, the Japanese PTC 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 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/PVC 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 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 PTC industry, and will greatly affect the national economy. .) 3. Actions The actions took to date by the Association are as follows: 3-l) Tie Labor Health Committee was organized inside the Japanese PVC Association &s for discussing thi3 VCM problem, and also Medical Group and Technical Group were established as the sub-committees. i 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. im tz z & z 5-- 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 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. ) 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 " 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 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 was water-jet cleaned, and then hand scraping was 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. S4322C08 6-- 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 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. JAPANESE PVC ASSOCIATION VCM/PVC Manufacturers i Japan Annex 1 manufacturer and plant Asahi Glass Co.,Ltd. Chiba (VCM/PVC) Kashima Vinyl Chloride Monomer Co.,Ltd. Kashina (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. Kikumoto (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, Fukushima 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 Ichirata-shi, Chiba Kawasaki-shi, Kanagava --8 JAPANESE PVC ASSOCIATION Chisso Corporation Minamata (VCM/PVC) Mizushima (PVC) Goi (PVC) Chiba VCM Co.,Ltd.. Chiba (VCM) Tekkosha Co.,Ltd. Yokkaichi (PVC) Denki Kagakli 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) Ni3sin Chemical Industry Co.,Ltd Takefu (PVC) Nippon Zeon Co.,Ltd. Takaoka (VCM/PVC) Mizushima (PVC) Chiyoda--ku, Tokyo Minamata-3hi, Kumamoto Kurashiki-shi, Okayama Ichihara-shi, Chiba Ichihara--shi, Chiba Chuo--ku, Tokyo Yokkaichi--3hi, 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 ' Ichihara-shi, Chiba Chiyoda-ku, Tokyo Takefu--shi, Pukui Chiyoda-ku, Tokyo , Takaoka-shi, Toyama Kurashiki--shi, Okayama 9-- 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-ahi, Mie Chiyoda-ku, Tokyo Kurashiki-shi, Okayama Namerikawa-shi, Toyama ) V lQ Z z z v z ro-- -- i CM X CD *C <c ! I i i VO CM O IT\ T-i os 0 CM O **" *" O OJ t-- C^- C-- ON CM CM r*V*- ON r--co vo vo 0 vo r-- 0 - r*') CM CD i | ctOd p o P P-* ! : ca ; > I^ c* to o C !-: oO T5 r-i P rH C W H *** 'O s 1-1 o P -p o a? ToJ CO rH 04 0 U 01 t- CM co ^ C-- ON " u'' '4' a- "4- 5Jr* r* r* 1-- 1-- O SflCNO -rvj- CM *-- CM t- O - rn p- ro (M CM CM t-- T-- T" 1" ^-- vo OS CO O os os O rO CM VO VO ^ O <"0 ON O CO LTN 1-- LfN O 'J-NCO P-if' irvcc co (-0 r+~\ rjr*~\ O ON <"0 CO ^3* ao vo ^OONr--r-- vo vo VO ro ro CM CM CM CM CM CM o >i p-t i m r^i VO UTN t- O CO VO cooror-'*- <-"> r-"> -sj- rD r~\ rO LTN GO rn *- c-- O 'T vr vf O MS t-- rO CO ^ as ^ on co ^3* ITN ON OO CM CO O LTN LTV LfN O -P G i> a } i p *M t 0c) si P o w CP SO CcD Orl4 -fH-| S! P i CO i C C rH P o} 3 TOd fn CM <-- t-- VfN VO vO ON r<N rO 4" OS ^ O VO *^T ro Tj* ITS [-- IfScO CM rO ON rj-vO r- Oi^OCD CM r*N t-- CM rD MD lAr* no M- CO ON^r^VO tTN ON O co Mn ON O cTNr-- no t-- CM W fO ro M' Vf VO rl ITNcO CO 0 ro t-- MN tCN rn CO C-- r-- r\j ITNVO C-- O -r-* r^\ ro trv r- ono T- T-- CO CM ICN OS O T-- >-oos rn US ITN VO CM tO i ii I | a C oc roH p i Po O -rl 2U Hd P 0 01 --S OO VO TON CM *- CM cm m CM iCN O t- SO -sr T- SO CM UTN O VO TJ-VO CM -d-so C-- OS 00 ON t- CM tTN ITS t- 0 co OS irvoo on t*-- r-- r*\ go rn CM ir>o ONt-in 0 O ^ t- CO r- -- CM si- Os 00 CO OO ON CO 00 so os t-- r-- lTS vo on vo O C--O O CM CM O On t- t- CM ao ^ ^ M3 Os O ^ ON ON rO t- t-- rO O rD T-- t-- C o rH P H O o a >o o. c cOOf cO o ?H 3 O CO t CTN vO t-- CO Os O t- CM (O 3- ICS vo C--CO Os O CC LTN ltn ITS ITS LfS itsso VO so VO VO SO vovovovor ON ON Os On OS OS OS Os Os Os Os Os Cn On ON ON ON -- // -- 1971 1972 1973 A CO to to o CO I i JAPANESE PVC ASSOCIATION Annex 3 I Guide to Vinyl Chloride Operation Manual for Safe Handling and Use j-- 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-pre3sure 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 Firai aid 3.8 Education and training 4. Medical Screaming 5. Other Protection Procedures S43Z2014 IZ -- JAPANESE PVC ASSOCIATION 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". (b) 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. SV&ZZ2VZ 13 JAPANESE PVC ASSOCIATION o H +> <0 i-i +> in o c o 500 g ppm O > Start ventilation 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 CO (V) to o 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 /S JAPANESE PVC ASSOCIATION 4. 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 24322018 JAPANESE PVC ASSOCIATION I To All Members Annex 4 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. 24322019 -- /7 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. Sine erely, JAPANESE PVC ASSOCIATION M. Shimamura, President** ** 24322020 1 /Q -- JAPANESE PVC ASSOCIATION Prftss Re1esse Brief history of occupational health and safety for exposures to vinyl chloride monomer Annex 5 June 12, 1974 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. 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. 24322021 /9 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 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 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. 20 Annex 6 June loth, 1974 Sanitation of PVC food containers In the United States sonic VCM was detected in whisky packed in PVC containers sometime ago. Subsequently FDA unnounccd a ban against PVC containers used for alcoholic beverages us a provisional measure in May, 1973. Ve, Japan Hygienic PVC Association, followed to the FDA announcement without fulling 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 suspcctable 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 24322023 Japan Hygienic PVC Association -------- its organization -- Annex 7 CHAIRMAN BOARD OP 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 AFPAIRS Negotiation and. liaison vith the related official Agencies and refereiiteed Associations. Management of General affairs 22 -- Annex 8 VCM Migration from PVC Bottles June 1, 1974 j jJapan Hygienic PYC Association Experiment jl* VCM migration into alcoholic solvents with use PVC resins containing different levels of xesidual PVC bottles containing various levels of residua^ VCM ( l~ca. 20 ppm ) were moulded. Pilled with 20 and 50 ? alcoholic solutions intoVthe 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`fo 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 No. 2 No v 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?C alcoholic solution and sake from PVC bottles containing various levels of residual VCM by the same manner as in Table 1 . -- 23 24322025 Table 2 bottle weigth bottle volume VCM in bottle VCM in solution VCM migration ( gram ) ( ml ) ( ppm ) rate from solutions^ bottle ( $ ) 20$ alcohol II tt 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 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 VCH content in PVC compound and bottle i 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. % ZQZZ2VZ 24-------------- r c, Table 3 VCM in PVC compound ( PPn ) 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 96 Control method for YCM 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 ( ) from compounding process to bottle bloving process. f : VCM migration rate from PVC bottle into bottled food. Residual VCM amount in PYC compound = Xx A -------------------------- k . _f_ 10O X 100 Accordingly, to keep x -- value below 0.05 00m ; j In case of spirits, supposing A=10, k=80?6, f=30?6 are fixed 0. 05 |x 10 0.8 x 0.3 1 =' 2 |pp" ( 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. -- 26 r JAPANESE FVC ASSOCIATION Annex 9 Determination of Vinyl Chloride in the Worfcdnp- Environment ( draft ) 1. Scope The following procedure describes a method for the quantitative deteraination of vinyl chloride ( VCM ) in the working environment. 2. Outline of Method Air sample is drawn into a gaatight syringe and injected into the gas chromatograph and the area of the VCM peak measured. This area is compared to that of the calibration staudards. 3. . Apparatus (l ) G33 sampler 11.-, (2) Class bottle 201. (3) Gastight syringe (4 J Syringe (5) Vacuum Pump 200ml . 6) Mercury manometer !7; Gas chromatograph, equipped with flame ionization detector. 4. Reagents fl ) Liquified high purity VCH in bomb (2) Nj in bomb Gas Chromatograph Operating Conditions Column Stainless steel tubing 3 mm ID x 5 I* Stationary liquid 2O56 Tricresyl phosphate on stationary ; ( weight percent ) Stationary sbiidi Detector Injector temperature Column temperature Carrier gas Chromosorb V AV 60 ~80 mesh Hydrogen flame ionization detector 150 C 70 C Na at 60ml./ min Sample size Chart speed 5 ml. 20 mm / min <SZQZZtrZ 27 6. Standardization A. YCK Gas Sampling \ (I ) The assembly of apparatus for saapling of 7CM 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 VCJf bomb ( G ). (4) Open the valve of the 7CH bomb ( G ) gradually and introduce slowly 7CB gas into the gas sampler ( A ). (5) When the mercury manometer shows one atomospherie pressure, close the v value of the 7CM bomb ( G ). (6) Turn the three - way cock ( F ) to the vacuum pump and evacuate the gas sampler ( A ) again. (7) Repeat steps (3) -- (6) three times. (8) Finally, introduce 7CM gas into the ga3 sampler ( A )slightly higher ( Ca. 30 mmHg ) than 1 atomospherie 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 stanrdlards s is shown in Fig. 2. (2) Open the cock ( L ) and ( K ), and evacuate the 201 glass bottle ( H ). (3) Close tha code ( L ) and ( K ). (4) Drmm the 7CX gas into the gastight syringe through the silicon rubber septum ( P ) of the glass sampler ( a ) , and inject the 7CX gas to tm measured into the '201 glass bottle ( H ). 24322830 ZQ -- Volume of VCM to be drawn into gastight syringe 2 ml. 1 ml. 200 yi. 100 M1* 20 A*1 * VCM concentration of calibration standards 100 ppm 50 ppm 10 ppm 5 ppm 1 ppm . (5) Open the cock ( J ), then introduce slowly the Ha 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 VCM in the standard by following formula. ppm VCM Volume of VCM gas injected (jH.) Volume of 203. 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. 29 7. Procedure (l ) Set instrument parameters at tbe 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 -- Stturtless flmdh CP) Tij. I . Assembly on. i/ctf Am Sanpfw 3/ 24322033 a <;r>i c liiMaiSiliilftff^frr; :)rl!;gjpjfltr^ssfgBrafpgt;`h5-&?e: ;~ felijHrjMliiiigiifUinrrhhUmjntirrMHrH^^i'rrilir^rU-i-.-frinriLOU- pxi - na 7 -H ; :r. I r: rtSru p: trirrrj 24322034 iilLiliUiU2LH4'C.a'JliPAevJA eyv^ZiZAJM. ytOICL(LC :jjS1i111 Uj^r:;: ;:: ft:r` 1; - :. :;:::|: :L;jrl::|: r::j ^| i SUc :i8OrX250Tt) Annex 10 Method for the determination of vinyl chloride in PVC resin*and/or in food * 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 CTrlF) 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 ol of tetrahydrofuran* (THF) and close the tube tightly with a ground glass stopper or silicon rubber stopper. '.Vhen PVC resins are completely dissolved, 5~10yal 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 beverage's and edible oil, can be determined by injecting directly 5--lO^ttl aliquots of these foods into gas chromatograph. -- 33 24322035 3 .Preparation of standard solutions of vinyl chloride (i) Stock solution. About 1000 PPrt 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 -50vC with methanol-dry ice. Cii) 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, tjia 1 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 VYg : Weight of 1 ml stock solution cooled at ~50"C 34 24322636 b) About 0.05--0.2 PPM Vinyl Chloride Transfer aliquot z of about 10 PPM standard solution prepared as above to 100 ml olumetric flask to prepare about 0.05i 0.07t r 0.10, 0.15 and 0.2 PPM solutions, and dilute to volume with ethanol. Table 1 Gas Chromatography Conditions Column Carrier (i) A 3 x 3/ (i.d) coiled glass column packed with 25 wtSs PEG-20M on 60~80 mesh Chromosorb W-A'.V (ii) A 3TM x 3o/m Ci.d) coil glass column packed with 10 ivt/J Ucon oil LB-550X on 60~>8o aesh Aaakrom SD (iii) A 3 x 3/ (id) coiled glass column packed with lO wtSS Silicon DC-550 on 60~8o mesh Gasport A Any of these columns may be used. N2 2Q~60 ml/min H^Air Optimized Temp. Column ; 60~?0"C, Cample size 5~ 10 jjX Injector ; 150~200"C tSQZZZVZ --35 -- f