JP4329547B2 - Method for producing cross-linked ethylene resin tube - Google Patents
Method for producing cross-linked ethylene resin tube Download PDFInfo
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- JP4329547B2 JP4329547B2 JP2004010177A JP2004010177A JP4329547B2 JP 4329547 B2 JP4329547 B2 JP 4329547B2 JP 2004010177 A JP2004010177 A JP 2004010177A JP 2004010177 A JP2004010177 A JP 2004010177A JP 4329547 B2 JP4329547 B2 JP 4329547B2
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- ethylene
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- ethylene resin
- ethylenically unsaturated
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- 229920005989 resin Polymers 0.000 title claims description 118
- 239000011347 resin Substances 0.000 title claims description 118
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 86
- 239000005977 Ethylene Substances 0.000 title claims description 86
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- -1 unsaturated silane compound Chemical class 0.000 claims description 34
- 239000008188 pellet Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000009833 condensation Methods 0.000 claims description 18
- 230000005494 condensation Effects 0.000 claims description 18
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 18
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 17
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 description 14
- 238000005452 bending Methods 0.000 description 13
- 229920013716 polyethylene resin Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004711 α-olefin Substances 0.000 description 8
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000000155 melt Substances 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920003355 Novatec® Polymers 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- ZICNIEOYWVIEQJ-UHFFFAOYSA-N (2-methylbenzoyl) 2-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1C ZICNIEOYWVIEQJ-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- PGWCWELYDMCGJX-UHFFFAOYSA-N 2-butylperoxycarbonylbenzenecarboperoxoic acid Chemical compound CCCCOOC(=O)C1=CC=CC=C1C(=O)OO PGWCWELYDMCGJX-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QZEJHHGVNNHHSU-UHFFFAOYSA-N hexyl benzenecarboperoxoate Chemical compound CCCCCCOOC(=O)C1=CC=CC=C1 QZEJHHGVNNHHSU-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Description
本発明は、架橋エチレン系樹脂管の製造方法に関し、更に詳しくは、シラン変性エチレン系樹脂の水架橋方法を用いて、樹脂の熱劣化を抑制して安定した品質を有するのみならず、曲げ加工性に優れ、且つ、耐クリープ性にも優れる架橋エチレン系樹脂管を製造することができる架橋エチレン系樹脂管の製造方法に関する。 The present invention relates to a method for producing a crosslinked ethylene resin tube, and more specifically, by using a water crosslinking method for a silane-modified ethylene resin, not only has a stable quality by suppressing thermal deterioration of the resin, but also bending processing. The present invention relates to a method for producing a crosslinked ethylene resin pipe capable of producing a crosslinked ethylene resin pipe having excellent properties and excellent creep resistance.
従来より、エチレン性不飽和シラン化合物によるシラン変性エチレン系樹脂の水架橋方法は、従来の有機過酸化物による化学架橋方法や電子線照射による方法に比して、架橋作業が比較的容易なこと、及び、架橋のための設備投資が著しく少なくてすること等の工業的価値を有することから、架橋エチレン系樹脂管の製造等において多用されている。 Conventionally, the water cross-linking method of silane-modified ethylene resin with an ethylenically unsaturated silane compound is relatively easy to cross-link compared with the conventional chemical cross-linking method with organic peroxide and the method of electron beam irradiation. And since it has industrial value such as significantly reducing the capital investment for crosslinking, it is frequently used in the production of crosslinked ethylene-based resin pipes.
しかしながら、シラン変性エチレン系樹脂の水架橋方法を用いた従来の架橋エチレン系樹脂管の製造方法は、例えばポリエチレン樹脂を、エチレン性不飽和シラン化合物とラジカル発生剤と共に押出機等で溶融混練してエチレン性不飽和シラン化合物で変性したシラン変性ポリエチレン樹脂ペレットとなし、該シラン変性ポリエチレン樹脂ペレットに、別に作製したシラノール縮合触媒のマスターバッチを配合し、再度、押出機で溶融混練し管状に溶融押出成形して変性ポリエチレン樹脂管となし、次いで、水分と接触させて架橋させるという、押出機を少なくとも２回通過させる方法が採られ、樹脂としては熱劣化を受け易い条件のもとでなされていた。 However, a conventional method for producing a crosslinked ethylene resin tube using a water crosslinking method of a silane-modified ethylene resin is, for example, a method in which a polyethylene resin is melt-kneaded with an extruder or the like together with an ethylenically unsaturated silane compound and a radical generator. A silane-modified polyethylene resin pellet modified with an ethylenically unsaturated silane compound is used, and a master batch of a silanol condensation catalyst prepared separately is blended into the silane-modified polyethylene resin pellet, and melt-kneaded again with an extruder and melt-extruded into a tube. A method of forming a modified polyethylene resin tube to form a modified polyethylene resin tube and then cross-linking it by contacting with moisture was adopted at least twice through an extruder. .
これに対して、エチレン系樹脂としてパウダー状のポリエチレン樹脂を用い、シラン変性樹脂ペレットの段階を経由することなく、ポリエチレン樹脂パウダー、エチレン性不飽和シラン化合物、及びラジカル発生剤を押出機に供給し溶融混練して、ポリエチレン樹脂をエチレン性不飽和シラン化合物で変性し、管状に溶融押出成形して変性ポリエチレン樹脂管となし、その際、シラノール縮合触媒を適宜の手段で押出機に供給し、次いで、水分と接触させて架橋ポリエチレン樹脂管となす、直接成形法が提案されている（例えば、特許文献１、及び特許文献２参照。）。しかしながら、本発明者等の検討によると、これらの方法では、得られる架橋ポリエチレン樹脂管における樹脂の架橋度としてのゲル分率のバラツキが大きく、品質が安定しないという問題が内在することが判明した。
そして、本発明者等は、そのシラン変性エチレン系樹脂の水架橋方法を用いて、樹脂の熱劣化を抑制して安定した品質の架橋エチレン系樹脂管を製造するべく、エチレン系樹脂として、低密度ポリエチレン等の樹脂ペレットと樹脂パウダーとを併用する方法を見出し、先に特許出願した（例えば、特許文献３、及び特許文献４参照。）。しかしながら、引き続いて検討を進めたところ、これらの方法により得られる架橋エチレン系樹脂管は、曲げ加工性を追求するあまり、熱間内圧クリープ性が劣り、例えば、ＪＩＳ Ｋ６７６９に準拠した、９５℃、円周応力４．８ＭＰａ、１時間の条件下での熱間内圧クリープ試験において、割れや漏れが生じてしまうことが判明した。
本発明は、前述の従来技術に鑑みてなされたもので、従って、本発明は、シラン変性エチレン系樹脂の水架橋方法を用いて、樹脂の熱劣化を抑制して安定した品質を有するのみならず、曲げ加工性に優れ、且つ、耐クリープ性にも優れる架橋エチレン系樹脂管を製造することができる架橋エチレン系樹脂管の製造方法を提供することを目的とする。 The present invention has been made in view of the above-described prior art, and therefore, the present invention only has a stable quality by suppressing the thermal degradation of the resin by using the water crosslinking method of the silane-modified ethylene resin. In addition, an object of the present invention is to provide a method for producing a crosslinked ethylene resin pipe capable of producing a crosslinked ethylene resin pipe having excellent bending workability and excellent creep resistance.
本発明は、密度が０．９４５〜０．９６０ｇ／ｃｍ ３ のエチレン系樹脂ペレットに対して、少なくとも、密度が０．９１０〜０．９３０ｇ／ｃｍ ３ のエチレン系樹脂パウダー、エチレン性不飽和シラン化合物、及びラジカル発生剤を添加し混合した後、押出機のホッパーに供給し溶融混練して、エチレン系樹脂をエチレン性不飽和シラン化合物で変性し、管状に溶融押出成形して変性エチレン系樹脂管となし、次いで、シラノール縮合触媒の存在下に水分と接触させて該変性エチレン系樹脂を架橋させる架橋エチレン系樹脂管の製造方法、を要旨とする。 The present invention is, relative density is 0.94 5~0.960 g / cm 3 ethylene-based resin pellets, at least, the density of 0.910~ 0.93 0 g / cm 3 ethylene-based resin powder, ethylene After adding and mixing the unsaturated silane compound and the radical generator, the mixture is supplied to the hopper of the extruder and melt-kneaded, and the ethylene resin is modified with the ethylenically unsaturated silane compound and melt-extruded into a tubular shape. The gist is a modified ethylene-based resin tube, and then a method for producing a crosslinked ethylene-based resin tube in which the modified ethylene-based resin is crosslinked by contacting with moisture in the presence of a silanol condensation catalyst.
本発明によれば、シラン変性エチレン系樹脂の水架橋方法を用いて、樹脂の熱劣化を抑制して安定した品質を有するのみならず、曲げ加工性に優れ、且つ、耐クリープ性にも優れる架橋エチレン系樹脂管を製造することができる架橋エチレン系樹脂管の製造方法を提供することができる。 According to the present invention, by using the water crosslinking method of a silane-modified ethylene resin, not only has a stable quality by suppressing thermal deterioration of the resin, but also has excellent bending workability and excellent creep resistance. A method for producing a crosslinked ethylene resin tube capable of producing a crosslinked ethylene resin tube can be provided.
本発明において、エチレン系樹脂としては、エチレンの単独重合体、エチレンと、プロピレン、１−ブテン、３−メチル−１−ブテン、１−ペンテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテン、１−デセン等の炭素数２〜２０程度の他のα−オレフィンや、酢酸ビニル、（メタ）アクリル酸、（メタ）アクリル酸エステル等との共重合体等が挙げられ、具体的には、例えば、低・中・高密度ポリエチレン等（分岐状又は直鎖状）のエチレン単独重合体、及び、エチレン−プロピレン共重合体、エチレン−１−ブテン共重合体、エチレン−４−メチル−１−ペンテン共重合体、エチレン−１−ヘキセン共重合体、エチレン−１−オクテン共重合体、エチレン−酢酸ビニル共重合体、エチレン−（メタ）アクリル酸共重合体、エチレン−（メタ）アクリル酸エチル共重合体等が挙げられ、これらエチレン系樹脂のメルトフローレートは、ＪＩＳ Ｋ７２１０に準拠して、温度１９０℃、荷重２１．１８Ｎで測定した値として、０．２〜２０ｇ／１０分であるのが好ましい。 In the present invention, the ethylene-based resin includes ethylene homopolymer, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, -Copolymers with other α-olefins having about 2 to 20 carbon atoms such as octene and 1-decene, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, etc. For example, ethylene homopolymers such as low, medium and high density polyethylene (branched or linear), ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-4-methyl -1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, Examples include lene- (meth) acrylic acid ethyl copolymers, and the melt flow rate of these ethylene resins is 0.2 as a value measured at a temperature of 190 ° C. and a load of 21.18 N in accordance with JIS K7210. It is preferably ˜20 g / 10 min.
そして、本発明においては、前記エチレン系樹脂として、密度が０．９４５〜０．９６０ｇ／ｃｍ ３ の前記エチレン系樹脂ペレットと、密度が０．９１０〜０．９３０ｇ／ｃｍ ３ の前記エチレン系樹脂パウダーとを併用することを必須とする。ペレットのみ、或いはパウダーのみでは、安定した品質の架橋エチレン系樹脂管を製造することが困難となり、又、ペレットとして用いる前記エチレン系樹脂の密度が前記範囲未満、及び、パウダーとして用いる前記エチレン系樹脂の密度が前記範囲超過では、曲げ加工性と耐クリープ性を両立させることが困難となる。 Then, in the present invention, as the ethylene-based resin, and the ethylene-based resin pellets having a density of 0.94 5~0.960 g / cm 3, density of 0.910~ 0.93 0 g / cm 3 It is essential to use the ethylene resin powder together. It is difficult to produce a stable quality crosslinked ethylene resin tube with only pellets or powder, and the density of the ethylene resin used as pellets is less than the above range, and the ethylene resin used as powder. If the density exceeds the above range, it becomes difficult to achieve both bending workability and creep resistance.
本発明において、前記エチレン系樹脂ペレットとしては、０．９４５〜０．９６０ｇ／ｃｍ３の密度の範囲である樹脂であり、直鎖状のエチレン単独重合体、或いは直鎖状のエチレン−α−オレフィン共重合体が特に好ましい。又、前記エチレン系樹脂パウダーとしては、０．９１０〜０．９３０ｇ／ｃｍ３の密度の範囲である樹脂であり、分岐状のエチレン単独重合体、或いは、直鎖状のエチレン−α−オレフィン共重合体が特に好ましい。 In the present invention, the ethylene-based resin pellets include 0 . A resin having a density in the range of 945 to 0.960 g / cm 3 , and a linear ethylene homopolymer or a linear ethylene-α-olefin copolymer is particularly preferable. Further, the ethylene resin powder is preferably 0 . It is a resin having a density range of 910 to 0.930 g / cm 3 , and a branched ethylene homopolymer or a linear ethylene-α-olefin copolymer is particularly preferable.
尚、ここで、ペレットとしては、円柱状、角柱状、板状、球状、楕円球状等の通常の形状であって、大径が１〜５ｍｍ程度の大きさのものが用いられ、又、パウダーとしては、平均粒径が５００μｍ以下程度のものが用いられる。 Here, as the pellets, those having a normal shape such as a columnar shape, a prismatic shape, a plate shape, a spherical shape, an elliptical spherical shape and a large diameter of about 1 to 5 mm are used. In this case, those having an average particle diameter of about 500 μm or less are used.
又、本発明において、エチレン性不飽和シラン化合物としては、エチレン性不飽和結合を有するシラン化合物であれば特に限定されるものではないが、下記一般式（Ｉ）で表される化合物が好ましい。 In the present invention, the ethylenically unsaturated silane compound is not particularly limited as long as it is a silane compound having an ethylenically unsaturated bond, but a compound represented by the following general formula (I) is preferable.
〔式（Ｉ）中、Ｒ1 はエチレン性不飽和ハイドロカーボン基又はハイドロカーボンオキシ基、Ｒ2 はハイドロカーボン基、Ｙは加水分解可能な有機基を表し、ｎは０〜２の整数である。〕 [In the formula (I), R 1 represents an ethylenically unsaturated hydrocarbon group or hydrocarbonoxy group, R 2 represents a hydrocarbon group, Y represents a hydrolyzable organic group, and n is an integer of 0 to 2. . ]
ここで、Ｒ1 としては、例えば、ビニル基、プロペニル基、ブテニル基、シクロヘキセニル基、γ−（メタ）アクリロイルオキシプロピル基等が、Ｒ2 としては、例えば、メチル基、エチル基、プロピル基、デシル基、フェニル基等が、Ｙとしては、例えば、メトキシ基、エトキシ基、ホルミルオキシ基、アセトキシ基、プロピオニルオキシ基、アルキルアミノ基、アリールアミノ基等が、それぞれ挙げられ、このようなエチレン性不飽和シラン化合物の具体例としては、例えば、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、γ−メタクリロイルオキシプロピルトリメトキシシラン等が挙げられる。 Here, examples of R 1 include a vinyl group, a propenyl group, a butenyl group, a cyclohexenyl group, and a γ- (meth) acryloyloxypropyl group. Examples of R 2 include a methyl group, an ethyl group, and a propyl group. , Decyl group, phenyl group and the like, and examples of Y include, for example, methoxy group, ethoxy group, formyloxy group, acetoxy group, propionyloxy group, alkylamino group, arylamino group, etc. Specific examples of the unsaturated silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.
又、本発明において、ラジカル発生剤としては、例えば、ジイソプロピルベンゼンヒドロパーオキサイド、２，５−ジメチル−２，５−ジ（ヒドロパーオキシ）ヘキサン等のヒドロパーオキサイド類、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド、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等のジアルキルパーオキサイド類、ビス−３，５，５−トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、ベンゾイルパーオキサイド、ｏ−メチルベンゾイルパーオキサイド、２，４−ジクロロベンゾイルパーオキサイド等のジアシルパーオキサイド類、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシピバレート、ｔ−ブチルパーオキシオクトエート、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシベンゾエート、ジ−ｔ−ブチルジパーオキシフタレート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキシン−３等のパーオキシエステル類、メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド等のケトンパーオキサイド類等の有機過酸化物、アゾビスイソブチロニトリル、アゾビス（２，４−ジメチルバレロニトリル）等のアゾ化合物等が挙げられ、中で、有機過酸化物が好ましい。 In the present invention, examples of the radical generator include hydroperoxides such as diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di (hydroperoxy) hexane, and di-t-butylperoxide. Oxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxide) Oxy) hexyne-3 and other dialkyl peroxides, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, 2,4-dichlorobenzoyl peroxide Diacyl peroxides such as t-butylperoxyacete T-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxy octoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxybenzoate, di-t- Peroxyesters such as butyldiperoxyphthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3, Examples include organic peroxides such as ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, and azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile). Peroxides are preferred.
そして、本発明においては、前記エチレン系樹脂ペレットに対して、少なくとも、前記エチレン系樹脂パウダー、前記エチレン性不飽和シラン化合物、及び前記ラジカル発生剤を添加し混合した後、押出機のホッパーに供給し溶融混練して、エチレン系樹脂をエチレン性不飽和シラン化合物で変性し、管状に溶融押出成形して変性エチレン系樹脂管となす。 In the present invention, at least the ethylene resin powder, the ethylenically unsaturated silane compound, and the radical generator are added to and mixed with the ethylene resin pellets, and then supplied to the hopper of the extruder. Then, it is melt-kneaded, the ethylene resin is modified with an ethylenically unsaturated silane compound, and melt-extruded into a tube to form a modified ethylene resin tube.
ここで、前記エチレン系樹脂パウダーの添加量は、前記エチレン系樹脂ペレット１００重量部に対して、１〜２０重量部とするのが好ましく、２〜１８重量部とするのが更に好ましく、３〜１６重量部とするのが特に好ましい。エチレン系樹脂パウダーの添加量が前記範囲未満では、樹脂が押出機スクリュー上で滑り易く、押出変動が発生したり、高ゲル分率の架橋度の架橋エチレン系樹脂管を得ることが困難な傾向となり、一方、前記範囲超過では、液体状のエチレン性不飽和シラン化合物やラジカル発生剤の分散が不均一となって、安定した品質の架橋エチレン系樹脂管を製造することが困難な傾向となる。 Here, the addition amount of the ethylene resin powder is preferably 1 to 20 parts by weight, more preferably 2 to 18 parts by weight, with respect to 100 parts by weight of the ethylene resin pellets. 16 parts by weight is particularly preferable. If the addition amount of the ethylene resin powder is less than the above range, the resin tends to slip on the extruder screw, and the extrusion fluctuation tends to occur or it is difficult to obtain a crosslinked ethylene resin tube having a high gel fraction and a crosslinking degree. On the other hand, if the above range is exceeded, the dispersion of the liquid ethylenically unsaturated silane compound and the radical generator becomes non-uniform, and it tends to be difficult to produce a stable quality crosslinked ethylene resin tube. .
又、前記エチレン性不飽和シラン化合物、及び前記ラジカル発生剤の添加量は、前記エチレン系樹脂ペレットと前記エチレン系樹脂パウダーの合計量１００重量部に対して、エチレン性不飽和シラン化合物１〜６重量部、及びラジカル発生剤０．０２〜０．６重量部とするのが好ましい。エチレン性不飽和シラン化合物、及びラジカル発生剤の添加量が前記範囲未満では、高ゲル分率の架橋度の架橋エチレン系樹脂管を得ることが困難な傾向となり、一方、前記範囲超過では、得られる架橋エチレン系樹脂管にフィッシュアイやブツ等が発生して管としての機械的強度等が低下する傾向となる。 The ethylenically unsaturated silane compound and the radical generator are added in an amount of ethylenically unsaturated silane compounds 1 to 6 with respect to 100 parts by weight of the total amount of the ethylene resin pellets and the ethylene resin powder. It is preferable to use 0.02 to 0.6 parts by weight of a weight generator and a radical generator. If the addition amount of the ethylenically unsaturated silane compound and the radical generator is less than the above range, it tends to be difficult to obtain a cross-linked ethylene resin tube having a high gel fraction and a cross-linking degree. In such a cross-linked ethylene resin pipe, fish eyes, blisters and the like are generated, and the mechanical strength of the pipe tends to be lowered.
前記エチレン系樹脂ペレットに対して、前記エチレン系樹脂パウダー、前記エチレン性不飽和シラン化合物、及び前記ラジカル発生剤を添加し混合するには、例えば、タンブラーブレンダー、リボンブレンダー、Ｖ型ブレンダー、ヘンシェルミキサー等の混合機を用い、該混合物を押出機のホッパーに供給し、通常１５０〜３００℃程度の温度範囲内で、用いたラジカル発生剤の分解温度以上の温度で溶融混練して、エチレン系樹脂をエチレン性不飽和シラン化合物で変性し、マンドレルを備えた環状ダイより管状に溶融押出し、内部サイジング或いは外部サイジングすることにより成形して変性エチレン系樹脂管となす。 In order to add and mix the ethylene resin powder, the ethylenically unsaturated silane compound, and the radical generator to the ethylene resin pellet, for example, a tumbler blender, a ribbon blender, a V-type blender, a Henschel mixer The mixture is supplied to the hopper of the extruder, and melt-kneaded at a temperature equal to or higher than the decomposition temperature of the used radical generator within a temperature range of about 150 to 300 ° C. Is modified with an ethylenically unsaturated silane compound, melt-extruded into a tube from an annular die equipped with a mandrel, and molded by internal sizing or external sizing to form a modified ethylene resin tube.
次いで、その変性エチレン系樹脂管を、シラノール縮合触媒の存在下に水分と接触させて該変性エチレン系樹脂を架橋させるにおいて、用いられるシラノール縮合触媒としては、シリコーンのシラノール間の脱水縮合反応を促進するものであり、具体的には、例えば、ジブチル錫ジアセテート、ジブチル錫ジラウテート、ジブチル錫ジオクテート、ジオクチル錫ジラウテート等が挙げられる。 Next, the modified ethylene resin tube is brought into contact with moisture in the presence of a silanol condensation catalyst to crosslink the modified ethylene resin. As the silanol condensation catalyst used, a dehydration condensation reaction between silanols of silicone is promoted. Specifically, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate and the like can be mentioned.
又、そのシラノール縮合触媒の使用量は、前記エチレン系樹脂ペレットと前記エチレン系樹脂パウダーの合計量１００重量部に対して０．０１〜０．５重量部とするのが好ましい。シラノール縮合触媒の使用量が前記範囲未満では、高ゲル分率の架橋度の架橋エチレン系樹脂管を得ることが困難な傾向となり、一方、前記範囲超過では、得られる架橋エチレン系樹脂管にフィッシュアイやブツ等が発生して管としての機械的強度等が低下する傾向となる。 Moreover, it is preferable that the usage-amount of the silanol condensation catalyst shall be 0.01-0.5 weight part with respect to 100 weight part of total amounts of the said ethylene resin pellet and the said ethylene resin powder. If the amount of the silanol condensation catalyst used is less than the above range, it tends to be difficult to obtain a crosslinked ethylene resin tube having a high gel fraction and a crosslinking degree. Eyes, bumps and the like are generated, and the mechanical strength of the tube tends to decrease.
又、前記シラノール縮合触媒の使用方法としては、シラノール縮合触媒を、前記エチレン系樹脂パウダー、前記エチレン性不飽和シラン化合物、及びラジカル発生剤と共に前記エチレン系樹脂ペレットに添加し混合する方法、シラノール縮合触媒を押出機の途中に設けた注入孔から圧入する方法、又は、シラノール縮合触媒を溶液又は分散液として変性エチレン系樹脂管表面に塗布するか、或いは、その溶液又は分散液に変性エチレン系樹脂管を含浸させる等の方法が採られる。中で、本発明においては、シラノール縮合触媒を、前記エチレン系樹脂パウダー、前記エチレン性不飽和シラン化合物、及びラジカル発生剤と共に前記エチレン系樹脂ペレットに添加し混合する方法、又は、シラノール縮合触媒を押出機の途中に設けた注入孔から圧入する方法によるのが好ましく、シラノール縮合触媒を、前記エチレン系樹脂パウダー、前記エチレン性不飽和シラン化合物、及びラジカル発生剤と共に前記エチレン系樹脂ペレットに添加し混合する方法によるのが特に好ましい。 The silanol condensation catalyst may be used by adding the silanol condensation catalyst to the ethylene resin pellets together with the ethylene resin powder, the ethylenically unsaturated silane compound, and the radical generator, and mixing the silanol condensation catalyst. A method in which a catalyst is press-fitted from an injection hole provided in the middle of an extruder, or a silanol condensation catalyst is applied as a solution or a dispersion on the surface of a modified ethylene resin tube, or a modified ethylene resin in the solution or dispersion A method such as impregnation of a tube is employed. In the present invention, in the present invention, a silanol condensation catalyst is added to the ethylene resin pellets together with the ethylene resin powder, the ethylenically unsaturated silane compound, and a radical generator, and the silanol condensation catalyst is mixed. It is preferable to use a method of press-fitting from an injection hole provided in the middle of the extruder, and a silanol condensation catalyst is added to the ethylene resin pellet together with the ethylene resin powder, the ethylenically unsaturated silane compound, and a radical generator. It is particularly preferable to use a mixing method.
水架橋は、しかる後、前記変性エチレン系樹脂管を、常温〜２００℃程度、通常は常温〜１００℃程度の液状又は蒸気状の水に１時間〜１週間程度、通常は３〜１２時間程度にわたって接触させることによりなされ、得られる架橋エチレン系樹脂管における樹脂の架橋度としてのゲル分率は、６５％以上とするのが好ましい。 After the water crosslinking, the modified ethylene-based resin tube is then immersed in liquid or vaporized water at room temperature to about 200 ° C., usually from room temperature to about 100 ° C. for about 1 hour to about 1 week, usually about 3 to 12 hours. The gel fraction as the degree of cross-linking of the resin in the obtained cross-linked ethylene-based resin pipe is preferably 65% or more.
尚、本発明における前記架橋エチレン系樹脂管には、本発明の効果を損なわない範囲で、前記エチレン性不飽和シラン化合物変性エチレン系樹脂以外の熱可塑性樹脂やゴム、及び、酸化防止剤、光安定剤、紫外線吸収剤、造核剤、中和剤、帯電防止剤、滑剤、ブロッキング防止剤、分散剤、流動性改良剤、可塑剤、離型剤、難燃剤、着色剤、充填材等が添加されていてもよい。 The crosslinked ethylene resin tube of the present invention includes a thermoplastic resin or rubber other than the ethylenically unsaturated silane compound-modified ethylene resin, an antioxidant, light, and the like within a range not impairing the effects of the present invention. Stabilizers, UV absorbers, nucleating agents, neutralizing agents, antistatic agents, lubricants, antiblocking agents, dispersants, fluidity improvers, plasticizers, mold release agents, flame retardants, colorants, fillers, etc. It may be added.
以下、本発明を実施例により更に具体的に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
実施例１
密度０．９５１ｇ／ｃｍ3 、１９０℃でのメルトフローレート６ｇ／１０分のエチレン−α−オレフィン共重合体樹脂ペレット（日本ポリケム社製「ノバテックＨＤ ＨＪ３６０」）１００重量部に、密度０．９２３ｇ／ｃｍ3 、１９０℃でのメルトフローレート５０ｇ／１０分のエチレン−α−オレフィン共重合体樹脂パウダー（日本ポリケム社製「ノバテックＬＬ ＵＪ７９０Ｇ」）を８重量部、並びに、これらのエチレン系樹脂ペレットとエチレン系樹脂パウダーの合計量１００重量部に対して、エチレン性不飽和シラン化合物としてのビニルトリエトキシシラン（東レダウコーニングシリコーン社製「ＳＺ６３００ ＳＩＬＡＮＥ」）３重量部、ラジカル発生剤としての２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン（日本油脂社製「パーヘキサ２５Ｂ」）０．１重量部、及び、シラノール縮合触媒としてのジブチル錫ジオクテート（三共有機合成社製「ＳＴＡＮＮ＝ＳＮＴ＝１Ｆ」）０．１重量部を添加し、ヘンシェルミキサーで混合した後、口径５０ｍｍ、Ｌ／Ｄ２４の押出機（アイ・ケージ社製）のホッパーに供給し１９０℃で溶融混練して、エチレン系樹脂をエチレン性不飽和シラン化合物で変性し、管状に溶融押出して冷却させることにより変性エチレン系樹脂管となし、次いで、８０℃の温水を管内に８時間通水することにより、外径１７ｍｍ、肉厚１．９ｍｍの架橋エチレン系樹脂管を製造した。
Example 1
Density of 0.951 g / cm 3 and 100 parts by weight of ethylene-α-olefin copolymer resin pellets (“Novatech HD HJ360” manufactured by Nippon Polychem Co., Ltd.) at a melt flow rate of 6 g / 10 min at 190 ° C. / cm 3, a melt flow rate 50 g / 10 min ethylene -α- olefin copolymer resin powder at 190 ° C. (Nippon Polychem Co., Ltd., "Novatec LL UJ790G") 8 parts by weight, and, these ethylene-based resin pellets 3 parts by weight of vinyltriethoxysilane (“SZ6300 SILANE” manufactured by Toray Dow Corning Silicone) as an ethylenically unsaturated silane compound, 5-dimethyl-2,5-di (benzoylperoxy) hexane ( 0.1 part by weight of “Perhexa 25B” manufactured by Nippon Oil & Fats Co., Ltd. and 0.1 part by weight of dibutyltin dioctate (“SANN = SNT = 1F” manufactured by Sansha Co., Ltd.) as a silanol condensation catalyst were added, and Henschel After mixing with a mixer, it is supplied to a hopper of an extruder (made by I-Cage) having an aperture of 50 mm and L / D24, melted and kneaded at 190 ° C., an ethylene resin is modified with an ethylenically unsaturated silane compound, and tubular A modified ethylene-based resin tube is formed by melting and extruding to 80 ° C., and then passing hot water of 80 ° C. through the tube for 8 hours to produce a crosslinked ethylene-based resin tube having an outer diameter of 17 mm and a wall thickness of 1.9 mm. did.
得られた架橋エチレン系樹脂管について、以下に示す方法で、曲げ強度を測定したところ２２５Ｎであり、又、耐クリープ性を試験したところ、管に割れや漏れは生じなかった。
＜曲げ強度＞
得られた架橋エチレン系樹脂管から長さ１５０ｍｍをサンプリングし、支点間距離１００ｍｍで中央部を５０ｍｍ／分の速度で押し下げる３点曲げ試験を行い、１０ｍｍ押し下げたときの荷重を測定した。
＜耐クリープ性＞
ＪＩＳ Ｋ６７６９に準拠して、９５℃、円周応力４．８ＭＰａ、１時間の条件下での熱間内圧クリープ試験を行い、管の割れや漏れの発生状況を観察した。
When the bending strength of the obtained crosslinked ethylene resin pipe was measured by the following method, it was 225N. When the creep resistance was tested, the pipe was not cracked or leaked.
<Bending strength>
A sample having a length of 150 mm was sampled from the obtained cross-linked ethylene resin tube, a three-point bending test was performed in which the center portion was pushed down at a speed of 50 mm / min at a distance between fulcrums of 100 mm, and the load when pushed down by 10 mm was measured.
<Creep resistance>
In accordance with JIS K6769, a hot internal pressure creep test was performed under the conditions of 95 ° C., circumferential stress of 4.8 MPa, and 1 hour, and the occurrence of cracks and leakage of the tube was observed.
比較例１
エチレン系樹脂パウダーを添加せず、密度０．９４５ｇ／ｃｍ3 、１９０℃でのメルトフローレート５．５ｇ／１０分のエチレン−α−オレフィン共重合体樹脂ペレット（日本ポリオレフィン社製「ジェイレクスＬＬ ＡＲ４９１０」）１００重量部のみを用いた外は、実施例１と同様にして架橋エチレン系樹脂管を製造した。得られた架橋エチレン系樹脂管は、曲げ強度２６１Ｎと高く、又、耐クリープ性の試験においては、３８〜４５分で管に割れが生じた。
Comparative Example 1
Ethylene-α-olefin copolymer resin pellets having a density of 0.945 g / cm 3 and a melt flow rate of 5.5 g / 10 min at 190 ° C. without addition of ethylene resin powder (“Jyrex LL AR4910 manufactured by Nippon Polyolefin Co., Ltd.) ]) A crosslinked ethylene resin tube was produced in the same manner as in Example 1 except that only 100 parts by weight was used. The obtained cross-linked ethylene resin pipe had a high bending strength of 261 N, and in the creep resistance test, the pipe cracked in 38 to 45 minutes.
比較例２
エチレン系樹脂パウダーに代えて、密度０．９２３ｇ／ｃｍ3 、１９０℃でのメルトフローレート５０ｇ／１０分のエチレン−α−オレフィン共重合体樹脂ペレット（日本ポリケム社製「ノバテックＬＬ ＵＪ７９０」）を用いた外は、実施例１と同様にして架橋エチレン系樹脂管を製造した。得られた架橋エチレン系樹脂管は、曲げ強度２４７Ｎと高く、又、耐クリープ性の試験においては、２５〜３３分で管に割れが生じた。
Comparative Example 2
Instead of ethylene-based resin powder, an ethylene-α-olefin copolymer resin pellet having a density of 0.923 g / cm 3 and a melt flow rate of 50 g / 10 min at 190 ° C. (“NOVATEC LL UJ790” manufactured by Nippon Polychem Co., Ltd.) A crosslinked ethylene resin tube was produced in the same manner as in Example 1 except that it was used. The obtained cross-linked ethylene resin tube had a high bending strength of 247 N, and in the creep resistance test, the tube cracked in 25 to 33 minutes.
比較例３
エチレン系樹脂パウダーとして、密度０．９５２ｇ／ｃｍ3 、１９０℃でのメルトフローレート２．５ｇ／１０分のエチレン−α−オレフィン共重合体樹脂パウダー（日本ポリケム社製「ノバテックＨＤ ＨＹ３５０Ｐ」）を用いた外は、実施例１と同様にして架橋エチレン系樹脂管を製造した。得られた架橋エチレン系樹脂管は、耐クリープ性の試験においては、管に割れや漏れは生じなかったものの、曲げ強度は２７０Ｎと高く、曲げ加工性の劣るものであった。
Comparative Example 3
As an ethylene-based resin powder, an ethylene-α-olefin copolymer resin powder having a density of 0.952 g / cm 3 and a melt flow rate of 2.5 g / 10 minutes at 190 ° C. (“Novatech HD HY350P” manufactured by Nippon Polychem Co., Ltd.) A crosslinked ethylene resin tube was produced in the same manner as in Example 1 except that it was used. In the creep resistance test, the obtained crosslinked ethylene-based resin pipe had no bending or leakage, but had a high bending strength of 270 N and a poor bending workability.
本発明の製造方法による架橋エチレン系樹脂管は、安定した品質を有するのみならず、曲げ加工性に優れ、且つ、耐クリープ性にも優れることから、例えば床暖房用温水管等として有用である。 The crosslinked ethylene-based resin pipe according to the production method of the present invention is useful not only for stable quality but also for excellent bending workability and creep resistance, so that it is useful, for example, as a hot water pipe for floor heating. .
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