JPH11265618A - Crosslinkable resin composition for electrical insulation, electrical insulator, electric wire / cable - Google Patents
Crosslinkable resin composition for electrical insulation, electrical insulator, electric wire / cableInfo
- Publication number
- JPH11265618A JPH11265618A JP6794698A JP6794698A JPH11265618A JP H11265618 A JPH11265618 A JP H11265618A JP 6794698 A JP6794698 A JP 6794698A JP 6794698 A JP6794698 A JP 6794698A JP H11265618 A JPH11265618 A JP H11265618A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polyethylene
- parts
- group
- resin composition
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 238000010292 electrical insulation Methods 0.000 title claims abstract description 7
- 239000000615 nonconductor Substances 0.000 title claims description 4
- -1 polyethylene Polymers 0.000 claims abstract description 143
- 239000004698 Polyethylene Substances 0.000 claims abstract description 128
- 229920000573 polyethylene Polymers 0.000 claims abstract description 128
- 238000002844 melting Methods 0.000 claims abstract description 48
- 230000008018 melting Effects 0.000 claims abstract description 48
- 238000004132 cross linking Methods 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 125000000962 organic group Chemical group 0.000 claims abstract description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 4
- 239000003707 silyl modified polymer Substances 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 239000003963 antioxidant agent Substances 0.000 claims description 50
- 230000003078 antioxidant effect Effects 0.000 claims description 47
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 30
- 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 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004020 conductor Substances 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 6
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 3
- CWJHMZONBMHMEI-UHFFFAOYSA-N 1-tert-butylperoxy-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1 CWJHMZONBMHMEI-UHFFFAOYSA-N 0.000 claims description 2
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 claims description 2
- PMAAOHONJPSASX-UHFFFAOYSA-N 2-butylperoxypropan-2-ylbenzene Chemical compound CCCCOOC(C)(C)C1=CC=CC=C1 PMAAOHONJPSASX-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- 229910000077 silane Inorganic materials 0.000 abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000003989 dielectric material Substances 0.000 abstract description 5
- 240000005572 Syzygium cordatum Species 0.000 abstract description 3
- 235000006650 Syzygium cordatum Nutrition 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 description 50
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 31
- 239000012975 dibutyltin dilaurate Substances 0.000 description 31
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 238000002156 mixing Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000006378 damage Effects 0.000 description 8
- 239000004594 Masterbatch (MB) Substances 0.000 description 7
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000006232 furnace black Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- ZNHPPXDUJKXBNM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)hexane Chemical compound CC(C)(C)OOC(C)CCC(C)OOC(C)(C)C ZNHPPXDUJKXBNM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920003020 cross-linked polyethylene Polymers 0.000 description 3
- 239000004703 cross-linked polyethylene Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- IZOFRDJGAYUGTP-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O IZOFRDJGAYUGTP-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SZXBKUCBXJGWOC-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)propanehydrazide Chemical compound CC(C)(C)C1=CC(CCC(=O)NN)=C(O)C(C(C)(C)C)=C1 SZXBKUCBXJGWOC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- MDLJJZBHMAKNRH-UHFFFAOYSA-N N-(3,5-ditert-butylphenyl)-1,3,5-triazin-2-amine Chemical compound C(C)(C)(C)C=1C=C(NC2=NC=NC=N2)C=C(C=1)C(C)(C)C MDLJJZBHMAKNRH-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- KCYVHFFDTZVJAD-UHFFFAOYSA-N [4-(2,4-dimethyl-4-phenyl-3-propan-2-ylpentan-2-yl)peroxy-2,4-dimethyl-3-propan-2-ylpentan-2-yl]benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C(C)C)C(C)(C)OOC(C)(C)C(C(C)C)C(C)(C)C1=CC=CC=C1 KCYVHFFDTZVJAD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MHXOSBZVBRALMN-UHFFFAOYSA-N but-3-enoxy(dimethyl)silane Chemical compound C[SiH](C)OCCC=C MHXOSBZVBRALMN-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- ORHSGYTWJUDWKU-UHFFFAOYSA-N dimethoxymethyl(ethenyl)silane Chemical compound COC(OC)[SiH2]C=C ORHSGYTWJUDWKU-UHFFFAOYSA-N 0.000 description 1
- BDQBOORCNIHICP-UHFFFAOYSA-N dimethyl(prop-2-enoxy)silane Chemical compound C[SiH](C)OCC=C BDQBOORCNIHICP-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Abstract
(57)【要約】
【課題】押出成形性に優れ、加熱変形率と伸び、耐水ト
リー性、特に耐ボウタイトリー特性を大幅に改善できる
シラングラフト・水架橋法により架橋できる電気絶縁用
樹脂組成物及び当該樹脂組成物からなる電気絶縁物及び
電線・ケーブルの提供。
【解決手段】高圧ラジカル重合により合成され、融点が
１１５℃以上で密度が０．９２５〜０．９３５ｇ／cm3
のポリエチレン（ａ）を主体とするポリマ、又は前記ポ
リエチレン（ａ）９９〜５０重量部と密度が０．９１５
〜０．９２５ｇ／cm3 のポリエチレン（ｂ）１〜５０重
量部を含むブレンドポリエチレンを主体とするポリマ
と、一般式
ＲＲ′ＳｉＹ2
（式中Ｒはオレフィン性不飽和炭化水素基あるいはハイ
ドロカーボンオキシ基であり、Ｙは加水分解可能な有機
基であり、Ｒ′は前記Ｒ基かＹ基である）で表されるシ
ランとを、遊離ラジカルを生じさせる化合物の存在下で
反応させて得られるシラン変性ポリマからなる架橋性電
気絶縁用樹脂組成物。(57) [Summary] [Problem] A resin composition for electrical insulation which can be crosslinked by a silane grafting / water crosslinking method, which has excellent extrusion moldability, and can significantly improve the heat deformation rate and elongation, the water tree resistance, especially the bow titlery resistance. And an electric insulator and an electric wire / cable comprising the resin composition. The composition is synthesized by high pressure radical polymerization, has a melting point of 115 ° C. or more and a density of 0.925 to 0.935 g / cm 3.
A polymer mainly composed of polyethylene (a), or 99 to 50 parts by weight of the polyethylene (a) and a density of 0.915
A polymer mainly composed of a blended polyethylene containing 1 to 50 parts by weight of polyethylene (b) having a molecular weight of 0.95 g / cm 3 and a general formula RR′SiY 2 wherein R is an olefinically unsaturated hydrocarbon group or a hydrocarbonoxy group; Y is a hydrolyzable organic group, and R ′ is the above-mentioned R group or Y group) in the presence of a compound generating free radicals. A crosslinkable resin composition for electrical insulation comprising a silane-modified polymer.
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、水分と接触させる
ことにより架橋させることができる架橋性電気絶縁用樹
脂組成物及びこの組成物からなる電気絶縁物並びに電線
・ケーブルに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable resin composition for electric insulation which can be crosslinked by contact with moisture, an electric insulator comprising the composition, and an electric wire / cable.
【０００２】[0002]
【従来技術】ポリオレフィン系樹脂にビニルアルコキシ
シラン等のシランを添加し、遊離ラジカルを生じさせる
化合物（以下「遊離ラジカル発生剤」とう）の存在下で
反応させて得られたシラングラフトポリオレフィンを、
シラノール縮合触媒の存在下で水分と接触させることに
より架橋させる、いわゆるシラングラフト・水架橋法
は、有機過酸化物を用いて架橋を行う化学架橋方式より
も低コストで架橋ポリエチレン材料を提供できるため、
電線・ケーブルの絶縁層やシース並びに電線・ケーブル
の付属品等の架橋方法として広く用いられている。2. Description of the Related Art A silane-grafted polyolefin obtained by adding a silane such as vinylalkoxysilane to a polyolefin resin and reacting in the presence of a compound generating free radicals (hereinafter referred to as "free radical generator") is obtained.
The so-called silane grafting / water crosslinking method of crosslinking by contact with water in the presence of a silanol condensation catalyst can provide a crosslinked polyethylene material at a lower cost than the chemical crosslinking method of crosslinking using an organic peroxide. ,
It is widely used as a method for bridging insulation layers and sheaths of electric wires and cables and accessories of electric wires and cables.
【０００３】この方法は、より具体的には、高温の成形
加工機（例えば押出機）中で、少量の有機過酸化物を遊
離ラジカル発生剤として用い、ポリオレフィン系樹脂に
ビニルアルコキシシラン等のシランをグラフト共重合さ
せてから押出して成形体とし、その後、高温高湿度雰囲
気（または温水中）に成形体をさらすことにより水分と
接触させ、成形体中に混合された又は成形体表面から浸
透させたジブチル錫ジラウレート等のシラノール縮合触
媒の作用により、ポリオレフィン系樹脂にグラフトした
シランの加水分解および縮合を起こさせて架橋するもの
である。[0003] More specifically, this method uses a small amount of an organic peroxide as a free radical generator in a high-temperature molding machine (eg, an extruder) and uses a silane such as vinylalkoxysilane as a polyolefin resin. Is extruded into a molded article after graft copolymerization, and then exposed to moisture by exposing the molded article to a high-temperature, high-humidity atmosphere (or hot water) to allow the molded article to be mixed with or penetrated from the surface of the molded article. The reaction is effected by the action of a silanol condensation catalyst such as dibutyltin dilaurate or the like to cause hydrolysis and condensation of the silane grafted to the polyolefin-based resin to cause crosslinking.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、このシ
ラングラフト・水架橋法には、加熱変形率等の高温特性
を高める目的で架橋度を高く設定すると、化学架橋法に
比べて伸びが著しく低下するという問題がある。However, in this silane graft / water crosslinking method, if the degree of crosslinking is set high for the purpose of enhancing the high-temperature properties such as the heat deformation rate, the elongation is significantly reduced as compared with the chemical crosslinking method. There is a problem.
【０００５】また、銅導体、銅テープと直接触れるもの
には、銅イオンによる促進熱劣化、いわゆる金属害を防
ぐため、サリチル酸誘導体やヒドラジド誘導体に代表さ
れる金属害防止剤を配合するのが一般的であるが、融点
が２００℃以上と高く、ポリエチレン中で溶融分散させ
にくい。また、溶媒にも溶解させにくいため、ビニルア
ルコキシシランに溶解してポリエチレンに供給すること
が困難である。そのため、ポリエチレン中での分散性が
悪く、絶縁体中で異物となり、耐水トリー特性、特に耐
ボウタイトリー特性を悪くする可能性がある。[0005] In addition, in order to prevent accelerated thermal deterioration due to copper ions, so-called metal damage, a metal damage inhibitor typified by a salicylic acid derivative or a hydrazide derivative is generally added to a copper conductor or a material that directly contacts a copper tape. However, the melting point is as high as 200 ° C. or higher, and it is difficult to melt and disperse in polyethylene. Further, since it is difficult to dissolve in a solvent, it is difficult to dissolve it in vinylalkoxysilane and supply it to polyethylene. For this reason, the dispersibility in polyethylene is poor, and it becomes a foreign substance in the insulator, which may deteriorate the water-tree resistance, especially the bow titlery resistance.
【０００６】本発明は、このような実情に鑑みてなされ
たもので、押出成形性に優れ、加熱変形率と伸び、耐水
トリー性、特に耐ボウタイトリー特性を大幅に改善でき
るシラングラフト・水架橋法により架橋できる電気絶縁
用樹脂組成物及び当該樹脂組成物からなる電気絶縁物及
び電線・ケーブルの提供を目的とするものである。The present invention has been made in view of the above circumstances, and has excellent extrudability, silane graft / water crosslinking which can significantly improve the heat deformation rate and elongation, and the water tree resistance, especially the bow titlery resistance. It is an object of the present invention to provide a resin composition for electric insulation which can be crosslinked by a method, an electric insulator comprising the resin composition, and an electric wire / cable.
【０００７】[0007]
【課題を解決するための手段】本発明は、前記目的を達
成するために、高圧ラジカル重合により合成され、融点
が１１５℃以上で密度が０．９２５〜０．９３５ｇ／cm
3 のポリエチレン（ａ）を主体とするポリマ、又は前記
ポリエチレン（ａ）９９〜５０重量部と密度が０．９１
５〜０．９２５ｇ／cm3 のポリエチレン（ｂ）１〜５０
重量部を含むブレンドポリエチレンを主体とするポリマ
と、一般式 ＲＲ′ＳｉＹ2 （式中Ｒはオレフィン性不飽和炭化水素基あるいはハイ
ドロカーボンオキシ基であり、Ｙは加水分解可能な有機
基であり、Ｒ′は前記Ｒ基かＹ基である）で表されるシ
ランとを、遊離ラジカルを生じさせる化合物の存在下で
反応させて得られるシラン変性ポリマからなる架橋性電
気絶縁用樹脂組成物を提供するものである。According to the present invention, in order to achieve the above object, the present invention is synthesized by high pressure radical polymerization and has a melting point of 115 ° C. or more and a density of 0.925 to 0.935 g / cm.
( 3 ) a polymer mainly composed of polyethylene (a), or 99 to 50 parts by weight of the polyethylene (a) and a density of 0.91
5 to 0.925 g / cm 3 of polyethylene (b) 1 to 50
A polymer composed mainly of a blended polyethylene containing parts by weight and a general formula RR′SiY 2 (where R is an olefinically unsaturated hydrocarbon group or a hydrocarbonoxy group, Y is a hydrolyzable organic group, R 'is the above-mentioned R group or Y group). A crosslinkable resin composition for electrical insulation comprising a silane-modified polymer obtained by reacting the silane with a silane represented by the following formula: Is what you do.
【０００８】また、本発明は上記目的を達成するため、
前記架橋性電気絶縁用樹脂組成物からなる成形体をシラ
ノール縮合触媒の存在下で水分と接触させることにより
架橋度が４０％以上になるように架橋されている電気絶
縁物を提供するものである。[0008] In order to achieve the above object, the present invention provides:
An object of the present invention is to provide an electric insulator which is cross-linked so that the degree of cross-linking becomes 40% or more by contacting a molded article comprising the resin composition for cross-linking electric insulation with moisture in the presence of a silanol condensation catalyst. .
【０００９】更に、本発明は前記目的を達成するため
に、導体または導体遮蔽層上に前記架橋性電気絶縁用樹
脂組成物からなる絶縁層を有し、当該絶縁層がシラノー
ル縮合触媒の存在下で水分と接触させることにより架橋
度が４０％以上になるように架橋されている電線・ケー
ブルを提供するものである。Further, in order to achieve the above object, the present invention has an insulating layer comprising the above-mentioned crosslinkable resin composition for electric insulation on a conductor or a conductor shielding layer, wherein the insulating layer is formed in the presence of a silanol condensation catalyst. The present invention provides an electric wire / cable which is cross-linked so as to have a degree of cross-linking of 40% or more by contact with water.
【００１０】[0010]
【発明の実施の形態】本発明者は、種々のポリエチレン
について鋭意検討した結果、高圧ラジカル重合により合
成され、示差走査熱量計（ＤＳＣ）の結晶融点ピークで
表した融点が１１５℃以上で密度が０．９２５〜０．９
３５ｇ／cm3 のポリエチレン（ａ）を使用することによ
り、押出成形性に優れ、低い加熱変形率と高い伸びを有
する架橋成形体を実現できることを見出し、本発明に至
ったものである。このように押出成形性に優れるのは、
ポリエチレン（ａ）の分子構造によるもので、長鎖分岐
があるためと考えられる。また、この密度の範囲のポリ
エチレン（ａ）は、高温での結晶化度が高いため、ゲル
分率を低く設定しても加熱変形率を小さくでき、また、
ゲル分率を低く設定することにより高い伸びを得ること
ができる。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies on various polyethylenes, and as a result, have been synthesized by high-pressure radical polymerization, and have a melting point of 115 ° C. or more as indicated by a crystalline melting point peak of a differential scanning calorimeter (DSC) and a density of 115 ° C. 0.925-0.9
It has been found that by using 35 g / cm 3 of polyethylene (a), a cross-linked molded article having excellent extrudability and having a low heat deformation rate and a high elongation can be realized. Such excellent extrudability is due to
This is due to the molecular structure of polyethylene (a), which is considered to be due to long chain branching. In addition, polyethylene (a) having this density range has a high degree of crystallinity at high temperatures, so that even if the gel fraction is set low, the heating deformation rate can be reduced, and
High elongation can be obtained by setting the gel fraction low.
【００１１】本発明において、ポリエチレン（ａ）の融
点を１１５℃以上としたのは、規定値未満では加熱変形
率が大きくなるためである。又、ポリエチレン（ａ）の
密度を０．９２５〜０．９３５ｇ／cm3 としたのは、規
定値未満では、結晶化度が下がるため加熱変形率が大き
くなり、規定値を越えると、高圧ラジカル重合法での合
成が困難なためである。In the present invention, the reason why the melting point of polyethylene (a) is set to 115 ° C. or more is that if it is less than the specified value, the heating deformation rate becomes large. The reason why the density of polyethylene (a) is set to 0.925 to 0.935 g / cm 3 is that if the density is less than the specified value, the degree of crystallinity decreases and the heating deformation rate increases. This is because the synthesis by the polymerization method is difficult.
【００１２】本発明においては、高圧ラジカル重合によ
り合成され、融点が１１５℃以上で密度が０．９２５〜
０．９３５ｇ／cm3 のポリエチレン（ａ）９９〜５０重
量部に対し、密度が０．９１５〜０．９２５ｇ／cm3 の
ポリエチレン（ｂ）を１〜５０重量部含有させることに
より、電気絶縁物の伸びを更に大きくすることができ
る。密度が０．９１５〜０．９２５ｇ／cm3 のポリエチ
レン（ｂ）としては、高圧ラジカル重合のポリエチレ
ン、チーグラ系、クロム系又はメタロセン系の触媒によ
り合成される直鎖状ポリエチレンが挙げられる。ここ
で、ポリエチレン（ｂ）の含有量を１〜５０重量部とし
たのは、５０重量部を越えるとポリマの結晶化度が下が
り、加熱変形率が大きくなるためである。In the present invention, the polymer is synthesized by high-pressure radical polymerization and has a melting point of 115 ° C. or more and a density of 0.925 to 0.95.
To polyethylene (a) 99-50 parts by weight of 0.935 g / cm 3, by density is contained 1 to 50 parts by weight of polyethylene (b) of 0.915~0.925g / cm 3, an electrical insulator Can be further increased. Examples of the polyethylene (b) having a density of 0.915 to 0.925 g / cm 3 include polyethylene of high-pressure radical polymerization, and linear polyethylene synthesized by a Ziegler-based, chromium-based, or metallocene-based catalyst. Here, the reason why the content of the polyethylene (b) is set to 1 to 50 parts by weight is that if it exceeds 50 parts by weight, the crystallinity of the polymer decreases and the heating deformation rate increases.
【００１３】本発明において用いられる一般式、 ＲＲ′ＳｉＹ2 で表されるシランにおいて、Ｒはオレフィン性不飽和炭
化水素基あるいはハイドロカーボンオキシ基であり、ビ
ニル基、アルリル基、ブテニル基、ジクロヘキセニル
基、シクロペンタジエニル基等をあげることができ、中
でもビニル基が好適である。Ｙは加水分解可能な有機基
であり、メトキシ基、エトキシ基、ブトキシ基のような
アルコキシ基、ホルミルオキシ基、アセトキシ基、プロ
ピオノキシ基のようなアシロキシ基、その他オキシム
基、アルキノアミノ基、アリールアミノ基等をあげるこ
とができ中でもアルコキシ基が好適である。Ｒ′は前記
Ｒ基かＹ基である。最も好適なシランは、ビニルアルコ
キシシランであり、具体的には、ビニルトリメトキシシ
ラン、ビニルトリエトキシシラン、ビニルトリアセトキ
シシラン、ビニルジメトキシメチルシラン、ビニルジエ
トキシメチルシラン、ビニルメトキシジメチルシラン、
ビニルエトキシジメチルシランなどがあげられ、これら
は単独、もしくは２種類以上組合わせて使用しても差し
支えない。シランの添加量は特に規定されないが、ポリ
エチレン（ａ）単独又はポリエチレン（ａ）とポリエチ
レン（ｂ）のブレンドからなるポリマ１００重量部に対
し０．１〜１０重量部の範囲が好ましい。In the silane represented by the general formula RR'SiY 2 used in the present invention, R is an olefinically unsaturated hydrocarbon group or a hydrocarbonoxy group, and is a vinyl group, an allyl group, a butenyl group, a dicyclohexenyl group. And a cyclopentadienyl group, among which a vinyl group is preferred. Y is a hydrolyzable organic group, such as an alkoxy group such as a methoxy group, an ethoxy group or a butoxy group, an acyloxy group such as a formyloxy group, an acetoxy group, or a propionoxy group; another oxime group; an alkynamino group; and an arylamino group. Among them, an alkoxy group is preferable. R 'is the aforementioned R group or Y group. The most preferred silanes are vinylalkoxysilanes, specifically vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinylmethoxydimethylsilane,
And vinylethoxydimethylsilane. These may be used alone or in combination of two or more. The amount of the silane is not particularly limited, but is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of the polymer composed of polyethylene (a) alone or a blend of polyethylene (a) and polyethylene (b).
【００１４】ポリマにシランをグラフトする際に用いら
れる遊離ラジカル発生剤としては、ジクミルパーオキサ
イド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパー
オキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔ
−ブチルパーオキシ）ヘキシン−３、α, α’−ビス
（ｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼ
ン、ブチルクミルパーオキサイド、イソプロピルクミル
−ｔ−ブチルパーオキサイドなどがあげられ、これらは
単独もしくは２種類以上組み合わせて使用しできる。ラ
ジカル発生剤の添加量は、ポリマ１００重量部に対して
０．０５〜０．１５重量部が望ましく、０．０５重量部
未満では架橋度が不十分となる傾向にあり、０．１５重
量部越えると絶縁体内にラジカル開始剤の分解生成物に
起因するボイドが発生しやすくなる。The free radical generator used when grafting silane to the polymer includes dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 2,5-dimethyl −2,5-di (t
-Butylperoxy) hexyne-3, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, butylcumyl peroxide, isopropylcumyl-t-butyl peroxide and the like. Alternatively, two or more kinds can be used in combination. The amount of the radical generator to be added is desirably 0.05 to 0.15 parts by weight based on 100 parts by weight of the polymer. If the amount is less than 0.05 part by weight, the degree of crosslinking tends to be insufficient. If it exceeds, voids due to the decomposition products of the radical initiator tend to be generated in the insulator.
【００１５】本発明においては、更に、酸化防止剤とし
て、２，２−チオ−ジエチレンビス［３−（３，５−ジ
−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネー
ト］、ペンタエリスリチル−テトラキス［３−（３，５
−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオ
ネート］、オクタデシル３−（３，５−ジ−ｔ−ブチル
−４−ヒドロキシフェニル）プロピオネート、２，４−
ビス−（ｎ−オクチルチオ）−６−（４−ヒドロキシ−
３，５−ジ−ｔ−ブチルアニリノ）−１，３，５−トリ
アジンから選ばれる１種類または２種類以上とジラウリ
ルチオプロピオネートをそれぞれ、０．０５〜０．５重
量部添加ずつ添加することにより、耐熱老化特性、特
に、金属害を防止できる。これらは、単独で使用しても
効果は小さく、併用することによって著しい相乗効果が
発揮される。これらの酸化防止剤は、予めポリエチレン
に高濃度に練り込んだマスターバッチの形やポリエチレ
ンにドライブレンドした形で供給することはもちろん、
シランに溶解して押出機内のポリエチレンに注入するこ
とも可能である。酸化防止剤各々の添加量は０．０５〜
０．５重量部とするのが好ましく、０．０５重量部未満
では、酸化防止、金属害防止の効果が少なく、また、
０．５重量部を越えるとポリエチレンの表面に析出する
いわゆるブルーム現象が生じる可能性がある。In the present invention, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and pentaerythrityl-tetrakis are further used as antioxidants. [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-
Bis- (n-octylthio) -6- (4-hydroxy-
One or two or more kinds selected from (3,5-di-t-butylanilino) -1,3,5-triazine and dilaurylthiopropionate are each added in an amount of 0.05 to 0.5 part by weight. This can prevent heat aging characteristics, particularly metal damage. These have little effect even when used alone, and a remarkable synergistic effect is exhibited when used in combination. Of course, these antioxidants are supplied in the form of a masterbatch kneaded in high concentration in polyethylene in advance or in a dry-blended form in polyethylene.
It is also possible to dissolve in silane and inject into polyethylene in the extruder. The amount of each antioxidant added is 0.05-
It is preferably 0.5 part by weight, and if less than 0.05 part by weight, the effect of preventing oxidation and preventing metal damage is small, and
If the amount exceeds 0.5 parts by weight, a so-called bloom phenomenon that precipitates on the surface of polyethylene may occur.
【００１６】本発明においては、架橋を促進するために
シラノール縮合触媒を直鎖状ポリエチレン中に添加、あ
るいは、成形物表面から直鎖状ポリエチレン中に浸透さ
せる。このようなシラノール縮合触媒は、一般に、錫、
亜鉛、鉄、鉛、コバルト等の金属のカルボン酸塩、有機
塩基、無機酸、有機酸などである。具体的にはジブチル
錫ジラウレート、ジブチル錫ジアセテート、ジブチル錫
ジオクタエート、酢酸第一錫、カブリル酸第一錫、ナフ
テン酸鉛、カブリル酸亜鉛、ナフテン酸コバルト、エチ
ルアミン、ジブチルアミン、ヘキシルアミン、ピリジ
ン、硫酸、塩酸などの無機酸、トルエンスルホン酸、酢
酸、ステアリン酸、マレイン酸などの有機酸が挙げられ
る。これらは、特に規定しないがポリマ１００重量部に
対して、０．０１〜０．１重量部添加して用いられる。In the present invention, in order to promote crosslinking, a silanol condensation catalyst is added to the linear polyethylene, or is penetrated from the surface of the molded product into the linear polyethylene. Such silanol condensation catalysts are generally tin,
Examples include carboxylate salts of metals such as zinc, iron, lead, and cobalt, organic bases, inorganic acids, and organic acids. Specifically, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, stannous acetate, stannous carboxylate, lead naphthenate, zinc cabrate, cobalt naphthenate, ethylamine, dibutylamine, hexylamine, pyridine, Examples include inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as toluenesulfonic acid, acetic acid, stearic acid, and maleic acid. These are not particularly specified, but are used by adding 0.01 to 0.1 part by weight to 100 parts by weight of the polymer.
【００１７】シラノール縮合触媒を含有する成形体の製
造方法としては、次のような２つの方法を挙げることが
できる。一つは、シラノール縮合触媒を高濃度に含むポ
リマのマスターバッチを作製し、予め作製したシラング
ラフトポリマと一緒に押出機に供給して成形する２ショ
ット法またはサイオプラス法といわれる方法である。他
の方法は、シラノール縮合触媒、ラジカル発生剤を含む
配合剤を押出機内のポリマに供給し、ビニルアルコキシ
シランの直鎖状ポリエチレンへのグラフト反応と成形を
１つの押出機で同時に行う１ショット法またはモノシル
法と呼ばれる方法である。本発明は、上記のいずれの方
法をも採用可能である。As a method for producing a molded article containing a silanol condensation catalyst, the following two methods can be mentioned. One is a method called a two-shot method or a Sioplus method in which a master batch of a polymer containing a high concentration of a silanol condensation catalyst is prepared and supplied to an extruder together with a silane graft polymer prepared in advance and molded. Another method is a one-shot method in which a compounding agent containing a silanol condensation catalyst and a radical generator is supplied to a polymer in an extruder, and a graft reaction of vinylalkoxysilane to linear polyethylene and molding are simultaneously performed in one extruder. Or a method called the monosil method. The present invention can employ any of the above methods.
【００１８】ポリエチレン（ａ）又はポリエチレン
（ａ）とポリエチレン（ｂ）のブレンドポリエチレンを
主体とする電気絶縁物の架橋度を４０％以上としたの
は、高温での加熱変形率を小さくするためであり、この
値未満では変形が大きくなる。The reason why the degree of cross-linking of an electrical insulator mainly composed of polyethylene (a) or a blend of polyethylene (a) and polyethylene (b) is set to 40% or more is to reduce the heat deformation rate at high temperatures. Yes, below this value the deformation will be large.
【００１９】本発明においては、上記化合物の他に、耐
候性を付与するためにカーボンブラックの添加や、滑
剤、着色剤等の添加剤を加えることは一向に差し支えな
い。さらに、ポリマにエチレン−酢酸エチル共重合体や
エチレン−エチルアクリレート共重合体等のエチレン系
ポリマを少量ブレンドすることもできる。In the present invention, in addition to the above-mentioned compounds, addition of carbon black and additives such as a lubricant and a coloring agent for imparting weather resistance may be used without any problem. Further, a small amount of an ethylene-based polymer such as an ethylene-ethyl acetate copolymer or an ethylene-ethyl acrylate copolymer can be blended with the polymer.
【００２０】本発明の電線・ケーブルにおいては、導体
として、水の走水を防止するため、水密コンパウンドを
充填した水密導体を使用することも可能である。さら
に、本架橋ポリエチレン絶縁層の上に半導電性樹脂組成
物からなる絶縁体遮蔽層を設けることもできる。In the electric wire / cable of the present invention, a watertight conductor filled with a watertight compound can be used as the conductor in order to prevent water running. Further, an insulator shielding layer made of a semiconductive resin composition can be provided on the crosslinked polyethylene insulating layer.
【００２１】[0021]
【実施例】＜実施例１＞密度が０．９２５、融点が１１
５℃の高圧ラジカル重合ポリエチレン（ポリエチレン
（Ｉ））１００重量部に対して、酸化防止剤としての
２，２−チオ−ジエチレンビス［３−（３，５−ジ−ｔ
−ブチル−４−ヒドロキシフェニル）プロピオネート］
（酸化防止剤（Ｉ））を０．１重量部、ビニルトリメト
キシシランを１．５重量部、遊離ラジカル発生剤として
のジクミルパーオキサイド（遊離ラジカル発生剤
（Ｉ））を０．１５重量部、ジブチル錫ジラウレートを
０．０５重量部の割合で２００℃に設定した１３０mm押
出機に投入した。なお、酸化防止剤、遊離ラジカル発生
剤及びジブチル錫ジラウレートはビニルトリメトキシシ
ランに溶解させて押出機のホッパ下部から注入した。<Example 1> Density is 0.925 and melting point is 11.
2,2-thio-diethylenebis [3- (3,5-di-t) as an antioxidant is added to 100 parts by weight of a high-pressure radical polymerization polyethylene (polyethylene (I)) at 5 ° C.
-Butyl-4-hydroxyphenyl) propionate]
0.1 parts by weight of (antioxidant (I)), 1.5 parts by weight of vinyltrimethoxysilane, and 0.15 parts by weight of dicumyl peroxide (free radical generator (I)) as a free radical generator Parts and dibutyltin dilaurate in a ratio of 0.05 parts by weight were put into a 130 mm extruder set at 200 ° C. The antioxidant, free radical generator and dibutyltin dilaurate were dissolved in vinyltrimethoxysilane and injected from the lower part of the hopper of the extruder.
【００２２】上記コンパウンンドを断面積６０mm2 の軟
銅撚線上に０．７mm厚の内部半導電層及び０．７mm厚の
外部半導電層と共に４．５mm厚さに押出し、その後、８
０℃、９５％水蒸気の雰囲気に２４時間放置して架橋さ
せ、架橋絶縁層を有する電気ケーブルを作製した。The above compound was extruded onto a soft copper stranded wire having a cross-sectional area of 60 mm 2 with an inner semiconductive layer having a thickness of 0.7 mm and an outer semiconductive layer having a thickness of 0.7 mm to a thickness of 4.5 mm.
It was left standing for 24 hours in an atmosphere of 0 ° C. and 95% water vapor for cross-linking to prepare an electric cable having a cross-linked insulating layer.
【００２３】＜実施例２＞配合成分を、密度が０．９２
７、融点が１１５℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（II））を１００重量部、酸化防止剤と
してのペンタエリスリチル−テトラキス［３−（３，５
−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオ
ネート］（酸化防止剤（II））を０．１重量部、ビニル
トリメトキシシランを１．０重量部、ジクミルパーオキ
サイド（遊離ラジカル発生剤（Ｉ））を０．１重量部、
ジブチル錫ジラウレートを０．０５重量部とし、実施例
１と同様にして電気ケーブルを作製した。<Example 2> A blending component was prepared with a density of 0.92.
7, 100 parts by weight of high-pressure radically polymerized polyethylene (polyethylene (II)) having a melting point of 115 ° C., and pentaerythrityl-tetrakis [3- (3,5)
-Di-t-butyl-4-hydroxyphenyl) propionate] (antioxidant (II)), 0.1 part by weight of vinyltrimethoxysilane, dicumyl peroxide (free radical generator ( I)) is 0.1 part by weight,
An electric cable was produced in the same manner as in Example 1 except that dibutyltin dilaurate was used in an amount of 0.05 part by weight.
【００２４】＜実施例３＞配合成分を、密度が０．９３
２、融点が１１８℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（III ））を１００重量部、２，２−チ
オ−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−
４−ヒドロキシフェニル）プロピオネート］（酸化防止
剤（Ｉ））を０．１重量部、ビニルトリメトキシシラン
を１．０重量部、遊離ラジカル発生剤としての２，５−
ジメチル−２，５−ジ−（ｔ−ブチルパーオキシ）ヘキ
サン（遊離ラジカル発生剤（II））を０．０７重量部、
ジブチル錫ジラウレートを０．０５重量部とし、実施例
１と同様にして電気ケーブルを作製した。<Example 3> A blending component was prepared with a density of 0.93.
2. 100 parts by weight of high-pressure radically polymerized polyethylene (polyethylene (III)) having a melting point of 118 ° C., and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate] (antioxidant (I)) 0.1 part by weight, vinyltrimethoxysilane 1.0 part by weight, 2,5-
0.07 parts by weight of dimethyl-2,5-di- (t-butylperoxy) hexane (free radical generator (II)),
An electric cable was produced in the same manner as in Example 1 except that dibutyltin dilaurate was used in an amount of 0.05 part by weight.
【００２５】＜実施例４＞配合成分を、密度が０．９２
５、融点が１１５℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｉ））を９５重量部、密度が０．９２
０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を５重量部、ペンタエリスリチ
ル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−
ヒドロキシフェニル）プロピオネート］（酸化防止剤
（II））を０．１重量部、ビニルトリメトキシシランを
１．２重量部、２，５−ジメチル−２，５−ジ−（ｔ−
ブチルパーオキシ）ヘキサン（遊離ラジカル発生剤（I
I））を０．１重量部、ジブチル錫ジラウレートを０．
０５重量部とし、実施例１と同様にして電気ケーブルを
作製した。<Example 4> A blending component was prepared with a density of 0.92.
5. 95 parts by weight of a high-pressure radical polymerized polyethylene (polyethylene (I)) having a melting point of 115 ° C. and a density of 0.92
0, 5 parts by weight of a high-pressure radical-polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C, and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-).
(Hydroxyphenyl) propionate] (antioxidant (II)) in an amount of 0.1 part by weight, vinyltrimethoxysilane in an amount of 1.2 parts by weight, 2,5-dimethyl-2,5-di- (t-
Butylperoxy) hexane (free radical generator (I
I)) is 0.1 part by weight, and dibutyltin dilaurate is 0.1 part by weight.
An electric cable was manufactured in the same manner as in Example 1 except that the amount was 05 parts by weight.
【００２６】＜実施例５＞配合成分を、密度が０．９２
５、融点が１１５℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｉ））を９５重量部、密度が０．９２
０、融点が１２３℃の直鎖状ポリエチレン（ポリエチレ
ン（VI））を５重量部、酸化防止剤として２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））とジラウリルチオプロピオネート（酸化防止剤
（III ））をそれぞれ０．１重量部併用、ビニルトリメ
トキシシランを１．０重量部、ジクミルパーオキサイド
（遊離ラジカル発生剤（Ｉ））を０．１重量部、ジブチ
ル錫ジラウレートを０．０５重量部とし、実施例１と同
様にして電気ケーブルを作製した。<Example 5> The blended components were prepared with a density of 0.92.
5. 95 parts by weight of a high-pressure radical polymerized polyethylene (polyethylene (I)) having a melting point of 115 ° C. and a density of 0.92
0, 5 parts by weight of linear polyethylene having a melting point of 123 ° C. (polyethylene (VI)), and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4) as an antioxidant.
-Hydroxyphenyl) propionate] (antioxidant (I)) and dilaurylthiopropionate (antioxidant (III)) in amounts of 0.1 parts by weight each, vinyltrimethoxysilane in an amount of 1.0 parts by weight, An electric cable was produced in the same manner as in Example 1 except that 0.1 part by weight of the milk peroxide (free radical generator (I)) and 0.05 part by weight of dibutyltin dilaurate were used.
【００２７】＜実施例６＞配合成分を、密度が０．９３
２、融点が１１８℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（III ））を５０重量部、密度が０．９
２０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を５０重量部、２，２−チオ−
ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４−
ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ビニルトリメトキシシランを
１．０重量部、ジクミルパーオキサイド（遊離ラジカル
発生剤（Ｉ））を０．１重量部、ジブチル錫ジラウレー
トを０．０５重量部とし、実施例１と同様にして電気ケ
ーブルを作製した。<Example 6> The ingredients were mixed at a density of 0.93.
2. 50 parts by weight of a high-pressure radical polymerized polyethylene (polyethylene (III)) having a melting point of 118 ° C. and a density of 0.9
20, 50 parts by weight of high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., 2,2-thio-
Diethylenebis [3- (3,5-di-t-butyl-4-
(Hydroxyphenyl) propionate] (antioxidant (I)) 0.1 part by weight, vinyltrimethoxysilane 1.0 part by weight, dicumyl peroxide (free radical generator (I)) 0.1 part by weight An electric cable was produced in the same manner as in Example 1 except that dibutyltin dilaurate was used in an amount of 0.05 part by weight.
【００２８】＜実施例７＞配合成分を、密度が０．９３
３、融点が１１９℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（IV））を５０重量部、密度が０．９２
０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を５０重量部、２，２−チオ−
ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４−
ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ビニルトリメトキシシランを
１．０重量部、ジクミルパーオキサイド（遊離ラジカル
発生剤（））を０．１重量部、ジブチル錫ジラウレート
を０．０５重量部とし、実施例１と同様にして電気ケー
ブルを作製した。<Example 7> A blending component was prepared with a density of 0.93.
3. 50 parts by weight of high-pressure radically polymerized polyethylene (polyethylene (IV)) having a melting point of 119 ° C. and a density of 0.92
0, 50 parts by weight of high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., 2,2-thio-
Diethylenebis [3- (3,5-di-t-butyl-4-
(Hydroxyphenyl) propionate] (antioxidant (I)) 0.1 part by weight, vinyltrimethoxysilane 1.0 part by weight, dicumyl peroxide (free radical generator ()) 0.1 part by weight, An electric cable was produced in the same manner as in Example 1 except that dibutyltin dilaurate was used in an amount of 0.05 part by weight.
【００２９】＜実施例８＞配合成分を、密度が０．９２
７、融点が１１５℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（II））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ジラウリルチオプロピオネー
ト（酸化防止剤（III ））を０．１重量部、ビニルトリ
メトキシシランを１．０重量部、ジクミルパーオキサイ
ド（遊離ラジカル発生剤（Ｉ））を０．１重量部、ジブ
チル錫ジラウレートを０．０５重量部、更に、ポリエチ
レン（II）中にファーネスブラックが２５重量％含有さ
れるように調整したカーボンマスターバッチを４重量部
とし、実施例１と同様にして２００℃に設定した１３０
mm押出機に投入した。続いて、断面積６０mm2 の軟銅撚
線上に２．５mm厚さに押出し、その後、８０℃、９５％
水蒸気の雰囲気に２４時間放置して架橋させ、架橋絶縁
層を有する電気ケーブルを作製した。<Example 8> The blended components were prepared with a density of 0.92.
7, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (II)) having a melting point of 115 ° C., and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4) -4
-Hydroxyphenyl) propionate] (antioxidant (I)), 0.1 part by weight of dilaurylthiopropionate (antioxidant (III)), and 1.0 part by weight of vinyltrimethoxysilane. 0.1 part by weight of dicumyl peroxide (free radical generator (I)), 0.05 part by weight of dibutyltin dilaurate, and 25% by weight of furnace black in polyethylene (II) The carbon master batch adjusted as described above was adjusted to 4 parts by weight, and set to 200 ° C. in the same manner as in Example 1.
mm was fed into the extruder. Subsequently, it was extruded to a thickness of 2.5 mm on a soft copper stranded wire having a cross-sectional area of 60 mm 2 , and then 80 ° C., 95%
It was left standing in a steam atmosphere for 24 hours to be crosslinked, thereby producing an electric cable having a crosslinked insulating layer.
【００３０】＜実施例９＞配合成分を、密度が０．９３
２、融点が１１８℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（III ））を５０重量部、密度が０．９
２０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を５０重量部、２，２−チオ−
ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４−
ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ビニルトリメトキシシランを
１．０重量部、ジクミルパーオキサイド（遊離ラジカル
発生剤（Ｉ））を０．１重量部、ジブチル錫ジラウレー
トを０．０５重量部、ポリエチレン（III ）中にファー
ネスブラックが２５重量％含有されるように調整したカ
ーボンマスターバッチを４重量部とし、実施例８と同様
にして電気ケーブルを作製した。<Example 9> A blended component having a density of 0.93 was prepared.
2. 50 parts by weight of a high-pressure radical polymerized polyethylene (polyethylene (III)) having a melting point of 118 ° C. and a density of 0.9
20, 50 parts by weight of high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., 2,2-thio-
Diethylenebis [3- (3,5-di-t-butyl-4-
(Hydroxyphenyl) propionate] (antioxidant (I)) 0.1 part by weight, vinyltrimethoxysilane 1.0 part by weight, dicumyl peroxide (free radical generator (I)) 0.1 part by weight An electric cable was manufactured in the same manner as in Example 8, except that 0.05 parts by weight of dibutyltin dilaurate and 4 parts by weight of a carbon masterbatch adjusted to contain 25% by weight of furnace black in polyethylene (III) were used. did.
【００３１】＜比較例１＞配合成分を、密度が０．９２
７、融点が１１５℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（II））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ビニルトリメトキシシランを
０．５重量部、ジクミルパーオキサイド（遊離ラジカル
発生剤（Ｉ））を０．０５重量部、ジブチル錫ジラウレ
ートを０．０５重量部とし、実施例１と同様にして電気
ケーブルを作製した。<Comparative Example 1> A blended component having a density of 0.92
7, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (II)) having a melting point of 115 ° C., and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4) -4
-Hydroxyphenyl) propionate] (antioxidant (I)) 0.1 part by weight, vinyltrimethoxysilane 0.5 part by weight, dicumyl peroxide (free radical generator (I)) 0.05 part by weight Parts and dibutyltin dilaurate in 0.05 parts by weight, an electric cable was produced in the same manner as in Example 1.
【００３２】＜比較例２＞配合成分を、密度が０．９３
２、融点が１１８℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（III ））を５０重量部、密度が０．９
２０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を５０重量部、２，２−チオ−
ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４−
ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ビニルトリメトキシシランを
０．５重量部、ジクミルパーオキサイド（遊離ラジカル
発生剤（Ｉ））を０．０５重量部、ジブチル錫ジラウレ
ートを０．０５重量部とし、実施例１と同様にして電気
ケーブルを作製した。<Comparative Example 2> A blended component having a density of 0.93
2. 50 parts by weight of a high-pressure radical polymerized polyethylene (polyethylene (III)) having a melting point of 118 ° C. and a density of 0.9
20, 50 parts by weight of high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., 2,2-thio-
Diethylenebis [3- (3,5-di-t-butyl-4-
(Hydroxyphenyl) propionate] (antioxidant (I)) 0.1 part by weight, vinyltrimethoxysilane 0.5 part by weight, dicumyl peroxide (free radical generator (I)) 0.05 part by weight An electric cable was produced in the same manner as in Example 1 except that dibutyltin dilaurate was used in an amount of 0.05 part by weight.
【００３３】＜比較例３＞配合成分を、密度が０．９２
０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ビニルトリメトキシシランを
１．０重量部、ジクミルパーオキサイド（遊離ラジカル
発生剤（Ｉ））を０．１重量部、ジブチル錫ジラウレー
トを０．０５重量部とし、実施例１と同様にして電気ケ
ーブルを作製した。<Comparative Example 3> A blended component having a density of 0.92
0, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (antioxidant (I)) 0.1 part by weight, vinyltrimethoxysilane 1.0 part by weight, dicumyl peroxide (free radical generator (I)) 0.1 part by weight Parts and dibutyltin dilaurate in 0.05 parts by weight, an electric cable was produced in the same manner as in Example 1.
【００３４】＜比較例４＞配合成分を、密度が０．９２
０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ビニルトリメトキシシランを
２．５重量部、ジクミルパーオキサイド（遊離ラジカル
発生剤（Ｉ））を０．２重量部、ジブチル錫ジラウレー
トを０．０５重量部とし、実施例１と同様にして電気ケ
ーブルを作製した。<Comparative Example 4> A blended component having a density of 0.92
0, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (0.1 parts by weight of antioxidant (I)), 2.5 parts by weight of vinyltrimethoxysilane, and 0.2 parts by weight of dicumyl peroxide (free radical generator (I)) Parts and dibutyltin dilaurate in 0.05 parts by weight, an electric cable was produced in the same manner as in Example 1.
【００３５】＜比較例５＞配合成分を、チーグラ触媒に
より重合され、密度が０．９２０、融点が１２３℃の直
鎖状ポリエチレン（ポリエチレン（VI））を１００重量
部、２，２−チオ−ジエチレンビス［３−（３，５−ジ
−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネー
ト］（酸化防止剤（Ｉ））を０．１重量部、ビニルトリ
メトキシシランを１．０重量部、２，５−ジメチル−
２，５−ジ−（ｔ−ブチルパーオキシ）ヘキサン（遊離
ラジカル発生剤（II））を０．０７重量部、ジブチル錫
ジラウレートを０．０５重量部とし、実施例１と同様に
して電気ケーブルを作製した。Comparative Example 5 100 parts by weight of a linear polyethylene (polyethylene (VI)) having a density of 0.920 and a melting point of 123.degree. 0.1 parts by weight of diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (antioxidant (I)), 1.0 part by weight of vinyltrimethoxysilane, , 5-dimethyl-
An electric cable was prepared in the same manner as in Example 1 except that 0.07 part by weight of 2,5-di- (t-butylperoxy) hexane (free radical generator (II)) and 0.05 part by weight of dibutyltin dilaurate were used. Was prepared.
【００３６】＜比較例６＞配合成分を、密度が０．９３
２、融点が１１８℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（III ））を４０重量部、密度が０．９
２０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を６０重量部、２，２−チオ−
ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４−
ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ビニルトリメトキシシランを
１．０重量部、ジクミルパーオキサイド（遊離ラジカル
発生剤（Ｉ））を０．１重量部、ジブチル錫ジラウレー
トを０．０５重量部とし、実施例１と同様にして電気ケ
ーブルを作製した。<Comparative Example 6> A blended component having a density of 0.93
2. 40 parts by weight of high pressure radically polymerized polyethylene (polyethylene (III)) having a melting point of 118 ° C. and a density of 0.9
20, 60 parts by weight of a high-pressure radical polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., 2,2-thio-
Diethylenebis [3- (3,5-di-t-butyl-4-
(Hydroxyphenyl) propionate] (antioxidant (I)) 0.1 part by weight, vinyltrimethoxysilane 1.0 part by weight, dicumyl peroxide (free radical generator (I)) 0.1 part by weight An electric cable was produced in the same manner as in Example 1 except that dibutyltin dilaurate was used in an amount of 0.05 part by weight.
【００３７】＜比較例７＞配合成分を、密度が０．９２
０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ビニルトリメトキシシランを
１．０重量部、ジクミルパーオキサイド（遊離ラジカル
発生剤（Ｉ））を０．１重量部、ジブチル錫ジラウレー
トを０．０５重量部、ポリエチレン（Ｖ）中にファーネ
スブラックが２５重量％含有されるように調整したカー
ボンマスターバッチを４重量部とし、実施例８と同様に
して電気ケーブルを作製した。<Comparative Example 7> A blended component having a density of 0.92
0, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (antioxidant (I)) 0.1 part by weight, vinyltrimethoxysilane 1.0 part by weight, dicumyl peroxide (free radical generator (I)) 0.1 part by weight Parts by weight, 0.05 parts by weight of dibutyltin dilaurate, and 4 parts by weight of a carbon masterbatch adjusted to contain 25% by weight of furnace black in polyethylene (V). Produced.
【００３８】＜比較例８＞配合成分を、チーグラ触媒に
より重合され、密度が０．９２０、融点が１２３℃の直
鎖状ポリエチレン（ポリエチレン（VI））を１００重量
部、２，２−チオ−ジエチレンビス［３−（３，５−ジ
−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネー
ト］（酸化防止剤（Ｉ））を０．１重量部、ビニルトリ
メトキシシランを１．０重量部、ジクミルパーオキサイ
ド（遊離ラジカル発生剤（Ｉ））を０．１重量部、ジブ
チル錫ジラウレートを０．０５重量部、ポリエチレン
（VI）中にファーネスブラックが２５重量％含有される
ように調整したカーボンマスターバッチを４重量部と
し、実施例８と同様にして電気ケーブルを作製した。Comparative Example 8 100 parts by weight of a linear polyethylene (polyethylene (VI)) having a density of 0.920 and a melting point of 123 ° C. was polymerized by a Ziegler catalyst, and 100 parts by weight of 2,2-thio- 0.1 parts by weight of diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (antioxidant (I)), 1.0 part by weight of vinyltrimethoxysilane, Carbon master prepared such that 0.1 part by weight of a milk peroxide (free radical generator (I)), 0.05 part by weight of dibutyltin dilaurate, and 25% by weight of furnace black in polyethylene (VI). An electric cable was manufactured in the same manner as in Example 8, except that the batch was 4 parts by weight.
【００３９】実施例１〜９及び比較例１〜８の配合組成
を評価結果と共に表１及び表２に示した。なお、評価は
次に基づいて行った。押出性は外観により評価し、加熱
変形率はＪＩＳ Ｃ３００５に準拠し，１２０℃におけ
る電気ケーブルの加熱変形率が２５％以下のものを良、
２５％を越えるものを悪として示した。伸び、ゲル分率
は、ＪＩＳ Ｃ３００５に準拠して測定した。ボウタイ
トリー特性の評価試験は、導体内に注水した電気ケーブ
ルを９０℃の温水中に浸漬し、導体と水との間に５０Ｈ
ｚで９ｋＶの交流電圧を５００日間印加して行った。５
００日経過後、ケーブル断面を薄くスライスしてメチレ
ンブルー水溶液で煮沸染色し、光学顕微鏡を用いてボウ
タイトリー長さと２００μｍ以上のボウタイトリーの発
生数を計数した。The compositions of Examples 1 to 9 and Comparative Examples 1 to 8 are shown in Tables 1 and 2 together with the evaluation results. In addition, evaluation was performed based on the following. The extrudability is evaluated based on the appearance, and the heating deformation rate conforms to JIS C3005.
Those exceeding 25% were indicated as evil. The elongation and the gel fraction were measured according to JIS C3005. The evaluation test of the bow titley characteristics is as follows. An electric cable injected into a conductor is immersed in warm water of 90 ° C., and 50H is applied between the conductor and the water.
This was performed by applying an AC voltage of 9 kV for 500 days at z. 5
After a lapse of 00 days, the cable section was sliced thinly, stained by boiling with an aqueous methylene blue solution, and the length of the bow title tree and the number of bow title trees having a length of 200 μm or more were counted using an optical microscope.
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【表２】 [Table 2]
【００４２】表１に示したように、実施例１〜３は融点
と密度が請求項第１項の範囲の高圧ラジカル重合ポリエ
チレンを用いたもので、押出外観が良好で、ゲル分率が
高く、加熱変形率も良好である。また、伸び、ボウタイ
トリー等すべての特性が良好である。実施例４〜７は、
密度の小さいポリエチレンを請求項第２項の規定量の範
囲でブレンドしたもので、いずれの特性も良好で、特に
伸びが大きく良好である。実施例８と実施例９は、カー
ボンを配合したものであり、カーボンを添加してもいず
れの特性も良好である。一方、ゲル分率の値が本発明の
規定を外れて小さい比較例１と比較例２は加熱変形特性
に劣り、また、ボウタイトリーの発生数も多くなってい
る。融点と密度が本発明の規定を外れたポリエチレンを
用いた比較例３は、加熱変形の特性が悪く、ボウタイト
リー特性も劣っている。比較例４はビニルシランとラジ
カル開始剤を増量し架橋度を高くしたもので、加熱変形
率は良好であるが、伸びが小さい。また、ラジカル開始
剤が多いため、絶縁体中にボイドが発生した。本発明の
規定外のポリエチレンを用いた比較例５は、押出外観が
悪く、ボウタイトリーの発生も多い。また、密度が０．
９１５〜０．９２５ｇ／cm3 の範囲のポリエチレンの配
合量が規定量を越えた比較例６は、加熱変形率が劣って
いる。カーボンを添加した比較例７、８は本発明の規定
外のポリエチレンを用いたものであり、カーボン非充填
配合と同じ傾向を示しており、それぞれ、加熱変形と押
出性に劣る。As shown in Table 1, Examples 1 to 3 use a high-pressure radically polymerized polyethylene having a melting point and a density in the range of claim 1 and have good extruded appearance and high gel fraction. Also, the heat deformation rate is good. In addition, all properties such as elongation and bow title are good. Examples 4 to 7
Polyethylene having a low density is blended in the range of the amount specified in claim 2, and all properties are good, and particularly, the elongation is large and good. In Example 8 and Example 9, carbon was blended, and even when carbon was added, both characteristics were good. On the other hand, Comparative Examples 1 and 2 in which the value of the gel fraction is out of the range of the present invention and small are inferior in heat deformation characteristics, and the number of bow title trees generated is large. Comparative Example 3 using polyethylene whose melting point and density are out of the range specified in the present invention has poor heat-deformation characteristics and poor bow-tree characteristics. In Comparative Example 4, the degree of crosslinking was increased by increasing the amount of vinylsilane and the radical initiator, and the heat deformation rate was good, but the elongation was small. In addition, voids were generated in the insulator due to the large amount of radical initiator. In Comparative Example 5 using polyethylene out of the specified range of the present invention, the extruded appearance was poor and many bow titles were generated. In addition, the density is 0.
Comparative Example 6 in which the blending amount of polyethylene in the range of 915 to 0.925 g / cm 3 exceeded the specified amount was inferior in the heat deformation ratio. Comparative Examples 7 and 8 to which carbon was added use polyethylene outside the scope of the present invention, and show the same tendency as the non-carbon-filled blend, and are inferior in heat deformation and extrudability, respectively.
【００４３】＜実施例１０＞配合成分を、密度が０．９
２７、融点が１１５℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（II））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．０５重量部、ジラウリルチオプロピオネ
ート（酸化防止剤（III ））を０．０５重量部、ビニル
トリメトキシシランを１．０重量部、ジクミルパーオキ
サイド（遊離ラジカル発生剤（Ｉ））を０．１重量部、
ジブチル錫ジラウレートを０．０５重量部とし、実施例
１と同様にして押出機に投入し、続いて、断面積６０mm
2 の軟銅撚線上に２．５mm厚さに押出し、その後、８０
℃、９５％水蒸気の雰囲気に２４時間放置して架橋さ
せ、架橋絶縁層を有する電気ケーブルを作製した。<Example 10> The ingredients were mixed at a density of 0.9.
27, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (II)) having a melting point of 115 ° C, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (antioxidant (I)), 0.05 parts by weight of dilaurylthiopropionate (antioxidant (III)), and 1.0 parts by weight of vinyltrimethoxysilane. Parts by weight, 0.1 part by weight of dicumyl peroxide (free radical generator (I))
Dibutyltin dilaurate was added to an extruder in the same manner as in Example 1 except that the weight was 0.05 part by weight.
Extruded into 2.5mm thickness 2 of the soft copper twisted lines, then 80
The mixture was left standing for 24 hours in an atmosphere of water vapor at 95 ° C. and 95% water vapor to be crosslinked, thereby producing an electric cable having a crosslinked insulating layer.
【００４４】＜実施例１１＞配合成分を、密度が０．９
２７、融点が１１５℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（II））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ジラウリルチオプロピオネー
ト（酸化防止剤（III ））を０．１重量部、ビニルトリ
メトキシシランを１．０重量部、ジクミルパーオキサイ
ド（遊離ラジカル発生剤（Ｉ））を０．１重量部、ジブ
チル錫ジラウレートを０．０５重量部とし、実施例１０
と同様にして電気ケーブルを作製した。<Example 11> A blending component was prepared with a density of 0.9.
27, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (II)) having a melting point of 115 ° C, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (antioxidant (I)), 0.1 part by weight of dilaurylthiopropionate (antioxidant (III)), and 1.0 part by weight of vinyltrimethoxysilane. Example 10 was 10 parts by weight of dicumyl peroxide (free radical generator (I)) and 0.05 part by weight of dibutyltin dilaurate.
An electric cable was produced in the same manner as described above.
【００４５】＜実施例１２＞配合成分を、密度が０．９
２７、融点が１１５℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（II））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．５重量部、ジラウリルチオプロピオネー
ト（酸化防止剤（III ））を０．５重量部、ビニルトリ
メトキシシランを１．５重量部、ジクミルパーオキサイ
ド（遊離ラジカル発生剤（Ｉ））を０．１５重量部、ジ
ブチル錫ジラウレートを０．０５重量部とし、実施例１
０と同様にして電気ケーブルを作製した。<Example 12> A blending component was prepared with a density of 0.9.
27, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (II)) having a melting point of 115 ° C, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (0.5 parts by weight of antioxidant (I)), 0.5 parts by weight of dilaurylthiopropionate (antioxidant (III)), and 1.5 parts by weight of vinyltrimethoxysilane. Example 1 was 1 part by weight, 0.15 part by weight of dicumyl peroxide (free radical generator (I)) and 0.05 part by weight of dibutyltin dilaurate.
In the same manner as in Example No. 0, an electric cable was produced.
【００４６】＜実施例１３＞配合成分を、密度が０．９
３２、融点が１１８℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（III ））を５０重量部、密度が０．９
２０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を５０重量部、ペンタエリスリ
チル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（II））を０．１重量部、ジラウリルチオプロピオネー
ト（酸化防止剤（III ））を０．１重量部、ビニルトリ
メトキシシランを１．０重量部、２，５−ジメチル−
２，５−ジ−（ｔ−ブチルパーオキシ）ヘキサン（遊離
ラジカル発生剤（II））を０．１重量部、ジブチル錫ジ
ラウレートを０．０５重量部とし、実施例１０と同様に
して電気ケーブルを作製した。<Example 13> A blending component was prepared with a density of 0.9.
32, 50 parts by weight of a high-pressure radical polymerized polyethylene (polyethylene (III)) having a melting point of 118 ° C. and a density of 0.9
20, 50 parts by weight of a high-pressure radical polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (antioxidant (II)), 0.1 part by weight of dilaurylthiopropionate (antioxidant (III)), and 1.0 part by weight of vinyltrimethoxysilane. Parts by weight, 2,5-dimethyl-
An electric cable was prepared in the same manner as in Example 10 except that 0.1 part by weight of 2,5-di- (t-butylperoxy) hexane (free radical generator (II)) and 0.05 part by weight of dibutyltin dilaurate were used. Was prepared.
【００４７】＜実施例１４＞配合成分を、密度が０．９
３２、融点が１１８℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（III ））を５０重量部、密度が０．９
２０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を５０重量部、酸化防止剤とし
てのオクタデシル３−（３，５−ジ−ｔ−ブチル−４−
ヒドロキシフェニル）プロピオネート（酸化防止剤（I
V））を０．１重量部、ジラウリルチオプロピオネート
（酸化防止剤（III ））を０．１重量部、ビニルトリメ
トキシシランを０．７重量部、ジクミルパーイキサイド
（遊離ラジカル発生剤（Ｉ））を０．０５重量部、ジブ
チル錫ジラウレートを０．０５重量部とし、実施例１０
と同様にして電気ケーブルを作製した。<Example 14> A blending component was prepared with a density of 0.9.
32, 50 parts by weight of a high-pressure radical polymerized polyethylene (polyethylene (III)) having a melting point of 118 ° C. and a density of 0.9
20, 50 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., and octadecyl 3- (3,5-di-tert-butyl-4-) as an antioxidant
Hydroxyphenyl) propionate (Antioxidant (I
V)), 0.1 part by weight of dilauryl thiopropionate (antioxidant (III)), 0.7 part by weight of vinyltrimethoxysilane, dicumyl peroxide (free radical) Example 10 (generating agent (I)) and 0.05 parts by weight of dibutyltin dilaurate
An electric cable was produced in the same manner as described above.
【００４８】＜実施例１５＞配合成分を、密度が０．９
３２、融点が１１８℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（III ））を５０重量部、密度が０．９
２０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を５０重量部、酸化防止剤とし
ての２，４−ビス−（ｎ−オクチルチオ）−６−（４−
ヒドロキシ−３，５−ジ−ｔ−ブチルアニリノ）−１，
３，５−トリアジン（酸化防止剤（Ｖ））を０．１重量
部、ジラウリルチオプロピオネート（酸化防止剤（III
））を０．１重量部、ビニルトリメトキシシランを
１．０重量部、２，５−ジメチル−２，５−ジ−（ｔ−
ブチルパーオキシ）ヘキサン（遊離ラジカル発生剤（I
I））を０．１重量部、ジブチル錫ジラウレートを０．
０５重量部、ポリエチレン（III ）中にファーネスブラ
ックが２５重量％含有されるように調整したカーボンマ
スターバッチを４重量部とし、実施例１０と同様にして
電気ケーブルを作製した。<Example 15> A blending component having a density of 0.9
32, 50 parts by weight of a high-pressure radical polymerized polyethylene (polyethylene (III)) having a melting point of 118 ° C. and a density of 0.9
20, 50 parts by weight of high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., and 2,4-bis- (n-octylthio) -6- (4-
Hydroxy-3,5-di-t-butylanilino) -1,
0.1 parts by weight of 3,5-triazine (antioxidant (V)) and dilaurylthiopropionate (antioxidant (III
)), 0.1 part by weight of vinyltrimethoxysilane, 2,5-dimethyl-2,5-di- (t-
Butylperoxy) hexane (free radical generator (I
I)) is 0.1 part by weight, and dibutyltin dilaurate is 0.1 part by weight.
An electric cable was produced in the same manner as in Example 10, except that the carbon masterbatch was adjusted to be 0.5 parts by weight and the carbon master batch adjusted to contain 25% by weight of the furnace black in polyethylene (III).
【００４９】＜比較例９＞配合成分を、密度が０．９２
０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．０５重量部、金属害防止剤としてのＮ，
Ｎ′−ビス［３−（３，５−ジ−ｔ−ブチル−ヒドロキ
シフェニル）プロピオニル］ヒドラジンを０．０５重量
部、ビニルトリメトキシシランを１．０重量部、ジクミ
ルパーオキサイド（遊離ラジカル発生剤（Ｉ））を０．
１重量部、ジブチル錫ジラウレートを０．０５重量部と
し、実施例１０と同様にして電気ケーブルを作製した。
なお、金属害防止剤としてのＮ，Ｎ′−ビス［３−
（３，５−ジ−ｔ−ブチル−ヒドロキシフェニル）プロ
ピオニル］ヒドラジンはビニルトリメトキシシランに難
溶なので、ポリエチレン（Ｖ）に予めドライブレンドし
て押出機に投入した。<Comparative Example 9> A blended component having a density of 0.92
0, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (antioxidant (I)) in an amount of 0.05 part by weight;
0.05 parts by weight of N'-bis [3- (3,5-di-t-butyl-hydroxyphenyl) propionyl] hydrazine, 1.0 part by weight of vinyltrimethoxysilane, dicumyl peroxide (free radical generation Agent (I)).
An electric cable was produced in the same manner as in Example 10, except that 1 part by weight and 0.05 parts by weight of dibutyltin dilaurate were used.
In addition, N, N'-bis [3-
(3,5-Di-t-butyl-hydroxyphenyl) propionyl] hydrazine is hardly soluble in vinyltrimethoxysilane, so it was dry-blended with polyethylene (V) in advance and charged into an extruder.
【００５０】＜比較例１０＞配合成分を、密度が０．９
２０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、Ｎ，Ｎ′−ビス［３−（３，
５−ジ−ｔ−ブチル−ヒドロキシフェニル）プロピオニ
ル］ヒドラジンを０．０５重量部、ビニルトリメトキシ
シランを１．０重量部、２，５−ジメチル−２，５−ジ
−（ｔ−ブチルパーオキシ）ヘキサン（遊離ラジカル発
生剤（II））を０．０７重量部、ジブチル錫ジラウレー
トを０．０５重量部とし、比較例９と同様にして電気ケ
ーブルを作製した。<Comparative Example 10> A blended component having a density of 0.9
20, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (antioxidant (I)) in an amount of 0.1 part by weight and N, N'-bis [3- (3,
5-di-t-butyl-hydroxyphenyl) propionyl] hydrazine 0.05 parts by weight, vinyltrimethoxysilane 1.0 part by weight, 2,5-dimethyl-2,5-di- (t-butylperoxy) ) An electric cable was produced in the same manner as in Comparative Example 9 except that 0.07 part by weight of hexane (free radical generator (II)) and 0.05 part by weight of dibutyltin dilaurate were used.
【００５１】＜比較例１１＞配合成分を、密度が０．９
２０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．０３重量部、ジラウリルチオプロピオネ
ート（酸化防止剤（III ））を０．０３重量部、ビニル
トリメトキシシランを１．０重量部、ジクミルパーオキ
サイド（遊離ラジカル発生剤（Ｉ））を０．１重量部、
ジブチル錫ジラウレートを０．０５重量部とし、実施例
１０と同様にして電気ケーブルを作製した。<Comparative Example 11> A blended component having a density of 0.9
20, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (antioxidant (I)), 0.03 parts by weight of dilaurylthiopropionate (antioxidant (III)), and 1.0 parts by weight of vinyltrimethoxysilane. Parts by weight, 0.1 part by weight of dicumyl peroxide (free radical generator (I))
An electric cable was produced in the same manner as in Example 10 except that dibutyltin dilaurate was used in an amount of 0.05 part by weight.
【００５２】＜比較例１２＞配合成分を、密度が０．９
２０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．６重量部、ジラウリルチオプロピオネー
ト（酸化防止剤（III ））を０．６重量部、ビニルトリ
メトキシシランを１．０重量部、２，５−ジメチル−
２，５−ジ−（ｔ−ブチルパーオキシ）ヘキサン（遊離
ラジカル発生剤（II））を０．１重量部、ジブチル錫ジ
ラウレートを０．０５重量部とし、実施例１０と同様に
して電気ケーブルを作製した。<Comparative Example 12> A blending component was prepared with a density of 0.9.
20, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (antioxidant (I)) 0.6 parts by weight, dilauryl thiopropionate (antioxidant (III)) 0.6 parts by weight, vinyltrimethoxysilane 1.0 parts by weight Parts by weight, 2,5-dimethyl-
An electric cable was prepared in the same manner as in Example 10 except that 0.1 part by weight of 2,5-di- (t-butylperoxy) hexane (free radical generator (II)) and 0.05 part by weight of dibutyltin dilaurate were used. Was prepared.
【００５３】＜比較例１３＞配合成分を、密度が０．９
２０、融点が１１０℃の高圧ラジカル重合ポリエチレン
（ポリエチレン（Ｖ））を１００重量部、２，２−チオ
−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート］（酸化防止剤
（Ｉ））を０．１重量部、ビニルトリメトキシシランを
０．７重量部、ジクミルパーオキサイド（遊離ラジカル
発生剤（Ｉ））を０．０３重量部、ジブチル錫ジラウレ
ートを０．０５重量部とし、実施例１０と同様にして電
気ケーブルを作製した。<Comparative Example 13> A blended component having a density of 0.9
20, 100 parts by weight of a high-pressure radically polymerized polyethylene (polyethylene (V)) having a melting point of 110 ° C., and 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] (antioxidant (I)) 0.1 part by weight, vinyltrimethoxysilane 0.7 part by weight, dicumyl peroxide (free radical generator (I)) 0.03 part by weight Parts and dibutyltin dilaurate in 0.05 parts by weight, an electric cable was produced in the same manner as in Example 10.
【００５４】実施例１０〜１５及び比較例９〜１３の配
合組成を評価結果と共に表３及び表４に示した。なお、
評価は実施例１〜９、比較例１〜８の場合と同様にして
行ったが、金属害劣化特性は銅導体と接触した部分の変
色を調べ、変色の無いものを合格とした。The compositions of Examples 10 to 15 and Comparative Examples 9 to 13 are shown in Tables 3 and 4 together with the evaluation results. In addition,
The evaluation was performed in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 8. However, as for the metal damage deterioration characteristics, the discoloration of the portion in contact with the copper conductor was examined, and those having no discoloration were accepted.
【００５５】[0055]
【表３】 [Table 3]
【００５６】[0056]
【表４】 [Table 4]
【００５７】表３は、酸化防止剤を２種類以上併用して
添加した例であるが、実施例１０〜１５は押出性や加熱
変形特性等に加え、金属害劣化特性に優れている。ま
た、ボウタイトリー特性も良好である。一方、比較例
９、１０は従来の金属害防止剤を用いたもので、ボウタ
イトリーの発生が多い。酸化防止剤の添加量が本発明の
規定量よりも少ない比較例１１は、金属害劣化特性が悪
く、酸化防止剤の添加量が規定量よりも多い比較例１２
は、酸化防止剤が表面に析出し、汚れが生じた。また、
ラジカル開始剤量が少なく、本発明で規定する値以下の
架橋度を示す比較例１３は、加熱変形率が大きい。Table 3 shows examples in which two or more kinds of antioxidants are added in combination. Examples 10 to 15 are excellent in metal damage deterioration characteristics in addition to extrudability and heat deformation characteristics. Also, the bow titley characteristics are good. On the other hand, in Comparative Examples 9 and 10, the conventional metal harm inhibitor was used, and many bow title trees were generated. Comparative Example 11 in which the amount of the antioxidant added was smaller than the specified amount of the present invention had poor metal damage deterioration characteristics, and Comparative Example 12 in which the added amount of the antioxidant was larger than the specified amount.
In (2), the antioxidant was deposited on the surface, resulting in contamination. Also,
Comparative Example 13 in which the amount of the radical initiator is small and the degree of crosslinking is equal to or less than the value specified in the present invention is large in the heat deformation ratio.
【００５８】[0058]
【発明の効果】以上説明してきたように本発明によれ
ば、押出成形性、加熱変形率と伸び、耐ボウタイトリー
特性に優れる電気絶縁物及び架橋ポリエチレン絶縁電線
・ケーブルや付属品を安価に得ることができ、その工業
的価値は極めて高い。As described above, according to the present invention, it is possible to obtain inexpensively an electric insulator, a crosslinked polyethylene insulated wire / cable, and accessories having excellent extrudability, heat deformation rate and elongation, and anti-bow titley properties. And its industrial value is extremely high.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安部 淳一 茨城県日立市日高町５丁目１番１号 日立 電線株式会社パワーシステム研究所内 (72)発明者 野沢 英行 茨城県日立市日高町５丁目１番１号 日立 電線株式会社日高工場内 (72)発明者 古沢 健一 茨城県日立市日高町５丁目１番１号 日立 電線株式会社日高工場内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Junichi Abe 5-1-1 Hidaka-cho, Hitachi City, Ibaraki Prefecture Power Systems Research Laboratory, Hitachi Cable, Ltd. (72) Inventor Hideyuki Nozawa Hidaka-cho, Hitachi City, Ibaraki Prefecture 5-1-1, Hitachi Cable Co., Ltd. Hidaka Plant (72) Inventor Kenichi Furusawa 5-1-1, Hidaka-cho, Hitachi City, Ibaraki Prefecture Hitachi Cable Co., Ltd. Hidaka Plant
Claims (5)
１１５℃以上で密度が０．９２５〜０．９３５ｇ／cm3
のポリエチレン（ａ）を主体とするポリマ、又は前記ポ
リエチレン（ａ）９９〜５０重量部と密度が０．９１５
〜０．９２５ｇ／cm3 のポリエチレン（ｂ）１〜５０重
量部を含むブレンドポリエチレンを主体とするポリマ
と、一般式 ＲＲ′ＳｉＹ2 （式中Ｒはオレフィン性不飽和炭化水素基あるいはハイ
ドロカーボンオキシ基であり、Ｙは加水分解可能な有機
基であり、Ｒ′は前記Ｒ基かＹ基である）で表されるシ
ランとを、遊離ラジカルを生じさせる化合物の存在下で
反応させて得られるシラン変性ポリマからなることを特
徴とする架橋性電気絶縁用樹脂組成物。1. Synthesized by high-pressure radical polymerization, having a melting point of 115 ° C. or more and a density of 0.925 to 0.935 g / cm 3.
A polymer mainly composed of polyethylene (a), or 99 to 50 parts by weight of the polyethylene (a) and a density of 0.915
A polymer mainly composed of a blended polyethylene containing 1 to 50 parts by weight of polyethylene (b) having a weight of 0.95 g / cm 3 and a general formula RR′SiY 2 (where R is an olefinically unsaturated hydrocarbon group or a hydrocarbonoxy group) Y is a hydrolyzable organic group, and R ′ is the above-mentioned R group or Y group) in the presence of a compound generating free radicals. A crosslinkable resin composition for electrical insulation, comprising a silane-modified polymer.
ラジカルを生じさせる化合物として、ジクミルパーオキ
サイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパ
ーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ
（ｔ−ブチルパーオキシ）ヘキシン−３、α, α’−ビ
ス（ｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼ
ン、ブチルクミルパーオキサイド、イソプロピルクミル
−ｔ−ブチルパーオキサイドから選ばれる１種類または
２種類以上を０．０５〜０．１５重量部含有する請求項
１記載の架橋性電気絶縁用樹脂組成物。2. Dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5 -Dimethyl-2,5-di (t-butylperoxy) hexyne-3, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, butylcumyl peroxide, isopropylcumyl-t-butyl The crosslinkable resin composition for electrical insulation according to claim 1, which comprises one or more selected from peroxides in an amount of 0.05 to 0.15 parts by weight.
剤として、２，２−チオ−ジエチレンビス［３−（３，
５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピ
オネート］、ペンタエリスリチル−テトラキス［３−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）
プロピオネート］、オクタデシル３−（３，５−ジ−ｔ
−ブチル−４−ヒドロキシフェニル）プロピオネート、
２，４−ビス−（ｎ−オクチルチオ）−６−（４−ヒド
ロキシ−３，５−ジ−ｔ−ブチルアニリノ）−１，３，
５−トリアジンから選ばれる１種類または２種類以上を
０．０５〜０．５重量部とジラウリルチオプロピオネー
トを０．０５〜０．５重量部含有する請求項１記載の架
橋性電気絶縁用樹脂組成物。3. An antioxidant based on 100 parts by weight of the polymer is 2,2-thio-diethylenebis [3- (3,3).
5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], octadecyl 3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate,
2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,3
2. The crosslinkable electrical insulation according to claim 1, comprising 0.05 to 0.5 parts by weight of one or more kinds selected from 5-triazines and 0.05 to 0.5 parts by weight of dilaurylthiopropionate. Resin composition.
気絶縁用樹脂組成物からなる成形体をシラノール縮合触
媒の存在下で水分と接触させることにより架橋度が４０
％以上になるように架橋されていることを特徴とする電
気絶縁物。4. A molded article comprising the crosslinkable resin composition for electric insulation according to claim 1, which is brought into contact with moisture in the presence of a silanol condensation catalyst to have a degree of crosslinking of 40.
% Electrical insulator, characterized in that it is crosslinked so as to have a percentage of not less than 10%.
いずれかに記載の架橋性電気絶縁用樹脂組成物からなる
絶縁層を有し、当該絶縁層がシラノール縮合触媒の存在
下で水分と接触させることにより架橋度が４０％以上に
なるように架橋されていることを特徴とする電線・ケー
ブル。5. An insulating layer comprising the crosslinkable electrical insulating resin composition according to claim 1 on a conductor or a conductor shielding layer, wherein the insulating layer is formed in the presence of a silanol condensation catalyst. An electric wire or cable which is crosslinked so as to have a degree of crosslinking of 40% or more by contact with water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6794698A JPH11265618A (en) | 1998-03-18 | 1998-03-18 | Crosslinkable resin composition for electrical insulation, electrical insulator, electric wire / cable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6794698A JPH11265618A (en) | 1998-03-18 | 1998-03-18 | Crosslinkable resin composition for electrical insulation, electrical insulator, electric wire / cable |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11265618A true JPH11265618A (en) | 1999-09-28 |
Family
ID=13359629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6794698A Pending JPH11265618A (en) | 1998-03-18 | 1998-03-18 | Crosslinkable resin composition for electrical insulation, electrical insulator, electric wire / cable |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11265618A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008234883A (en) * | 2007-03-19 | 2008-10-02 | Yazaki Corp | Crosslinked polyethylene electric wire / cable and insulator resin composition |
-
1998
- 1998-03-18 JP JP6794698A patent/JPH11265618A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008234883A (en) * | 2007-03-19 | 2008-10-02 | Yazaki Corp | Crosslinked polyethylene electric wire / cable and insulator resin composition |
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