JPH01113447A - Radiation-resistant resin or resin composition - Google Patents
Radiation-resistant resin or resin compositionInfo
- Publication number
- JPH01113447A JPH01113447A JP26935287A JP26935287A JPH01113447A JP H01113447 A JPH01113447 A JP H01113447A JP 26935287 A JP26935287 A JP 26935287A JP 26935287 A JP26935287 A JP 26935287A JP H01113447 A JPH01113447 A JP H01113447A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- radiation
- polymn
- styrene
- random copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000005855 radiation Effects 0.000 title claims abstract description 26
- 229920005989 resin Polymers 0.000 title claims abstract description 9
- 239000011347 resin Substances 0.000 title claims abstract description 9
- 239000011342 resin composition Substances 0.000 title claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000005977 Ethylene Substances 0.000 claims abstract description 15
- 229920005604 random copolymer Polymers 0.000 claims abstract description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000573 polyethylene Polymers 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 230000005251 gamma ray Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WAUKBOOEPYNAGU-UHFFFAOYSA-N 1-phenylprop-2-enyl acetate Chemical compound CC(=O)OC(C=C)C1=CC=CC=C1 WAUKBOOEPYNAGU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical compound CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、原子力発電所や増殖炉等の放射線被曝環境下
で使用される耐放射線性樹脂もしくは樹脂組成物に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a radiation-resistant resin or resin composition used in radiation-exposed environments such as nuclear power plants and breeder reactors.
（従来の技術）
原子力発電所の格納容器内や使用済核燃料再処理プラン
ト内等の高放射線領域における各種配線用の電線やケー
ブルの被覆材等の材料に対しては、高度の耐放射線性が
強く要求されている。一般に、ポリエチレンはその優れ
た電気的特性、機械的特性および経済性などから電線や
ケーブルの絶縁材、外被材、作業衣、シート、パイプ等
に広く用いられ、原子炉周辺の配電線、機器類にも多く
使用されているが（１４１１％β線、γ線および中性子
などの放射線の被曝によって脆（なるという問題を有し
ている。(Prior technology) Materials such as coating materials for wires and cables used in various wiring in high radiation areas such as inside the containment vessels of nuclear power plants and inside spent nuclear fuel reprocessing plants have a high degree of radiation resistance. strongly requested. In general, polyethylene is widely used for insulation materials for electric wires and cables, sheathing materials, work clothes, sheets, pipes, etc. due to its excellent electrical properties, mechanical properties, and economic efficiency, as well as for power distribution lines and equipment around nuclear reactors. However, it has the problem of becoming brittle when exposed to radiation such as beta rays, gamma rays, and neutrons.
上記耐放射線性を改良する方法として耐放射線安定（防
御）剤としてアルキルピレンなどを配合する方法が知ら
れている（特開昭５０−１０６１７２号）。しかしなが
ら、これらの方法では配合剤の分散性や相溶性が悪く、
長期安定性に問題がある。また比較的安価な方法として
ポリスチレンをポリエチレンなどにブレンドしたり、ポ
リエチレンにスチレンをグラフト共重合する方法（特開
昭５９−８．９３４５号）などが提案されているが、前
者は相溶性が悪く相分離が生じ、後者においては、耐放
射線性効果が未だ充分ではなく実用性に乏しい。更に、
ポリイミド、ポリエーテルスルフォン、ポリエーテルエ
ーテルケドンなどの耐放射線性が良好なポリマーも考え
られるが高価であること、押出成形などが困難であるこ
と等経済性や加工性に問題がある。As a method for improving the above-mentioned radiation resistance, a method is known in which an alkylpyrene or the like is added as a radiation-resistant stabilizing (defensive) agent (Japanese Patent Application Laid-open No. 106172/1982). However, these methods have poor dispersibility and compatibility of compounding agents,
There are problems with long-term stability. In addition, relatively inexpensive methods have been proposed, such as blending polystyrene with polyethylene or graft copolymerizing styrene with polyethylene (Japanese Patent Application Laid-Open No. 1989-89345), but the former has poor compatibility. Phase separation occurs, and in the latter case, the radiation resistance effect is still insufficient and it is impractical. Furthermore,
Polymers with good radiation resistance such as polyimide, polyether sulfone, and polyether ether kedone are conceivable, but they have problems in economic efficiency and processability, such as being expensive and difficult to extrude.
（発明が解決しようとしている問題点）上記の如（、高
放射線領域における耐放射線性Ｓ：＊・ケーブル用絶縁
材、外被材あるいは作業衣、シート、パイプ等に使用さ
れている従来の組成物では、安価で、電気的性質、機械
的強度を損なわずに耐放射線性を向上せしめることは困
難であった。(Problem to be solved by the invention) As described above (radiation resistance S in high radiation areas: It has been difficult to improve the radiation resistance of materials without impairing their electrical properties and mechanical strength at low cost.
本発明は、この問題を鋭意検討した結果、電気的性質、
機械的強度を損なわずに安価で、優れた耐放射線性を有
する樹脂およびその組成物を見出−したものである。As a result of intensive study on this problem, the present invention has been developed based on the electrical properties,
A resin and a composition thereof have been discovered which are inexpensive and have excellent radiation resistance without sacrificing mechanical strength.
（発明の構成）
本発明は、実質的にエチレンとスチレン系単量体とのラ
ンダム共重合体であって、該共重合体もしくは該共重合
体を含む樹脂組成物中のスチレン系単量体含有量が５〜
３０重量％である耐放射線性樹脂もしくは樹脂組成物に
関するものである。(Structure of the Invention) The present invention provides a substantially random copolymer of ethylene and a styrenic monomer, the styrenic monomer in the copolymer or a resin composition containing the copolymer. Content is 5~
30% by weight of a radiation-resistant resin or resin composition.
本発明における実質的にエチレンとスチレン系単量体と
のランダム共重合体とはエチレン、またはエチレンおよ
び他のエチレン性不飽和単量体、とスチレン系単量体と
のランダム共重合体である。In the present invention, the substantially random copolymer of ethylene and a styrenic monomer is a random copolymer of ethylene, or ethylene and other ethylenically unsaturated monomers, and a styrenic monomer. .
本発明で用いるスチレン系単量体とは、例えばスチレン
、核置換スチレン（例えばメチルスチレン、ジメチルス
チレン、エチルスチレン、メトキシスチレン、エトキシ
スチレン、ビニル安息香Ｍ、ビニル安息香Ｍメチル、ビ
ニルベンジルアセテート、ヒドロキシスチレン）、α−
置換スチレン（例えｔｔ ａ−メチルスチレン、ａ−エ
チルスチレン、ａ−クロロ−スチレン）すどのスチレン
またはスチレン誘導体が挙げられる。The styrenic monomers used in the present invention include, for example, styrene, nuclear-substituted styrene (e.g., methylstyrene, dimethylstyrene, ethylstyrene, methoxystyrene, ethoxystyrene, vinylbenzoic M, vinylbenzoic M-methyl, vinylbenzyl acetate, hydroxystyrene). ), α−
Mention may be made of styrene or styrene derivatives such as substituted styrenes (eg, a-methylstyrene, a-ethylstyrene, a-chloro-styrene).
上記共重合体中のスチレン系単量体の含有量は、単量体
換算で、５ないし３０重量％を占め、好ましくは６な・
いし２０重量％を占めることが肝要である。The content of the styrene monomer in the above copolymer is 5 to 30% by weight, preferably 6% by weight, in terms of monomer.
It is important that the content of carbon be 20% by weight.
また本発明におけるエチレン性不飽和単量体とは、例え
ばプロピレン、ブテン−１、ペンテン−１、ヘキセン−
１，４−メチルペンテン−１、オクテン−１、デセン−
１などのａ−オレフィン類； ぎ酸ビニル、プロピオン
酸ビニル、酢酸ビニルなどのビニルエステル類；メタク
リル酸、アクリル酸、メタクリル酸エチル、アクリル酸
エチルなどの（メタ）クリル酸またはそのエステルおよ
びこれらの混合物などを例示することができる。これら
エチレン性不飽和単量体の含有量は、０〜２０重量％、
特に１５重量％以下が好ましい。In addition, the ethylenically unsaturated monomer in the present invention includes, for example, propylene, butene-1, pentene-1, hexene-1,
1,4-methylpentene-1, octene-1, decene-
a-olefins such as 1; vinyl esters such as vinyl formate, vinyl propionate, and vinyl acetate; (meth)acrylic acid or its esters such as methacrylic acid, acrylic acid, ethyl methacrylate, and ethyl acrylate; Examples include mixtures. The content of these ethylenically unsaturated monomers is 0 to 20% by weight,
In particular, it is preferably 15% by weight or less.
本発明においては前記のランダム共重合体に他のエチレ
ン系重合体を配合し得る。In the present invention, other ethylene polymers may be blended with the random copolymer.
上記他のエチレン系重合体としては、高、中、低密度ポ
リエチレン、エチレンとプロピレン、ブテン−１、ペン
テン−１、ヘキセン−１，４−メチルペンテン−１、オ
クテン−１、デセン−１等の炭素数３〜１２のａ−オレ
フィンとの共重合体、エチレン−プリピレン共重合体ゴ
ム、エチレン−プロピレン−ジエン共重合体ゴム、エチ
レンと酢酸ビニル、アクリル酸エチル、メタクリル酸、
メタクリル酸エチル、マレイン酸、無水マレイン酸等の
極性基含有モノマーとの共重合体、あるいは、前記エチ
レン単独もしくはエチレンとα−オレフィン共重合体を
アクリル酸、マレイン酸などの不飽和カルボン酸または
その誘導体で変性した重合体等およびそれらの混合物が
挙げられる。これらの中でも特に密度０．８５〜０．９
１ｇ／ｄの極低密度ポリエチレン、密度０．９２〜０．
９４ｇ／ｃ＋／の高圧法ポリエチレンまたはＩ［＃ｌＩ
状ポリエチレン、エチレン−プロピレン共重合体ゴム、
エチレン−プロピレン−ジエン共重合体ゴムなどが好ま
しく使用される。Other ethylene polymers include high, medium, and low density polyethylene, ethylene and propylene, butene-1, pentene-1, hexene-1,4-methylpentene-1, octene-1, decene-1, etc. Copolymers with a-olefins having 3 to 12 carbon atoms, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, ethylene and vinyl acetate, ethyl acrylate, methacrylic acid,
A copolymer with a polar group-containing monomer such as ethyl methacrylate, maleic acid, or maleic anhydride; Examples include polymers modified with derivatives and mixtures thereof. Among these, especially density 0.85-0.9
1g/d ultra-low density polyethylene, density 0.92-0.
94 g/c+/ high pressure polyethylene or I [#lI
polyethylene, ethylene-propylene copolymer rubber,
Ethylene-propylene-diene copolymer rubber and the like are preferably used.
上記ランダム共重合体を含む樹脂組成物においても組成
物中のスチレン単量体の含有量はこれら全樹脂の単量体
換算で、５ないし３０重量％、好ましくは６ないし２０
重量％を占めることが肝要である。In the resin composition containing the above-mentioned random copolymer, the content of styrene monomer in the composition is 5 to 30% by weight, preferably 6 to 20% by weight in terms of the monomer of all these resins.
It is important to account for the weight percentage.
該スチレン系単量体の含有量が５重量％未満では耐放射
線性を十分に改善できず、また、３０重量％を超えると
耐熱性が著しく低下する。If the content of the styrene monomer is less than 5% by weight, the radiation resistance cannot be sufficiently improved, and if it exceeds 30% by weight, the heat resistance will be significantly reduced.
本発明で用いる実質的にエチレンとスチレン系単量体と
のランダム共重合体は、ラジカル重合、イオン重合など
によって製造されたものであっても良く、特にその製造
条件を限定するものではない。しかし高圧ラジカル重合
法が電気的特性に悪影響を与える触媒残渣等がないこと
、グラフト変性においてしばしば認められるゲルの発生
がないことなどの点から好ましい。高圧ラジカル重合に
よる実質的にエチレンとスチレン系単量体からなるラン
ダム共重合体の製造方法は、ラジカル重合開始剤の存在
下で重合圧力５００〜４０００ｋｇ／ｃｄ、好ましくは
１Ｇ００〜３５００ｋｇ ／ ａｄ 、重合温度５０〜
４００℃、好ましくは１００〜３５０℃の条件下、連鎖
移動剤、必要に応じて助剤の存在下に種型または管型反
応容器内で該単量体を同時に、あるいは段階的に接触、
重合させる方法である。The substantially random copolymer of ethylene and styrene monomer used in the present invention may be produced by radical polymerization, ionic polymerization, etc., and the production conditions are not particularly limited. However, the high-pressure radical polymerization method is preferable because there is no catalyst residue that adversely affects electrical properties, and there is no gel formation that is often observed in graft modification. A method for producing a random copolymer consisting essentially of ethylene and styrene monomers by high-pressure radical polymerization involves polymerization at a polymerization pressure of 500 to 4000 kg/cd, preferably 1G00 to 3500 kg/ad, in the presence of a radical polymerization initiator. Temperature 50~
Contacting the monomers simultaneously or in stages at 400° C., preferably from 100 to 350° C., in the presence of a chain transfer agent and optionally an auxiliary agent in a seed-type or tubular reaction vessel;
This is a method of polymerization.
上記ラジカル開始剤としては、有機過酸化物、アゾ化合
物、アミンオキシド化合物、酸素などの通例の開始剤が
挙げられる。Examples of the radical initiator include conventional initiators such as organic peroxides, azo compounds, amine oxide compounds, and oxygen.
また、連鎖移動剤としては、水素、プロピレン、ブテン
−１，０１〜Ｃ２゜またはそれ以上の飽和脂肪族炭化水
素およびハロゲン置換炭化水素、例えばメタン、エタン
、プロパン、ブタン、イソブタン、ｎ−ヘキサン、シク
ロパラフィン類、クロロフォルム、および四塩化炭素、
Ｃ□〜Ｃ２゜またはそれ以上の飽和脂肪族アルコール、
例えばメタノール、エタノール、プロパツールおよびイ
ソプロパツール、Ｃ８〜Ｃ２゜またはそれ以上の飽和脂
肪族カルボニル化合物、例えば二酸化炭素、アセトンお
よびメチルエチルケトン並びに芳香族化合物、例えばト
ルエン、ジエチルベンゼンおよびキシレンのような化合
物等が挙げられる。Chain transfer agents include hydrogen, propylene, butene-1,01 to C2° or higher saturated aliphatic hydrocarbons, and halogen-substituted hydrocarbons, such as methane, ethane, propane, butane, isobutane, n-hexane, cycloparaffins, chloroform, and carbon tetrachloride,
Saturated aliphatic alcohol of C□~C2° or more,
Examples include methanol, ethanol, propatool and isopropanol, C8 to C2° or higher saturated aliphatic carbonyl compounds such as carbon dioxide, acetone and methyl ethyl ketone, and aromatic compounds such as toluene, diethylbenzene and xylene. Can be mentioned.
尚、本発明Ｃとおいて上記ランダム共重合体もしくはそ
の組成物に対してその使用目的に応じて他の熱可塑性樹
脂、合成ゴム、天然ゴムあるいは有機・無機フィラー、
難燃剤、酸化防止剤、滑剤、有機・無機系の各種顔料、
紫外線防止剤、分散剤、銅害防止剤、中和剤、発泡剤、
可塑剤、気泡防止剤、流れ性改良剤、ウェルド強度改良
剤、核剤等の添加剤を特性を低下させない範囲で加える
ことは何ら差し支えない。In Invention C, other thermoplastic resins, synthetic rubber, natural rubber, or organic/inorganic fillers may be added to the random copolymer or its composition depending on the purpose of use.
Flame retardants, antioxidants, lubricants, various organic and inorganic pigments,
UV inhibitor, dispersant, copper damage inhibitor, neutralizing agent, foaming agent,
There is no problem in adding additives such as plasticizers, anti-bubble agents, flowability improvers, weld strength improvers, nucleating agents, etc. to the extent that the properties do not deteriorate.
また、架橋構造を導入するため架橋剤（例えば有機過酸
化物、イオウ、シラン系架橋剤など）、架橋助剤を添加
したり、電離性放射線を照射することも何ら差し支えな
い。Further, in order to introduce a crosslinked structure, there is no problem in adding a crosslinking agent (for example, an organic peroxide, sulfur, a silane type crosslinking agent, etc.) or a crosslinking aid, or irradiating with ionizing radiation.
（実施例）
以下に実施例について示すが、本発明はこれらによって
何等限定、されるものではない。(Examples) Examples are shown below, but the present invention is not limited to these in any way.
例１〜３および 較例１〜３
窒素およびエチレンで充分に置換した攪拌機付き金属製
オートクレーブに所定量のエチレン、スチレンおよび連
鎖移動剤であるｎ−へブタンを仕込み、更に重合開始剤
であるジーｔａｒｔ−ブチルペルオキシドを注入し、重
合圧力１９００ｋｇ／ｃｄ１重合温度１８０℃、重合時
間４０分の重合条件で重合を行い、生成したポリマーを
精製、真空乾燥を行った。ここでエチレン、スチレンな
どの仕込量を湾えて種々のエチレン−スチレンランダム
共重合体（Ｅｔ−Ｓｔ共重合体と称する）を合成した。Examples 1 to 3 and Comparative Examples 1 to 3 A predetermined amount of ethylene, styrene, and n-hebutane as a chain transfer agent were charged into a metal autoclave equipped with a stirrer that had been sufficiently purged with nitrogen and ethylene, and then a polymerization initiator, di-hexane, was charged. Tart-butyl peroxide was injected and polymerization was carried out under the following conditions: polymerization pressure: 1900 kg/cd1, polymerization temperature: 180°C, polymerization time: 40 minutes, and the resulting polymer was purified and vacuum dried. Here, various ethylene-styrene random copolymers (referred to as Et-St copolymers) were synthesized by varying the amount of ethylene, styrene, etc. charged.
得られた上記ランダム共重合体および低密度ポリエチレ
ン（メルトインデックス（ＶＦＲ）−１０ｇ／１０ｍ＋
ｎ、密度（ｄ）＝Ｏ１９２２ｇ／ｃｄ 商品名：日石
しクスロンＷ２Ｏ００日本石油化学■製）、極低密度ポ
リエチレン（ＭＦＲ＝ １．０ｇ ７１０ｍ１ｎ、
ｄ ＝ ０．９０５ｇ ／ ｃｊ商品名：日石ソフトレ
ックス０９０５２ 日本石油化学■製）に酸化防止剤
（商品名ニックラック３００、大向新興化学■製）など
を第１表に示す部数となるように配合し、加熱ロールに
て良く混和し、この混和物を１８０℃にて３０分間プレ
ス成形し、１ｍおよび３ＩＩＩＩｌ厚の試験シートを作
成した。The obtained random copolymer and low density polyethylene (melt index (VFR) -10g/10m+
n, density (d) = O1922g/cd Product name: Nisseki Shixuron W2O00 manufactured by Nippon Petrochemicals ■), ultra-low density polyethylene (MFR = 1.0g 710m1n,
d = 0.905g / cjProduct name: Nisseki Softlex 09052 (manufactured by Nippon Petroleum Chemicals) and an antioxidant (product name: Nicklac 300, manufactured by Ohmukai Shinko Chemical), etc., in the number of copies shown in Table 1. The mixture was mixed well with a heated roll, and the mixture was press-molded at 180°C for 30 minutes to prepare test sheets of 1 m and 3IIIl thickness.
このようにして得られたシートにコバルト−６０、Ｓ源
を用いてγ線を常温、空気中で線量率０．５Ｍｒａｄ／
Ｈｒにて総線量２００Ｍｒａｄを照射し、照射前後の物
性を評価した。結果を第１表に示した。（各配合割合は
全て重量部である）。The thus obtained sheet was irradiated with gamma rays at room temperature using a cobalt-60 and S source at a dose rate of 0.5 Mrad/
Irradiation was performed at a total dose of 200 Mrad at Hr, and the physical properties before and after irradiation were evaluated. The results are shown in Table 1. (All blending ratios are parts by weight).
尚、試験法は以下の通りである。The test method is as follows.
１． 引張強度および伸び率： ＪＩＳ Ｋ ７１１３
に準拠２、 誘電正接 ： ＪＩＳ Ｃ２１
２３に準拠第１表
本（）内はスチレン含有量（ａｔ（６）１′ 高圧法低
密度ポリエチレン
２１ 極低密度ポリエチレン
この結果、スチレン含有量３重量％では、γ線照射後の
伸び率が著しく低下するのに対して本発明の範囲内にお
いてはγ線照射後でも１０倍以上の伸びを保持している
ことが解る。また極低密度ポリエチレンをブレンドした
ものも本発明の範囲内のスチレン含有量であれば機械特
性、電気特性を保持しつつ耐放射線性を向上させうろこ
とが解る。1. Tensile strength and elongation: JIS K 7113
Compliant with 2, dielectric loss tangent: JIS C21
Based on 23, the styrene content (at (6) 1' in parentheses in Table 1 is It can be seen that within the scope of the present invention, the elongation is maintained at more than 10 times even after γ-ray irradiation.In addition, products blended with extremely low density polyethylene are also included in the range of styrene within the scope of the present invention. It can be seen that if the content is high enough, radiation resistance can be improved while maintaining mechanical and electrical properties.
−４〜５および ４〜７
実施例１と同様にして合成した共重合体に、第２表に示
す量の老化防止剤、有機過酸化物（ジクミルパーオキサ
イド）を加え、良く混練した後１６０℃で３０分間プレ
ス成形し、１間厚の架橋シートを作製し、熱老化性（１
７０″ｃＸ７日間）、γ線照射後の機械的強度（引っ張
り強度、伸び率）を評価した結果を第２表に示した。-4 to 5 and 4 to 7 After adding an anti-aging agent and an organic peroxide (dicumyl peroxide) in the amounts shown in Table 2 to the copolymer synthesized in the same manner as in Example 1, and kneading well. Press molding was carried out at 160°C for 30 minutes to produce a cross-linked sheet with a thickness of 1 cm.
Table 2 shows the results of evaluating the mechanical strength (tensile strength, elongation rate) after γ-ray irradiation.
また比較例７は、比較例２で用いた低密度ポリエチレン
（ＨｐＬＤＰＥ）にスチレンモノマー８ｆｆｉ、１％を
グラフトさせ、老化防止剤とジクミルパーオキサイドを
加えて実施例４と同様に峙て架橋シートを作製し、評価
した結果を第２表に示した。In Comparative Example 7, 8ffi, 1% of styrene monomer was grafted onto the low density polyethylene (HpLDPE) used in Comparative Example 2, and an anti-aging agent and dicumyl peroxide were added, and a crosslinked sheet was prepared in the same manner as in Example 4. The results of the evaluation are shown in Table 2.
第２表
本（）内はスチレン含有量（ｗｔ（財）３７ スチレ
ングラフト低密度ポリエチレン手続補正書
昭和６２年１１月２５日
特許庁長官 小 川 邦 夫 殿
１、事件の表示
昭和６２年特許願第２６９３５２号
２、発明の名称
名称 日本石油化学株式会社
４、代理人
５、補正の対象
６、補正の内容
（１）明細書１３頁最下行の後に次の文を押入する。Table 2: Styrene content (wt) 37 Styrene-grafted low-density polyethylene procedural amendment November 25, 1985 Director General of the Patent Office Kunio Ogawa 1, Indication of the case 1988 Patent application No. 269352 2, Name of the invention: Japan Petrochemical Co., Ltd. 4, Agent 5, Subject of amendment 6, Contents of amendment (1) The following sentence should be inserted after the bottom line of page 13 of the specification.
「この結果、スチレン単量体含有量が３重量％および低
密度ポリエチレンでは耐放射線性が悪（、またスチレン
単量体含有量が３３重量％では耐放射線性には優れるも
のの耐熱老化性が劣るものであることがわかる。また低
密度ポリエチレンにスチレンモノマーをグラフト化して
も、耐放射線性の改良ができないだけでなく耐熱老化性
も低下してしまうことがわかる。``As a result, low-density polyethylene with a styrene monomer content of 3% by weight has poor radiation resistance (and a styrene monomer content of 33% by weight has excellent radiation resistance but poor heat aging resistance. Furthermore, it can be seen that even if styrene monomer is grafted onto low density polyethylene, not only the radiation resistance cannot be improved but also the heat aging resistance decreases.
（発明の効果）(Effect of the invention)
Claims (3)
ム共重合体であって、該共重合体もしくは該共重合体を
含む樹脂組成物中のスチレン系単量体含有量が５〜３０
重量％であることを特徴とする耐放射線性樹脂もしくは
樹脂組成物。(1) A substantially random copolymer of ethylene and a styrene monomer, wherein the copolymer or the resin composition containing the copolymer has a styrene monomer content of 5 to 30
% by weight of a radiation-resistant resin or resin composition.
００ｋｇ／ｃｍ＾２、重合温度５０〜４００℃の高圧ラ
ジカル重合法によって得られるものである特許請求の範
囲第１項記載の耐放射線性樹脂もしくは樹脂組成物。(2) The random copolymer has a polymerization pressure of 500 to 40
2. The radiation-resistant resin or resin composition according to claim 1, which is obtained by high-pressure radical polymerization at a polymerization temperature of 50 to 400°C.
レン系重合体を配合してなる特許請求の範囲第１項また
は第２項記載の耐放射線性樹脂組成物。(3) The radiation-resistant resin composition according to claim 1 or 2, wherein the resin composition is formed by blending the random copolymer with another ethylene polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26935287A JPH01113447A (en) | 1987-10-27 | 1987-10-27 | Radiation-resistant resin or resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26935287A JPH01113447A (en) | 1987-10-27 | 1987-10-27 | Radiation-resistant resin or resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01113447A true JPH01113447A (en) | 1989-05-02 |
Family
ID=17471184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26935287A Pending JPH01113447A (en) | 1987-10-27 | 1987-10-27 | Radiation-resistant resin or resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01113447A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999048972A1 (en) * | 1998-03-23 | 1999-09-30 | Denki Kagaku Kogyo Kabushiki Kaisha | Resin composition |
| EP0906932A3 (en) * | 1997-10-01 | 2000-04-26 | Denki Kagaku Kogyo Kabushiki Kaisha | Film and stretch packaging film |
| EP0869146A4 (en) * | 1996-10-23 | 2000-11-08 | Mitsui Chemicals Inc | Ethylene copolymer composition and moldings |
-
1987
- 1987-10-27 JP JP26935287A patent/JPH01113447A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0869146A4 (en) * | 1996-10-23 | 2000-11-08 | Mitsui Chemicals Inc | Ethylene copolymer composition and moldings |
| EP0906932A3 (en) * | 1997-10-01 | 2000-04-26 | Denki Kagaku Kogyo Kabushiki Kaisha | Film and stretch packaging film |
| US6248850B1 (en) | 1997-10-01 | 2001-06-19 | Denki Kagaku Kogyo Kabushiki Kaisha | Film and stretch packaging film |
| US6417308B2 (en) | 1997-10-01 | 2002-07-09 | Denki Kagaku Kogyo Kabushiki Kaisha | Film and stretch packaging film |
| WO1999048972A1 (en) * | 1998-03-23 | 1999-09-30 | Denki Kagaku Kogyo Kabushiki Kaisha | Resin composition |
| US6410649B1 (en) | 1998-03-23 | 2002-06-25 | Denki Kagaku Kogyo Kabushiki Kaisha | Resin composition |
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