JP6137353B2 - Polyethylene resin composition for three-dimensional network structure and method for producing the same - Google Patents
Polyethylene resin composition for three-dimensional network structure and method for producing the same Download PDFInfo
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- JP6137353B2 JP6137353B2 JP2016013983A JP2016013983A JP6137353B2 JP 6137353 B2 JP6137353 B2 JP 6137353B2 JP 2016013983 A JP2016013983 A JP 2016013983A JP 2016013983 A JP2016013983 A JP 2016013983A JP 6137353 B2 JP6137353 B2 JP 6137353B2
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- Prior art keywords
- ethylene
- network structure
- dimensional network
- weight
- olefin copolymer
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- 239000011342 resin composition Substances 0.000 title claims description 27
- 229920013716 polyethylene resin Polymers 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 75
- -1 unsaturated silane compound Chemical class 0.000 claims description 70
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 69
- 239000005977 Ethylene Substances 0.000 claims description 69
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 63
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 30
- 238000009833 condensation Methods 0.000 claims description 21
- 230000005494 condensation Effects 0.000 claims description 21
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000005227 gel permeation chromatography Methods 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000001451 organic peroxides Chemical class 0.000 claims description 5
- 229920005678 polyethylene based resin Polymers 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000012968 metallocene catalyst Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 150000004714 phosphonium salts Chemical class 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000000034 method Methods 0.000 description 27
- 238000004132 cross linking Methods 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 238000000465 moulding Methods 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 15
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 14
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 12
- 230000004927 fusion Effects 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229910000077 silane Inorganic materials 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 230000006378 damage Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 125000005372 silanol group Chemical group 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 150000008040 ionic compounds Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-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
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- LVYLCBNXHHHPSB-UHFFFAOYSA-N 2-hydroxyethyl salicylate Chemical compound OCCOC(=O)C1=CC=CC=C1O LVYLCBNXHHHPSB-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 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
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000002912 oxalic acid derivatives Chemical class 0.000 description 2
- 125000003431 oxalo group Chemical group 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- DBQOUEWUAIHCNY-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)alumane Chemical compound Fc1c(F)c(F)c([AlH2])c(F)c1F DBQOUEWUAIHCNY-UHFFFAOYSA-N 0.000 description 1
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 description 1
- BGPSZAKAMDJTIH-UHFFFAOYSA-N (2-hydroxy-4-methoxyphenyl)-phenylmethanone;(2-hydroxy-4-octoxyphenyl)-phenylmethanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1.OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 BGPSZAKAMDJTIH-UHFFFAOYSA-N 0.000 description 1
- BKBUTURKEFUGJM-UHFFFAOYSA-N (3,4,5-trifluorophenyl)boron Chemical compound [B]C1=CC(F)=C(F)C(F)=C1 BKBUTURKEFUGJM-UHFFFAOYSA-N 0.000 description 1
- OMWSZDODENFLSV-UHFFFAOYSA-N (5-chloro-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=C(Cl)C=C1C(=O)C1=CC=CC=C1 OMWSZDODENFLSV-UHFFFAOYSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- ZYQFBLZLYJJOJD-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C=2C=3N=NNC=3C=CC=2)=C1O ZYQFBLZLYJJOJD-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
- KNBIXDXLOIHINH-UHFFFAOYSA-N 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoic acid Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(O)=O KNBIXDXLOIHINH-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- WMDUFKYEWRGPSB-UHFFFAOYSA-N 2-ethyl-2-[(2-methylpropan-2-yl)oxy]hexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OC(C)(C)C WMDUFKYEWRGPSB-UHFFFAOYSA-N 0.000 description 1
- SMSVUYQRWYTTLI-UHFFFAOYSA-L 2-ethylhexanoate;iron(2+) Chemical compound [Fe+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O SMSVUYQRWYTTLI-UHFFFAOYSA-L 0.000 description 1
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
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- LMPPLQCHTQMREC-UHFFFAOYSA-N tetrakis(2,3,4,5,6-pentafluorophenyl)antimony Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1[Sb](C=1C(=C(F)C(F)=C(F)C=1F)F)(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F LMPPLQCHTQMREC-UHFFFAOYSA-N 0.000 description 1
- CRUVUWATNULHFA-UHFFFAOYSA-M tetramethylphosphanium;hydroxide Chemical compound [OH-].C[P+](C)(C)C CRUVUWATNULHFA-UHFFFAOYSA-M 0.000 description 1
- CTNFMWSFOVTSNU-UHFFFAOYSA-N tetraphenylantimony Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CTNFMWSFOVTSNU-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 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
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- DWCSXQCXXITVKE-UHFFFAOYSA-N triethyloxidanium Chemical compound CC[O+](CC)CC DWCSXQCXXITVKE-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 1
- OGBBLSOPKGNKHZ-UHFFFAOYSA-N triphenyloxidanium Chemical compound C1=CC=CC=C1[O+](C=1C=CC=CC=1)C1=CC=CC=C1 OGBBLSOPKGNKHZ-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- GIIXTFIYICRGMZ-UHFFFAOYSA-N tris(2,3-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C(=C(C)C=CC=2)C)C=2C(=C(C)C=CC=2)C)=C1C GIIXTFIYICRGMZ-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
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- Graft Or Block Polymers (AREA)
Description
本発明は、立体網目状構造体用ポリエチレン系樹脂組成物及び立体網目状構造体に関し、より詳しくは、家具、ベッド等の寝具、車両用座席、船舶用座席等に適したクッション性と耐熱性に優れた立体網目状構造体用のポリエチレン系樹脂組成物及びその構造体に関するものである。 The present invention relates to a polyethylene-based resin composition for a three-dimensional network structure and a three-dimensional network structure, and more specifically, cushioning properties and heat resistance suitable for furniture, bedding such as beds, vehicle seats, ship seats, and the like. The present invention relates to an excellent polyethylene resin composition for a three-dimensional network structure and its structure.
従来、家具、ベッド等の寝具、車両用座席、船舶用座席等のクッション材には、発泡ウレタン、非弾性捲縮繊維詰綿、及び非弾性捲縮繊維を接着した樹脂綿や硬綿などが使用されている。
近年、熱可塑性樹脂を押出成形によりループ状に押出し、このストランドを熱接着後、冷却固化して得られる三次元網目状構造体を当該クッション材として使用する試みがなされている。当該熱可塑性樹脂として、ポリエステル系エラストマー、ポリウレタン系エラストマー、ポリアミド系エラストマーを用いることが知られている（特許文献１：特開平７−６８０６１号公報）。ところが、これらの樹脂は高価格であり、リサイクルも難しい。
一方、特許文献２（特開２００４−２１８１１６号公報）や特許文献３（特開２００６−２００１１７号公報）には、エチレン−酢酸ビニル共重合体（ＥＶＡ）やエチレン・α−オレフィン共重合体であるポリエチレン系樹脂が開示されているが、これらのポリエチレン系樹脂を用いた三次元網目状構造体は優れた性能を有するものの、柔軟性能や熱接着性を重視しているため樹脂の融点が低くなり耐熱性が劣るという問題がある。このため、ポリエチレン系樹脂を用いた場合、自動車のクッションや緩衝部品、暖房機能付与のベッド用クッションへの適用には大きな制限があった。
Conventionally, cushioning materials for furniture, bedding such as beds, vehicle seats, ship seats, etc. include foamed urethane, non-elastic crimped fiber-filled cotton, and resin cotton or hard cotton bonded with non-elastic crimped fiber. It is used.
In recent years, an attempt has been made to use a three-dimensional network structure obtained by extruding a thermoplastic resin in a loop shape by extrusion molding, heat-bonding the strands, and cooling and solidifying the strands as the cushioning material. As the thermoplastic resin, it is known to use a polyester-based elastomer, a polyurethane-based elastomer, or a polyamide-based elastomer (Patent Document 1: JP-A-7-68061). However, these resins are expensive and difficult to recycle.
On the other hand, Patent Document 2 (Japanese Patent Laid-Open No. 2004-218116) and Patent Document 3 (Japanese Patent Laid-Open No. 2006-2001117) describe an ethylene-vinyl acetate copolymer (EVA) and an ethylene / α-olefin copolymer. Although certain polyethylene resins have been disclosed, the three-dimensional network structure using these polyethylene resins has excellent performance, but because the emphasis is on flexibility and thermal adhesiveness, the melting point of the resin is low. There is a problem that the heat resistance is inferior. For this reason, when a polyethylene-based resin is used, there is a great limitation in application to automobile cushions, cushioning parts, and heating cushions.
本発明は、上記の事情に鑑みてなされたものであり、三次元網目状構造体用樹脂として、押出直後の熱接着性に代表される特殊な成形性を損なうことなく、ポリエチレン樹脂の大きなウィークポイントである耐熱性を向上させた立体網目状構造体用ポリエチレン系樹脂組成物及びその構造体を提供することを目的とする。
さらに、本発明の目的は、ポリエチレン樹脂の耐熱性を向上させる方法として従来から知られている有機過酸化物による架橋、ガンマー線及び電子線による架橋を採用することなく、高い成形温度にて押出し成形が可能であって、成形機内で架橋反応が進行し押し出すことができ、また押出外観が悪化することのないポリエチレン系樹脂組成物及びその構造体を提供することである。
The present invention has been made in view of the above circumstances, and as a resin for a three-dimensional network structure, a large weakness of polyethylene resin is obtained without impairing the special moldability typified by thermal adhesion immediately after extrusion. It is an object of the present invention to provide a polyethylene resin composition for a three-dimensional network structure with improved heat resistance, which is a point, and a structure thereof.
Furthermore, the object of the present invention is to extrude at a high molding temperature without employing cross-linking with an organic peroxide, cross-linking with gamma rays and electron beams, which has been conventionally known as a method for improving the heat resistance of a polyethylene resin. An object of the present invention is to provide a polyethylene-based resin composition and a structure thereof that can be molded, can be extruded through a crosslinking reaction in a molding machine, and do not deteriorate the extrusion appearance.
そこで本発明者らは、上記目的を達成するために鋭意研究を重ねた結果、三次元網目状構造体用樹脂として、特定のエチレン系重合体に、特定のエチレン性不飽和シラン化合物をグラフトさせ、得られたグラフト反応物にシラノール縮合触媒を含有させると、このポリエチレン系樹脂組成物は、押出直後の熱接着性に代表される特殊な成形性を損なうことなく、ポリエチレン樹脂の大きなウィークポイントである耐熱性を向上させることができ、高い成形温度にて押出し成形が可能であって、成形機内で架橋反応が進行し容易に押し出しでき、また押出外観が悪化することなく立体網目状構造体を製造するこができることを見出し、本発明を完成するに至った。 Therefore, as a result of intensive studies to achieve the above object, the present inventors grafted a specific ethylenically unsaturated silane compound to a specific ethylene polymer as a resin for a three-dimensional network structure. When the obtained graft reaction product contains a silanol condensation catalyst, this polyethylene resin composition has a large weak point of polyethylene resin without impairing the special moldability represented by thermal adhesiveness immediately after extrusion. It can improve certain heat resistance, can be extruded at a high molding temperature, can be easily extruded through a crosslinking reaction in a molding machine, and can form a three-dimensional network structure without deteriorating the extrusion appearance. The inventors have found that it can be manufactured and have completed the present invention.
すなわち、本発明の第１の発明によれば、メタロセン触媒によって重合されたエチレン・α−オレフィン共重合体であって、温度１９０℃、荷重２．１６ｋｇにて測定されるメルトフローレート（ＭＦＲ）が２〜５０ｇ／１０分であり、密度が０．８５０〜０．９２０ｇ／ｃｍ３であり、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）による重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比が３以下であるエチレン・α−オレフィン共重合体（ａ）１００重量部に対して、下記の一般式（Ｉ）で表されるエチレン性不飽和シラン化合物（ｂ）０．１〜１０重量部をラジカル発生剤（ｃ）０．００１〜５重量部の存在下でグラフトさせて得られるグラフト反応物（ｄ）にシラノール縮合触媒（ｅ）０．００１〜５重量部を含有させてなる立体網目状構造体用ポリエチレン系樹脂組成物が提供される。
［化１］ Ｒ１ＳｉＲ２ ｎＹ３−ｎ・・・（Ｉ）
（一般式（Ｉ）において、Ｒ１はエチレン性不飽和炭化水素基（酸素原子を有していてもよい）であり、Ｒ２は炭素数１〜１２のアルキル基、Ｙは加水分解可能な有機基であり、相互に同一でも異なっていてもよく、ｎは０〜２である）
That is, according to the first aspect of the present invention, an ethylene / α-olefin copolymer polymerized by a metallocene catalyst , which is measured at a temperature of 190 ° C. and a load of 2.16 kg (MFR). Is 2-50 g / 10 min, the density is 0.850-0.920 g / cm 3 , and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) by gel permeation chromatography (GPC) is 3 From 100 parts by weight of the ethylene / α-olefin copolymer (a) below, 0.1 to 10 parts by weight of the ethylenically unsaturated silane compound (b) represented by the following general formula (I) is radicalized. The graft reaction product (d) obtained by grafting in the presence of 0.001 to 5 parts by weight of the generator (c) contains 0.001 to 5 parts by weight of a silanol condensation catalyst (e). Steric network structure for the polyethylene resin composition is provided.
[Chemical Formula 1] R 1 SiR 2 n Y 3-n (I)
(In General Formula (I), R 1 is an ethylenically unsaturated hydrocarbon group (which may have an oxygen atom), R 2 is an alkyl group having 1 to 12 carbon atoms, and Y is hydrolyzable. An organic group, which may be the same or different from each other, and n is 0 to 2)
また、本発明の第２の発明によれば、第１の発明において、エチレン性不飽和シラン化合物（ｂ）は、下記の一般式（ＩＩ）で表される化合物であることを特徴とする立体網目状構造体用ポリエチレン系樹脂組成物が提供される。
［化２］ Ｈ２Ｃ＝Ｃ（Ｒ３）Ｓｉ（ＯＲ４）３・・・（ＩＩ）
（一般式（ＩＩ）において、Ｒ３は、Ｈ又はＣＨ３、Ｒ４は、相互に同一でも異なっていてもよい炭素数４以下の直鎖若しくは分岐アルキル基、又はフェニル基である）
According to the second invention of the present invention, in the first invention, the ethylenically unsaturated silane compound (b) is a compound represented by the following general formula (II): A polyethylene resin composition for a network structure is provided.
[Chemical Formula 2] H 2 C═C (R 3 ) Si (OR 4 ) 3 (II)
(In general formula (II), R 3 is H or CH 3 , and R 4 is a linear or branched alkyl group having 4 or less carbon atoms, which may be the same or different from each other, or a phenyl group)
また、本発明の第３の発明によれば、第１又は第２の発明において、ラジカル発生剤（ｃ）は、有機過酸化物又はアゾビス化合物から選択される１種以上の化合物であることを特徴とする立体網目状構造体用ポリエチレン系樹脂組成物が提供される。 According to the third invention of the present invention, in the first or second invention, the radical generator (c) is one or more compounds selected from organic peroxides or azobis compounds. A polyethylene resin composition for a three-dimensional network structure is provided.
また、本発明の第４の発明によれば、第１〜３のいずれかの発明において、シラノール縮合触媒（ｅ）は、金属有機酸塩、チタネート、ホウ酸塩、有機アミン、アンモニウム塩、ホスホニウム塩、無機酸及び有機酸からなる群から選択される１種以上の化合物であることを特徴とする立体網目状構造体用ポリエチレン系樹脂組成物が提供される。 According to the fourth invention of the present invention, in any one of the first to third inventions, the silanol condensation catalyst (e) is a metal organic acid salt, titanate, borate, organic amine, ammonium salt, phosphonium. There is provided a polyethylene resin composition for a three-dimensional network structure, which is one or more compounds selected from the group consisting of a salt, an inorganic acid and an organic acid.
また、本発明の第５の発明によれば、エチレン・α−オレフィン共重合体（ａ）、エチレン性不飽和シラン化合物（ｂ）及びラジカル発生剤（ｃ）は、６０〜１００℃で混合することを特徴とする第１〜４のいずれかの発明のポリエチレン系樹脂組成物の製造方法が提供される。 According to the fifth aspect of the present invention, the ethylene / α-olefin copolymer (a), the ethylenically unsaturated silane compound (b) and the radical generator (c) are mixed at 60 to 100 ° C. A method for producing a polyethylene resin composition according to any one of the first to fourth inventions is provided.
本発明の立体網目状構造体用ポリエチレン系樹脂組成物（以下、単に樹脂組成物ともいう）は、特定のエチレン・α−オレフィン共重合体（ａ）に、特定のエチレン性不飽和シラン化合物（ｂ）をラジカル発生剤（ｃ）の存在下でグラフトさせて得られるグラフト反応物（ｄ）にシラノール縮合触媒（ｅ）を含有させているので、押出直後の熱接着性に代表される特殊な成形性を損なうことなく、ポリエチレン樹脂の大きなウィークポイントである耐熱性が向上し、立体網目状構造体を容易に製造することが可能となる。
さらに、本発明の樹脂組成物を用いれば、高い成形温度にて押出し成形が可能であって、成形機内で架橋反応が進行するので容易に押し出しでき、また押出外観が悪化することのなく立体網目状構造体を製造することができる。
The polyethylene-based resin composition for a three-dimensional network structure of the present invention (hereinafter also simply referred to as a resin composition) includes a specific ethylene / α-olefin copolymer (a) and a specific ethylenically unsaturated silane compound ( Since the silanol condensation catalyst (e) is contained in the graft reaction product (d) obtained by grafting b) in the presence of the radical generator (c), a special typified by thermal adhesion immediately after extrusion is used. Without impairing moldability, the heat resistance, which is a large weak point of polyethylene resin, is improved, and a three-dimensional network structure can be easily manufactured.
Furthermore, if the resin composition of the present invention is used, extrusion molding is possible at a high molding temperature, and since the crosslinking reaction proceeds in the molding machine, it can be easily extruded and the three-dimensional network is not deteriorated without deteriorating the extrusion appearance. A shaped structure can be produced.
１．エチレン・α−オレフィン共重合体（ａ）
本発明においては、図２に示すように、まず、エチレン・α−オレフィン共重合体（ａ）を製造し、これにエチレン性不飽和シラン化合物（ｂ）とラジカル発生剤（ｃ）を混合し、シラン化合物をグラフト反応させ、次に、得られたグラフト反応物（ｄ）にシラノール縮合触媒（ｅ）を配合して樹脂組成物とする。
ここでエチレン・α−オレフィン共重合体（ａ）は、メタロセン触媒によって得られるものであり、メタロセン化合物及びメタロセン化合物と反応して安定なアニオンとなる化合物からなる触媒を使用して、主成分のエチレンと従成分のα−オレフィンとを共重合させる方法により製造される。
例えば、特開昭５８−１９３０９号公報、同５９−９５２９２号公報、同６０−３５００５号公報、同６０−３５００６号公報、同６０−３５００７号公報、同６０−３５００８号公報、同６０−３５００９号公報、同６１−１３０３１４号公報、特開平３−１６３０８８号公報、ヨーロッパ特許出願公開第４２０４３６号明細書、米国特許第５０５５４３８号明細書及び国際公開公報ＷＯ９１／０４２５７号明細書などに記載されている方法、いわゆるメタロセン触媒、特にメタロセン・アルモキサン触媒や、国際公開公報ＷＯ９２／０１７２３号明細書等に開示されているようなメタロセン化合物と以下に述べるメタロセン化合物と反応して安定なアニオンとなる化合物からなる触媒を使用して、主成分のエチレンと従成分のα−オレフィンとを共重合させる方法により製造されるものである。
1. Ethylene / α-olefin copolymer (a)
In the present invention, as shown in FIG. 2, first, an ethylene / α-olefin copolymer (a) is produced, and an ethylenically unsaturated silane compound (b) and a radical generator (c) are mixed therewith. Then, the silane compound is grafted, and then the silanol condensation catalyst (e) is blended with the obtained graft reaction product (d) to obtain a resin composition.
Here, the ethylene / α-olefin copolymer (a) is obtained by a metallocene catalyst, and a catalyst comprising a metallocene compound and a compound that reacts with the metallocene compound to become a stable anion, It is produced by a method of copolymerizing ethylene and a secondary α-olefin.
For example, JP-A-58-19309, 59-95292, 60-35005, 60-35006, 60-35007, 60-35008, 60-35209 No. 61-130314, Japanese Patent Laid-Open No. 3-163088, European Patent Application Publication No. 420436, US Pat. No. 5,055,438, and International Publication No. WO91 / 04257. A so-called metallocene catalyst, in particular, a metallocene-alumoxane catalyst, a metallocene compound as disclosed in International Publication No. WO92 / 01723, etc. and a compound that reacts with the metallocene compound described below to form a stable anion. Using a catalyst consisting of ethylene as the main component and α-olefin as the secondary component. It is manufactured by a method of copolymerizing and down.
上述のメタロセン化合物と反応して安定なアニオンとなる化合物とは、カチオンとアニオンのイオン対から形成されるイオン性化合物あるいは親電子性化合物であり、メタロセン化合物と反応して安定なイオンとなって重合活性種を形成するものである。
このうちイオン性化合物は、下記一般式（ＩＩＩ）で表される。
〔Ｑ〕ｍ＋〔Ｚ〕ｍ− ・・・ （ＩＩＩ） （ｍは１以上の整数）
式（ＩＩＩ）において、Ｑはイオン性化合物のカチオン成分であり、カルボニウムカチオン、トロピリウムカチオン、アンモニウムカチオン、オキソニウムカチオン、スルホニウムカチオン、ホスホニウムカチオン等があげられ、さらには、それ自身が還元され易い金属の陽イオンや有機金属の陽イオンなどもあげられる。
これらのカチオンは特表平１−５０１９５０号公報などに開示されているようなプロトンを与えることができるカチオンだけではなく、プロトンを与えないカチオンでも良い。これらのカチオンの具体例としては、トリフェニルカルボニウム、ジフェニルカルボニウム、シクロヘプタトリエニウム、イニデニウム、トリエチルアンモニウム、トリプロピルアンモニウム、トリブチルアンモニウム、Ｎ，Ｎ−ジメチルアニリニウム、ジプロピルアンモニウム、ジシクロヘキシルアンモニウム、トリフェニルホスホニウム、トリメチルホスホニウム、トリ（ジメチルフェニル）ホスホニウム、トリ（メチルフェニル）ホスホニウム、トリフェニルスルホニウム、トリフェニルオキソニウム、トリエチルオキソニウム、ピリリウム、また、銀イオン、金イオン、白金イオン、パラジウムイオン、水銀イオン、フェロセニウムイオン等が挙げられる。
また、Ｚはイオン性化合物のアニオン成分であり、メタロセン化合物と反応して安定なアニオンとなる成分であって、有機ホウ素化合物アニオン、有機アルミニウム化合物アニオン、有機ガリウム化合物アニオン、有機リン化合物アニオン、有機ヒ素化合物アニオン、有機アンチモン化合物アニオンなどがあげられ、具体的にはテトラフェニルホウ素、テトラキス（３，４，５−トリフルオロフェニル）ホウ素、テトラキス（３，５−ジ（トリフルオロメチル）フェニル）ホウ素、テトラキス（３，５−（ｔ−ブチル）フェニル）ホウ素、テトラキス（ペンタフルオロフェニル）ホウ素、テトラフェニルアルミニウム、テトラキス（３，４，５−トリフルオロフェニル）アルミニウム、テトラキス（３，５−ジ（トリフルオロメチル）フェニル）アルミニウム、テトラキス（３，５−ジ（ｔ−ブチル）フェニル）アルミニウム、テトラキス（ペンタフルオロフェニル）アルミニウム、テトラフェニルガリウム、テトラキス（３，４，５−トリフルオロフェニル）ガリウム、テトラキス（３，５−ジ（トリフルオロメチル）フェニル）ガリウム、テトラキス（３，５−ジ（ｔ−ブチル）フェニル）ガリウム、テトラキス（ペンタフルオロフェニル）ガリウム、テトラフェニルリン、テトラキス（ペンタフルオロフェニル）リン、テトラフェニルヒ素、テトラキス（ペンタフルオロフェニル）ヒ素、テトラフェニルアンチモン、テトラキス（ペンタフルオロフェニル）アンチモン、デカボレート、ウンデカボレート、カルバドデカボレート、デカクロロデカボレート等が挙げられる。
The compound that reacts with the above metallocene compound to become a stable anion is an ionic compound or electrophilic compound formed from an ion pair of a cation and an anion, and reacts with the metallocene compound to become a stable ion. It forms a polymerization active species.
Among these, an ionic compound is represented by the following general formula (III).
[Q] m + [Z] m− (III) (m is an integer of 1 or more)
In the formula (III), Q is a cation component of an ionic compound, and examples thereof include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. Examples include easy metal cations and organic metal cations.
These cations are not limited to cations that can give protons as disclosed in JP-A-1-501950 and the like, but also cations that do not give protons. Specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, inidenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, Triphenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, palladium ion, Examples include mercury ions and ferrocenium ions.
Z is an anionic component of an ionic compound, which is a component that reacts with a metallocene compound to become a stable anion, and is an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic phosphorus compound anion, an organic Examples include arsenic compound anions, organic antimony compound anions, and more specifically, tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis (3,5-di (trifluoromethyl) phenyl) boron , Tetrakis (3,5- (t-butyl) phenyl) boron, tetrakis (pentafluorophenyl) boron, tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) aluminum, tetrakis (3,5-di ( Trifluoromethyl) pheny ) Aluminum, tetrakis (3,5-di (t-butyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis (3,5 -Di (trifluoromethyl) phenyl) gallium, tetrakis (3,5-di (t-butyl) phenyl) gallium, tetrakis (pentafluorophenyl) gallium, tetraphenylphosphorus, tetrakis (pentafluorophenyl) phosphorus, tetraphenylarsenic Tetrakis (pentafluorophenyl) arsenic, tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, decaborate, undecaborate, carbadodecaborate, decachlorodecaborate and the like.
また、親電子性化合物としては、ルイス酸化合物として知られるもののうち、メタロセン化合物と反応して安定なアニオンとなって重合活性種を形成するものであり、種々のハロゲン化金属化合物や固体酸として知られている金属酸化物などが挙げられる。具体的には、ハロゲン化マグネシウムやルイス酸性無機酸化物などが例示される。 Among electrophilic compounds, among those known as Lewis acid compounds, they react with metallocene compounds to form stable anions to form polymerization active species, and as various metal halide compounds and solid acids, Known metal oxides may be mentioned. Specific examples include magnesium halides and Lewis acidic inorganic oxides.
ここで、α−オレフィンとしては、炭素数３〜１８のα−オレフィン、例えば、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−オクテン、１−ヘプテン、４−メチルペンテン−１、４−メチルヘキセン−１、４，４−ジメチルペンテン−１等が挙げられる。これらα−オレフィンの中で好ましいのは炭素数４〜１２であり、より好ましくは６〜１０の１種又は２種以上のα−オレフィン２〜６０重量％と、エチレン４０〜９８重量％とを共重合させる。
共重合方法としては、気相法、スラリー法、溶液法、高圧イオン重合法等を挙げることができる。これらの中では溶液法、高圧イオン重合法が好ましく、特に高圧イオン重合法で製造することが好ましい。なお、この高圧イオン重合法とは、特開昭５６−１８６０７号、特開昭５８−２２５１０６号の各公報に記載されている、圧力が１００ｋｇ／ｃｍ２以上、好ましくは２００〜２，０００ｋｇ／ｃｍ２、温度が１２５℃以上、好ましくは１３０〜２５０℃、特に１５０〜２００℃の反応条件下に行なわれるエチレン系重合体の連続的製造法である。
Here, as the α-olefin, an α-olefin having 3 to 18 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methylpentene-1, 4-methylhexene-1, 4, 4-dimethylpentene-1, etc. are mentioned. Among these α-olefins, those having 4 to 12 carbon atoms are preferred, more preferably 2 to 60% by weight of one or more α-olefins having 6 to 10 and 40 to 98% by weight of ethylene. Copolymerize.
Examples of the copolymerization method include a gas phase method, a slurry method, a solution method, and a high-pressure ion polymerization method. Among these, the solution method and the high-pressure ion polymerization method are preferable, and the production by the high-pressure ion polymerization method is particularly preferable. The high-pressure ion polymerization method is described in JP-A-56-18607 and JP-A-58-225106, and the pressure is 100 kg / cm 2 or more, preferably 200 to 2,000 kg / This is a continuous process for producing an ethylene polymer carried out under the reaction conditions of cm 2 and a temperature of 125 ° C. or higher, preferably 130 to 250 ° C., particularly 150 to 200 ° C.
本発明において、エチレン・α−オレフィン共重合体のメルトフローレート（ＭＦＲ）は、ＪＩＳ Ｋ６９２２−２：１９９７により温度１９０℃、荷重２．１６ｋｇにて測定され、１ｇ／１０分を超え１００ｇ／１０分以下であり、好ましくは２〜５０ｇ／１０分、更に好ましくは５〜３０ｇ／１０分である。
該ＭＦＲが上記の上限値より大きいと、複数のストランドを押し出して成形する時、ストランドのループが安定せず、ストランド径もストランド毎に異なり立体網状構造体としての均一性が劣り、製品としての性能低下を招き、さらにＭＦＲが大きくなると樹脂が流れ過ぎてダイス出口が液状になりストランドが引き取れず成形不可となる。また、ＭＦＲが上記の下限値より小さいと、成形時のモーター負荷、樹脂圧力が上昇し、ストランド表面も荒れてしまう。
ここで、ＭＦＲは、エチレン重合温度や連鎖移動剤の使用等により調整することができ、所望のものを得ることができる。即ち、エチレンとα−オレフィンとの重合温度を上げることにより分子量を下げ、結果としてＭＦＲを大きくすることができ、また、重合温度を下げることにより分子量を上げ、結果としてＭＦＲを小さくすることができる。また、エチレンとα−オレフィンとの共重合反応において、共存させる水素量（連鎖移動剤量）を増加させることにより分子量を下げ、結果としてＭＦＲを大きくすることができ、共存させる水素量（連鎖移動剤量）を減少させることにより分子量を上げ、結果としてＭＦＲを小さくすることができる。
In the present invention, the melt flow rate (MFR) of the ethylene / α-olefin copolymer is measured at a temperature of 190 ° C. and a load of 2.16 kg according to JIS K6922-2: 1997, and exceeds 1 g / 10 minutes to 100 g / 10. Or less, preferably 2 to 50 g / 10 minutes, more preferably 5 to 30 g / 10 minutes.
When the MFR is larger than the above upper limit value, when a plurality of strands are extruded and molded, the strand loops are not stable, the strand diameters are different for each strand, and the uniformity as a three-dimensional network structure is inferior. If the performance is lowered and the MFR is further increased, the resin flows too much, the die outlet becomes liquid, and the strand cannot be taken out and cannot be molded. Moreover, when MFR is smaller than said lower limit, the motor load at the time of shaping | molding and the resin pressure will rise, and the strand surface will also be roughened.
Here, MFR can be adjusted by ethylene polymerization temperature, use of a chain transfer agent, etc., and a desired thing can be obtained. That is, by increasing the polymerization temperature of ethylene and α-olefin, the molecular weight can be decreased, and as a result, the MFR can be increased. By decreasing the polymerization temperature, the molecular weight can be increased, and as a result, the MFR can be decreased. . In addition, in the copolymerization reaction between ethylene and α-olefin, the amount of coexisting hydrogen (amount of chain transfer agent) can be increased to lower the molecular weight, resulting in an increase in MFR. The molecular weight can be increased by decreasing the (drug amount), and as a result, the MFR can be reduced.
本発明にて用いられるエチレン・α−オレフィン共重合体は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）による重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比が通常４以下のものであり、好ましくは３以下、更に好ましくは２．５以下のものである。重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比の下限値は、通常１．０であり、好ましくは１．５以上、さらに好ましくは２以上である。重量平均分子量と数平均分子量の比が上記の上限値より大であるとストランドの熱接着性が悪化して製品強度が低下し、上記の下限値より小であると重合体の製造が難しくなる。
上記の要件は、重合触媒及び重合条件を適宜選択することにより達成することができる。
ゲルパーミエーションクロマトグラフィ（ＧＰＣ）は、サイズ排除クロマトグラフィーを用いて測定し、単分散ポリスチレンで、ユニバーサルな検量線を作成し、直鎖のポリエチレンの分子量として求められる。
The ethylene / α-olefin copolymer used in the present invention has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio of usually 4 or less by gel permeation chromatography (GPC), preferably 3 or less, more preferably 2.5 or less. The lower limit of the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 1.0, preferably 1.5 or more, more preferably 2 or more. If the ratio of the weight average molecular weight to the number average molecular weight is larger than the above upper limit value, the thermal adhesiveness of the strand deteriorates and the product strength decreases, and if it is smaller than the above lower limit value, it becomes difficult to produce a polymer. .
The above requirements can be achieved by appropriately selecting a polymerization catalyst and polymerization conditions.
Gel permeation chromatography (GPC) is measured using size exclusion chromatography, a universal calibration curve is created with monodisperse polystyrene, and the molecular weight of linear polyethylene is determined.
本発明にて用いられるエチレン・α−オレフィン共重合体は、密度（ＪＩＳ−Ｋ６９２２−１，２：１９９７にて測定）が０．８５０〜０．９２０ｇ／ｃｍ３であり、好ましくは０．８５０〜０．９１０ｇ／ｃｍ３である。密度が０．９２０ｇ／ｃｍ３より大であると熱接着性が悪化し、密度が０．８５０ｇ／ｃｍ３未満では製造が難しくなる傾向がある。
密度は、α−オレフィンの種類や含有量の制御などの方法で調整することができる。例えば、ポリエチレン中のα−オレフィン含有量を低くする（重合時のα−オレフィン添加量を低くする）、又は同じ含有量であれば、炭素数の小さいα−オレフィンを用いることにより、密度を高くすることができる。
The ethylene / α-olefin copolymer used in the present invention has a density (measured in accordance with JIS-K6922-1, 2: 1997) of 0.850 to 0.920 g / cm 3 , preferably 0.850. ˜0.910 g / cm 3 . When the density is higher than 0.920 g / cm 3 , the thermal adhesiveness is deteriorated, and when the density is lower than 0.850 g / cm 3 , the production tends to be difficult.
The density can be adjusted by a method such as control of the type and content of α-olefin. For example, if the α-olefin content in polyethylene is lowered (the α-olefin addition amount during polymerization is lowered) or the same content, the α-olefin having a small carbon number is used to increase the density. can do.
２．エチレン性不飽和シラン化合物（ｂ）
本発明では、エチレン性不飽和シラン化合物として、次の一般式（Ｉ）で表される化合物を使用する。
Ｒ１ＳｉＲ２ ｎＹ３−ｎ・・・（Ｉ）
2. Ethylenically unsaturated silane compound (b)
In the present invention, a compound represented by the following general formula (I) is used as the ethylenically unsaturated silane compound.
R 1 SiR 2 n Y 3-n (I)
一般式（Ｉ）において、Ｒ１は、エチレン性不飽和炭化水素基（酸素原子を有していてもよい）であり、ラジカル反応性を有するものである。このような基としては、炭素数２〜１２のアルケニル基、アリル基やオキシアルケニル基が好ましく、例えば、ビニル基、アリル基、イソプロペニル基、ブテニル基、γ−（メタ）アクリルオキシプロピル基等が挙げられる。Ｒ２は、炭素数１〜１２のアルキル基であり、例えば、メチル基、エチル基、プロピル基、デシル基等が挙げられる。Ｙは加水分解可能な有機基を表し、相互に同一でも異なっていてもよく、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、アリールアミノ基などが挙げられる。炭素数が１３以上のアルキル基では、反応性が小さくなる傾向がある。ｎは、通常０，１又は２であり、架橋性の観点から、好ましくは０である。
エチレン性不飽和シラン化合物（ｂ）の具体例としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン、アリルトリメトキシシラン、アリルトリエトキシシラン、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。
In the general formula (I), R 1 is an ethylenically unsaturated hydrocarbon group (which may have an oxygen atom) and has radical reactivity. Such a group is preferably an alkenyl group having 2 to 12 carbon atoms, an allyl group or an oxyalkenyl group, such as a vinyl group, an allyl group, an isopropenyl group, a butenyl group, or a γ- (meth) acryloxypropyl group. Is mentioned. R 2 is an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a decyl group. Y represents a hydrolyzable organic group and may be the same or different from each other, and examples thereof include a methoxy group, an ethoxy group, a formyloxy group, an acetoxy group, a propionyloxy group, and an arylamino group. When the alkyl group has 13 or more carbon atoms, the reactivity tends to be small. n is usually 0, 1 or 2, and preferably 0 from the viewpoint of crosslinkability.
Specific examples of the ethylenically unsaturated silane compound (b) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane. And methacryloyloxypropyltrimethoxysilane.
この化合物（ｂ）として、特に好ましいものは、次の一般式（ＩＩ）で表される化合物である。
Ｈ２Ｃ＝Ｃ（Ｒ３）Ｓｉ（ＯＲ４）３・・・（ＩＩ）
一般式（ＩＩ）において、Ｒ３は、Ｈ又はＣＨ３、Ｒ４は、相互に同一でも異なっていてもよい炭素数４以下の直鎖若しくは分岐アルキル基、又はフェニル基である。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、ビニルトリプロポキシシラン等が挙げられる。
Particularly preferred as this compound (b) is a compound represented by the following general formula (II).
H 2 C═C (R 3 ) Si (OR 4 ) 3 (II)
In the general formula (II), R 3 is H or CH 3 , and R 4 is a linear or branched alkyl group having 4 or less carbon atoms, which may be the same or different from each other, or a phenyl group. Specific examples include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltripropoxysilane.
エチレン性不飽和シラン化合物（ｂ）は、ラジカル発生剤（ｃ）の存在下で、そのエチレン性の基がラジカル反応によってエチレン・α−オレフィン共重合体（ａ）と反応してグラフト化され、グラフト反応物（ｄ）を生成する。
グラフト反応物（ｄ）では、エチレン性不飽和シラン化合物（ｂ）に由来する加水分解可能な有機基がエチレン・α−オレフィン共重合体に結合しており、この加水分解可能な有機基は、シラノール縮合触媒（ｅ）の存在下、水と反応して加水分解してシラノール基が生成し、シラノール基同士が脱水縮合することにより、グラフト反応物（ｄ）同士が結合し、架橋反応を起こす。エチレン性不飽和シラン化合物（ｂ）に含まれる加水分解可能な有機基は、アルコキシ基が好ましく、エチレン性不飽和シラン化合物（ｂ）一分子当たり、複数基、好ましくは３個有することが好適である。
In the presence of the radical generator (c), the ethylenically unsaturated silane compound (b) is grafted by reacting the ethylenic group with the ethylene / α-olefin copolymer (a) by a radical reaction, A graft reaction product (d) is produced.
In the graft reaction product (d), a hydrolyzable organic group derived from the ethylenically unsaturated silane compound (b) is bonded to the ethylene / α-olefin copolymer, and the hydrolyzable organic group is In the presence of the silanol condensation catalyst (e), it reacts with water and hydrolyzes to form silanol groups, and the silanol groups dehydrate and condense, and the graft reactants (d) are bonded to each other to cause a crosslinking reaction. . The hydrolyzable organic group contained in the ethylenically unsaturated silane compound (b) is preferably an alkoxy group, and preferably has a plurality of groups, preferably 3 groups, per molecule of the ethylenically unsaturated silane compound (b). is there.
グラフト変性させる反応系に存在させるエチレン性不飽和シラン化合物（ｂ）の量は、目的とする成型品の架橋度、反応条件（温度、時間）などにより決定されるが、経済性、反応前・反応中の取り扱いの容易性から、エチレン・α−オレフィン共重合体（ａ）１００重量部に対し、０．１〜１０重量部の範囲とすることが好ましい。より好ましくは、０．２〜５重量部であり、さらに好ましくは、０．５〜３重量部である。０．１重量部未満では十分なグラフト化及び架橋度を得ることができないことがあり、機械的強度、耐熱性、耐クリープ性等の諸特性が十分向上せず、１０重量部を超えると溶融粘度が高くなり過ぎて、押出機に負荷が加わり過ぎ作業性の悪化や成形不良を起こす傾向となる。 The amount of the ethylenically unsaturated silane compound (b) to be present in the reaction system to be graft-modified is determined by the degree of crosslinking of the target molded product, reaction conditions (temperature, time), etc. In view of ease of handling during the reaction, the amount is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin copolymer (a). More preferably, it is 0.2-5 weight part, More preferably, it is 0.5-3 weight part. If it is less than 0.1 part by weight, sufficient grafting and crosslinking degree may not be obtained, and various properties such as mechanical strength, heat resistance and creep resistance are not sufficiently improved. Since the viscosity becomes too high, the load is excessively applied to the extruder and the workability tends to be deteriorated or the molding is poor.
３．ラジカル発生剤（ｃ）
本発明で用いられるラジカル発生剤（ｃ）は、ポリオレフィンのグラフト化反応に一般的に用いられる化合物であればよく、特に限定されるものではないが、グラフト反応温度において６分未満の半減期を有する化合物の中から選ぶのが好ましい。より好ましくは、グラフト反応温度において１分間未満の半減期を有する化合物である。具体的には、有機過酸化物及び／又はアゾビス化合物が好ましく、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルオキシ−２−エチルヘキサノエートなどの有機過酸化物、アゾビスイソブチロニトリル、メチルアゾビスイソブチレートなどのアゾビス化合物が挙げられ、これらの１種もしくは２種以上が好適に用いられる。
これらの添加量は特に限定されるものではないが、エチレン・α−オレフィン共重合体（ａ）１００重量部に対し、好ましくは０．００１〜５重量、更に好ましくは０．０１〜２重量部である。０．００１重量部未満ではグラフト化反応が十分進行しないので所望のゲル分率が得られず耐熱性が不充分となり、５重量部を超えるとラジカル発生剤による目的としない架橋反応（過酸化物架橋）が進行し、スコーチ現象の発生、表面平滑性の低下、粘度の上昇等が起こり、作業性が悪化する傾向となる。
3. Radical generator (c)
The radical generator (c) used in the present invention is not particularly limited as long as it is a compound generally used for polyolefin grafting reaction, but has a half-life of less than 6 minutes at the grafting reaction temperature. It is preferable to select from the compounds having. More preferred are compounds having a half-life of less than 1 minute at the grafting reaction temperature. Specifically, organic peroxides and / or azobis compounds are preferable, and organic peroxides such as benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, and t-butyloxy-2-ethylhexanoate. Azobis compounds such as azobisisobutyronitrile and methylazobisisobutyrate, and one or more of these are preferably used.
The amount of these additives is not particularly limited, but is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin copolymer (a). It is. If the amount is less than 0.001 part by weight, the grafting reaction does not proceed sufficiently, so that the desired gel fraction cannot be obtained and the heat resistance is insufficient. Crosslinking) progresses, scorch phenomenon occurs, surface smoothness decreases, viscosity increases, and the workability tends to deteriorate.
４．グラフト反応
グラフト反応の方法には、エチレン・α−オレフィン共重合体（ａ）に、エチレン性不飽和シラン化合物（ｂ）及びラジカル発生剤（ｃ）を前もって混合させた後、グラフト反応を行なう方法、立体網目状構造体の成形時に、これらの各成分を直前に混合する方法、若しくは予め各成分を混合した混合物やマスターバッチ化したものを添加してグラフト反応及び成形を行なう方法がある。品質の安定性の観点から前もって混合させた後、グラフト反応を行なう方法が好ましく、コストを重視する場合は直前に混合するかマスターバッチ化したものなどを添加しグラフト反応を行なう方法が好ましい。
前述の様に、エチレン・α−オレフィン共重合体（ａ）の密度によっては、エチレン性不飽和シラン化合物（ｂ）及びラジカル発生剤（ｃ）が混合しにくく、安定した架橋性能を得ることが出来ないことがある。混合含浸の操作方法は特に限定されるものではないが、通常、加温が可能なミキサーを用いて６０〜１００℃で攪拌することにより行われる。
また、シラノール縮合触媒（ｅ）や安定剤（ｆ）は、前もってエチレン・α−オレフィン共重合体（ａ）と溶融混練した後、或いは粉状のエチレン・α−オレフィン共重合体（ａ）とミキサーなどを用いて混合した後、供給することが好ましい。ここで、上記エチレン・α−オレフィン共重合体（ａ）は、エチレン性不飽和シラン化合物（ｂ）やラジカル発生剤（ｃ）含んでいてもよい。また、シラノール縮合触媒（ｅ）や安定剤（ｆ）に加えて、着色剤、防錆剤、充填剤、難燃剤等を目的に応じて含有させることもできる。
4). Graft reaction The graft reaction is carried out by mixing the ethylene / α-olefin copolymer (a) with the ethylenically unsaturated silane compound (b) and the radical generator (c) in advance, and then performing the graft reaction. There are a method of mixing these components immediately before forming a three-dimensional network structure, or a method of performing a graft reaction and forming by adding a mixture of each component in advance or a master batch. From the standpoint of quality stability, a method in which the graft reaction is performed after mixing in advance is preferable. When importance is placed on the cost, a method in which the mixture is mixed immediately before or master batch is added and the graft reaction is performed is preferable.
As described above, depending on the density of the ethylene / α-olefin copolymer (a), it is difficult to mix the ethylenically unsaturated silane compound (b) and the radical generator (c), and stable crosslinking performance can be obtained. There are things that cannot be done. Although the operation method of mixing impregnation is not specifically limited, Usually, it is performed by stirring at 60-100 degreeC using the mixer which can be heated.
In addition, the silanol condensation catalyst (e) and the stabilizer (f) may be used after the melt-kneading with the ethylene / α-olefin copolymer (a) or the powdery ethylene / α-olefin copolymer (a). It is preferable to supply after mixing using a mixer or the like. Here, the ethylene / α-olefin copolymer (a) may contain an ethylenically unsaturated silane compound (b) and a radical generator (c). Further, in addition to the silanol condensation catalyst (e) and the stabilizer (f), a coloring agent, a rust preventive agent, a filler, a flame retardant, and the like can be contained depending on the purpose.
５．グラフト反応物（ｄ）
本発明におけるグラフト反応物（ｄ）は、エチレン・α−オレフィン共重合体（ａ）にエチレン性不飽和シラン化合物（ｂ）をラジカル発生剤（ｃ）の存在下でグラフトさせることにより生成する。グラフト反応物（ｄ）は、エチレン性不飽和シラン化合物（ｂ）に由来する加水分解可能な有機基がエチレン・α−オレフィン共重合体（ａ）に結合しており、この加水分解可能な有機基は、シラノール縮合触媒（ｅ）の存在下、水と反応して加水分解してシラノール基が生成し、シラノール基同士が脱水縮合することにより、グラフト反応物（ｄ）同士が結合し、架橋反応を起こす。その架橋した生成物は、立体網目状構造体にしたときに、エチレン・α−オレフィン共重合体（ａ）の場合よりも成形品としての圧縮残留ひずみを小さくすることができる。
5. Graft reaction product (d)
The graft reaction product (d) in the present invention is produced by grafting the ethylenically unsaturated silane compound (b) to the ethylene / α-olefin copolymer (a) in the presence of the radical generator (c). In the graft reaction product (d), a hydrolyzable organic group derived from the ethylenically unsaturated silane compound (b) is bonded to the ethylene / α-olefin copolymer (a). In the presence of the silanol condensation catalyst (e), the group reacts with water to hydrolyze to form a silanol group, and the silanol groups are dehydrated and condensed to bond the graft reaction products (d) to each other. Cause a reaction. When the crosslinked product is formed into a three-dimensional network structure, the compression residual strain as a molded product can be reduced as compared with the case of the ethylene / α-olefin copolymer (a).
６．シラノール縮合触媒（ｅ）
本発明で用いるシラノール縮合触媒（ｅ）としては、金属有機酸塩、チタネート、ホウ酸塩、有機アミン、アンモニウム塩、ホスホニウム塩、無機酸及び有機酸からなる群から選択される１種以上の化合物が好ましく使用できる。金属有機酸塩、チタネート、ホウ酸塩、有機アミン、アンモニウム塩、ホスホニウム塩としては、錫、亜鉛、鉄、鉛、コバルト等の金属カルボン酸塩、チタン酸エステル及びキレート化合物の有機金属化合物が挙げられる。
具体的には、ジブチル錫ジラウレート、ジオクチル錫ジラウレート、ジブチル錫ジアセテート、ジブチル錫ジオクトエート、酢酸第一錫、オクタン酸第一錫、ナフテン酸コバルト、オクチル酸鉛、ナフテン酸鉛、オクチル酸亜鉛、カプリル酸亜鉛、２−エチルヘキサン酸鉄、オクチル酸鉄、ステアリン酸鉄、チタン酸テトラブチルエステル、チタン酸テトラノニルエステル、ビス（アセチルアセトニトリル）ジ−イソプロピルチタネート、エチルアミン、ジブチルアミン、ヘキシルアミン、トリエタノールアミン、ジメチルソーヤアミン、テトラメチルグアニジン、ピリジン、炭酸アンモニウム、テトラメチルアンモニウムハイドロオキサイド、テトラメチルホスホニウムハイドロオキサイド、硫酸、塩酸、トルエンスルホン酸、酢酸、ステアリン酸、マレイン酸などが挙げられる。
これらの中で、好ましくは金属有機酸塩、更に好ましくは錫、亜鉛、鉄、鉛、コバルトの金属カルボン酸塩、例えばジブチル錫ジラウレート、ジオクチル錫ジラウレート、ジブチル錫ジアセテート、ジブチル錫ジオクトエートが挙げられる。
これらの添加量は特に限定されるものではないが、エチレン・α−オレフィン共重合体（ａ）１００重量部に対し、好ましくは０．００１〜５重量部であり、更に好ましくは０．００５〜２重量部である。０．００１重量部未満では十分な架橋反応が進まず耐熱性が不充分となり、５重量部を超えると押出機内で早期架橋が起こり、スコーチ現象が発生する傾向となる。
6). Silanol condensation catalyst (e)
The silanol condensation catalyst (e) used in the present invention is one or more compounds selected from the group consisting of metal organic acid salts, titanates, borates, organic amines, ammonium salts, phosphonium salts, inorganic acids and organic acids. Can be preferably used. Examples of metal organic acid salts, titanates, borates, organic amines, ammonium salts, and phosphonium salts include metal carboxylates such as tin, zinc, iron, lead, and cobalt, organometallic compounds of titanates and chelate compounds. It is done.
Specifically, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, stannous acetate, stannous octoate, cobalt naphthenate, lead octylate, lead naphthenate, zinc octylate, capryl Zinc acid, iron 2-ethylhexanoate, iron octylate, iron stearate, tetratitanate titanate, tetranonyl titanate, bis (acetylacetonitrile) di-isopropyl titanate, ethylamine, dibutylamine, hexylamine, triethanol Amine, dimethyl soyaamine, tetramethylguanidine, pyridine, ammonium carbonate, tetramethylammonium hydroxide, tetramethylphosphonium hydroxide, sulfuric acid, hydrochloric acid, toluenesulfonic acid, acetic acid, Phosphoric acid, and maleic acid.
Among these, metal organic acid salts, preferably metal carboxylates of tin, zinc, iron, lead, cobalt, such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctoate are preferable. .
The amount of these additives is not particularly limited, but is preferably 0.001 to 5 parts by weight, more preferably 0.005 to 100 parts by weight of the ethylene / α-olefin copolymer (a). 2 parts by weight. If the amount is less than 0.001 part by weight, sufficient crosslinking reaction does not proceed and heat resistance is insufficient. If the amount exceeds 5 parts by weight, early crosslinking occurs in the extruder and a scorch phenomenon tends to occur.
７．安定剤（ｆ）
本発明の樹脂組成物には、必要に応じて安定剤（ｅ）を使用することができる。具体的には、酸化防止剤、光安定剤、金属害防止剤等が使用できる。
酸化防止剤として、例えば、２，４−ジメチル−６−ｔ−ブチルフェノール、２，６−ジ−ｔ−ブチルフェノール、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、２，６−ジ−ｔ−ブチル−４−エチルフェノール、２，４，６−トリ−ｔ−ブチルフェノール、２，５−ジ−ｔ−ブチルハイドロキノン、ブチル化ヒドロキシアニソール、ｎ−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、ステアリル−β−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート等のモノフェノール系、４，４’−ジヒドロキシジフェニル、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、４，４’−メチレンビス（２，６−ジ−ｔ−ブチルフェノール）、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、２，６−ビス（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルベンジル）−４−メチルフェノール等のビスフェノール系、１，１，３−トリス（２’−メチル−４’−ヒドロキシ−５’−ｔ−ブチルフェニル）ブタン、１，３，５−トリメチル−２，４，６−トリス（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシベンジル）ベンゼン、トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）イソシアヌレート、トリス〔β−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシエチル〕イソシアヌレート、テトラキス〔メチレン−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〕メタン等のトリ以上のポリフェノール系、２，２’−チオビス（４−メチル−６−ｔ−ブチルフェノール）、４，４’−チオビス（２−メチル−６−ｔ−ブチルフェノール）、４，４’−チオビス（３−メチル−６−ｔ−ブチルフェノール）等のチオビスフェノール系、アルドール−α−ナフチルアミン、フェニル−α−ナフチルアミン、フェニル−β−ナフチルアミン等のナフチルアミン系、ｐ−イソプロポキシジフェニルアミン等のジフェニルアミン系、Ｎ，Ｎ’−ジフェニル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジ−β−ナフチル−ｐ−フェニレンジアミン、Ｎ−シクロヘキシル−Ｎ’−フェニル−ｐ−フェニレンジアミン、Ｎ−イソプロピル−Ｎ’−フェニル−ｐ−フェニレンジアミン等のフェニレンジアミン系のもの等が挙げられる。これらの中で、モノフェノール系、ビスフェノール系、トリ以上のポリフェノール系、チオビスフェノール系等が好ましい。
7). Stabilizer (f)
A stabilizer (e) can be used in the resin composition of the present invention as necessary. Specifically, antioxidants, light stabilizers, metal damage inhibitors and the like can be used.
Examples of the antioxidant include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,6-di-t. -Butyl-4-ethylphenol, 2,4,6-tri-t-butylphenol, 2,5-di-t-butylhydroquinone, butylated hydroxyanisole, n-octadecyl-3- (3 ', 5'-di -T-butyl-4'-hydroxyphenyl) propionate, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and other monophenols, 4,4'-dihydroxydiphenyl, 2, 2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebi (2,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,6-bis (2′-hydroxy-3′-tert-butyl-5 ′) -Methylbenzyl) -4-methylphenol and other bisphenols, 1,1,3-tris (2'-methyl-4'-hydroxy-5'-t-butylphenyl) butane, 1,3,5-trimethyl- 2,4,6-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, tris [ β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) Propi Nate] Triphenol or higher polyphenols such as methane, 2,2′-thiobis (4-methyl-6-tert-butylphenol), 4,4′-thiobis (2-methyl-6-tert-butylphenol), 4,4 Thiobisphenols such as' -thiobis (3-methyl-6-t-butylphenol), naphthylamines such as aldol-α-naphthylamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, and diphenylamines such as p-isopropoxydiphenylamine N, N′-diphenyl-p-phenylenediamine, N, N′-di-β-naphthyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, N-isopropyl-N ′ -Phenyl-p-phenylenediamine and other phenylenediamine-based ones . Of these, monophenol-based, bisphenol-based, tri- or higher polyphenol-based, and thiobisphenol-based are preferable.
光安定剤や紫外線吸収剤の具体例としては、４−ｔ−ブチルフェニルサリシレート、２，４−ジヒドロキシベンゾフェノン、２，２′−ジヒドロキシ−４−メトキシベンゾフェノン、エチル−２−シアノ−３，３′−ジフェニルアクリレート、２−エチルヘキシル−２−ジアノ−３，３′−ジフェニルアクリレート、２（２′−ヒドロキシ−３′−ｔ−ブチル−５′−メチルフェニル）−５−クロロベンゾトリアゾール、２（２′−ヒドロキシ−３，５′−ジ−ｔ−ブチルフェニル）ベンゾトリアゾール、２（２′−ヒドロキシ−５′−メチルフェニル）ベンゾトリアゾール、２−ヒドロキシ−５−クロルベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン−２−ヒドロキシ−４−オクトキシベンゾフェノン、２（２′−ヒドロキシ−４−オクトキシフェニル）ベンゾトリアゾール、モノグリコールサリチレート、オキザリック酸アミド、フェニルサリチレート、２，２′，４，４′−テトラヒドロキシベンゾフェノンなどが挙げられる。 Specific examples of the light stabilizer and the ultraviolet absorber include 4-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, ethyl-2-cyano-3,3 ′. -Diphenyl acrylate, 2-ethylhexyl-2-diano-3,3'-diphenyl acrylate, 2 (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 (2 '-Hydroxy-3,5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-5'-methylphenyl) benzotriazole, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4- Methoxybenzophenone-2-hydroxy-4-octoxybenzophenone, 2 (2'-hydro Shi-4-octoxyphenyl) benzotriazole, monoglycol salicylate, Okizarikku acid amide, phenyl salicylate, 2,2 ', 4,4'-like tetrahydroxy benzophenone.
金属害防止剤は、ヒドラジド誘導体、シュウ酸誘導体、サリチル酸誘導体などを挙げることができる。
ヒドラジド誘導体金属害防止剤としては、Ｎ，Ｎ′−ジアセチルアジピン酸ヒドラジド、アジピン酸ビス（α−フェノキシプロピオニルヒドラジド）、テレフタル酸ビス（α−フェノキシプロピオニルヒドラジド）、セバチン酸ビス（α−フェノキシプロピオニルヒドラジド）、イソフタル酸ビス（β−フェノキシプロピオニルヒドラジド）などが挙げられ、シュウ酸誘導体金属害防止剤としては、Ｎ，Ｎ′−ジベンザル（オキザリルジヒドラジド）、Ｎ−ベンザル−（オキザリルジヒドラジド）、オキザリルビス−４−メチルベンジリデンヒドラジド、オキザリルビス−３−エトキシベンジリデンヒドラジド等が挙げられ、また、サリチル酸誘導体金属害防止剤としては、３−（Ｎ−サリチロイル）アミノ−１，２，４−トリアゾール、デカメチレンジカルボン酸ジサリチロイルヒドラジドが挙げられる。
本発明において好ましい金属害防止剤は、サリチル酸誘導体金属害防止剤である。
Examples of the metal harm preventing agent include hydrazide derivatives, oxalic acid derivatives, salicylic acid derivatives and the like.
Examples of hydrazide derivative metal damage inhibitors include N, N'-diacetyladipate hydrazide, bis (α-phenoxypropionylhydrazide) adipate, bis (α-phenoxypropionylhydrazide) terephthalate, and bis (α-phenoxypropionylhydrazide) sebacate. ), Isophthalic acid bis (β-phenoxypropionyl hydrazide), and the like, and oxalic acid derivative metal harm inhibitors include N, N′-dibenzal (oxalyl dihydrazide), N-benzal- (oxalyl dihydrazide), oxalyl bis. -4-methyl benzylidene hydrazide, oxalyl bis-3-ethoxy benzylidene hydrazide and the like, and salicylic acid derivative metal hazard inhibitors include 3- (N-salicyloyl) amino-1,2,4-triazole, deca It includes Ji dicarboxylic acid disalicyloylhydrazide.
In the present invention, a preferred metal damage inhibitor is a salicylic acid derivative metal damage inhibitor.
これらの安定剤（ｆ）の添加量は、特に限定されるものではないが、エチレン・α−オレフィン共重合体（ａ）１００重量部に対し、好ましくは０．００１〜５重量部であり、更に好ましくは０．００１〜３重量部である。０．００１重量部未満では十分な安定化効果が得られず、５重量部を超えると着色等の影響が生じ、また成形不良を起こす傾向にあり、添加量の増加に見合うだけの効果が得られず経済的ではなくなる。
樹脂組成物中の安定剤（ｆ）は、蛍光Ｘ線分析、ガスクロマトグラフィー、液体クロマトグラフィーを用いて測定することができる。
本発明の樹脂組成物には、各種公知の添加剤、充填材等を適宜の量で添加できる。添加剤としては、上記のような酸化防止剤（フェノール系、リン系、イオウ系）、光安定剤のほかに、例えば、滑剤、帯電防止剤、紫外線吸収剤、着色剤、顔料、染料等を１種又は２種以上適宜併用することができる。また、充填材としては、例えばタルク、マイカ等を使用できるが、基本的には、本発明の目的を満たす限りにおいて、これらの添加剤は使用しない方が好ましい。
The amount of the stabilizer (f) added is not particularly limited, but is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin copolymer (a), More preferably, it is 0.001-3 weight part. If the amount is less than 0.001 part by weight, a sufficient stabilizing effect cannot be obtained. If the amount exceeds 5 parts by weight, there is a tendency to cause coloring and the like, and there is a tendency to cause molding failure. It will not be economical.
The stabilizer (f) in the resin composition can be measured using fluorescent X-ray analysis, gas chromatography, or liquid chromatography.
Various known additives, fillers and the like can be added to the resin composition of the present invention in appropriate amounts. As additives, in addition to the above antioxidants (phenolic, phosphorus, sulfur), light stabilizers, for example, lubricants, antistatic agents, ultraviolet absorbers, colorants, pigments, dyes, etc. 1 type, or 2 or more types can be used together suitably. Further, as the filler, for example, talc, mica and the like can be used, but basically it is preferable not to use these additives as long as the object of the present invention is satisfied.
８．立体網目状構造体の成形
本発明においては、その後、上記のようにして得られたグラフト反応物（ｄ）とシラノール縮合触媒（ｅ）を含む樹脂組成物を、図２に示すように押出成形しストランドとする。次に、このストランドを熱融着（熱接着）してから、水冷却（シラン架橋）して立体網目状構造体とする。
押出成形では、例えば特開２００２−８８６３１号公報に記載されているような製造装置及び成形方法により、樹脂組成物を立体網目状構造体に成形できる。
具体的には、樹脂組成物を押出機先端のダイスから複数のストランドとして押出し、ストランドが湾曲する力を利用し、隣同士のストランドを熱接着させロールに挟みながら水槽内で冷却固化させ三次元網目状の構造体を得る成形方法である。
構造体の成形は、ストランドが安定して押出され、表面が平滑でかつ熱接着しやすくなるような条件にする必要があり、具体的には成形温度、押出量、引取速度等で調整できる。また、ロールに挟む距離を調整することにより構造体の見掛け密度（空隙度）を調整することもできる。
8). Molding of three-dimensional network structure In the present invention, a resin composition containing the graft reaction product (d) and silanol condensation catalyst (e) obtained as described above is then extruded as shown in FIG. And strands. Next, this strand is thermally fused (thermally bonded), and then cooled with water (silane crosslinking) to form a three-dimensional network structure.
In extrusion molding, the resin composition can be molded into a three-dimensional network structure by a manufacturing apparatus and a molding method as described in, for example, Japanese Patent Application Laid-Open No. 2002-88631.
Specifically, the resin composition is extruded as a plurality of strands from a die at the tip of the extruder, and the three-dimensional shape is obtained by cooling and solidifying in a water tank while sandwiching the adjacent strands in a roll by utilizing the force of bending the strands. This is a molding method for obtaining a net-like structure.
The molding of the structure needs to be performed under such conditions that the strands are stably extruded, the surface is smooth, and the heat bonding is easy, and can be adjusted specifically by the molding temperature, the extrusion amount, the take-up speed, and the like. Further, the apparent density (void degree) of the structure can be adjusted by adjusting the distance between the rolls.
９．シラン架橋処理
上記方法によって得られた立体網目状構造体は、水雰囲気中に曝すことにより、架橋が進行し、架橋ポリエチレンとなる。水雰囲気中に曝す方法は、各種の条件を採用することができ、水分を含む空気中に放置する方法、水蒸気を含む空気を送風する方法、水浴中に浸漬する方法、温水を霧状に散水させる方法等が挙げられる。
本発明の立体網目状構造体は、上記のグラフト反応物（ｄ）の加水分解可能な有機基がシラノール縮合触媒（ｅ）の存在下、水と反応して加水分解してシラノール基が生成し、シラノール基同士が脱水縮合することにより、グラフト反応物（ｄ）同士が結合し、架橋反応を起こすことにより生成する。
架橋の進行速度は水雰囲気中に曝す条件によって決まるが、室温〜２００℃の温度範囲、かつ１０分〜１週間の範囲で曝せばよい。特に好ましい条件は、常温〜１３０℃の温度範囲、３０分〜１００時間の範囲である。水分を含む空気を使用する場合、相対湿度は、１〜１００％の範囲から選択される。
架橋ポリエチレンが長期間に亘って優れた特性を発揮するためには、ＩＳＯ １０１４７−１９９４に準拠して測定したゲル分率（架橋度）が６５％以上であることが好ましい。ゲル分率は、エチレン性不飽和シラン化合物のグラフト率、シラノール縮合触媒の種類、量、架橋させる際の条件（温度、時間）などを変えることにより、調整することができる。
特に、本発明におけるシラン架橋は成形時には架橋せずに成形ができるため、成形直後のループ性、熱接着性等特殊な成形性を必要とする網目状構造体を効率よく成形でき、しかも得られた成形品は、ポリエチレン樹脂の大きなウィークポイントである耐熱性を改善し、優れたクッション性を示す立体網目状構造体を提供することができる。
9. Silane cross-linking treatment The three-dimensional network structure obtained by the above-described method is subjected to cross-linking by being exposed to a water atmosphere to become a cross-linked polyethylene. Various conditions can be adopted for the method of exposure in a water atmosphere, a method of leaving in air containing moisture, a method of blowing air containing water vapor, a method of immersing in a water bath, and spraying hot water in a mist form And the like.
In the three-dimensional network structure of the present invention, the hydrolyzable organic group of the graft reaction product (d) reacts with water in the presence of the silanol condensation catalyst (e) to hydrolyze to form a silanol group. The silanol groups are dehydrated and condensed to form graft reaction products (d) which are bonded to each other to cause a crosslinking reaction.
The rate of cross-linking is determined by the conditions of exposure in a water atmosphere, but it may be exposed in the temperature range of room temperature to 200 ° C. and in the range of 10 minutes to 1 week. Particularly preferable conditions are a temperature range of room temperature to 130 ° C. and a range of 30 minutes to 100 hours. When using air containing moisture, the relative humidity is selected from a range of 1 to 100%.
In order for the crosslinked polyethylene to exhibit excellent properties over a long period of time, it is preferable that the gel fraction (degree of crosslinking) measured in accordance with ISO 10147-1994 is 65% or more. The gel fraction can be adjusted by changing the graft ratio of the ethylenically unsaturated silane compound, the type and amount of the silanol condensation catalyst, and the conditions (temperature, time) for crosslinking.
In particular, since the silane crosslinking in the present invention can be molded without crosslinking at the time of molding, it is possible to efficiently mold a network structure that requires special moldability such as loop properties immediately after molding, thermal adhesiveness, and the like. The molded article can improve heat resistance, which is a large weak point of polyethylene resin, and can provide a three-dimensional network structure having excellent cushioning properties.
１０．立体網目状構造体
本発明の立体網目状構造体は、特開２００６−２００１１７号公報に記載されているような構造を有する。図１に示すように、主として本発明の樹脂組成部からなる３００デシテックス以上の連続線状体を曲がりくねらせ多数のループを形成し、各々のループを互いに溶融状態で接触させ、接触部の大部分が互いに融着して三次元ランダムループからなる立体網目状構造を形成させたものである。このことで、非常に大きい応力で、大変形を与えても、融着一体化した三次元ランダムループからなる立体網目状構造全体が変形して応力を吸収し、応力が解除されると、構造体は少し時間をかけて元の形態に回復することができる。
これにより公知の熱可塑性樹脂からなる連続線状体で構成された立体網目状構造体をクッション材に用いた場合、連続線状体の繊度が大きかったり、あるいは立体網目状構造体の見掛け密度が高い場合、立体網目状構造体がクッション性を有さず、たとえ有したとしても塑性変形を生じたり、あるいは破壊されたりし、このような回復が起こらない。
10. Three-dimensional network structure The three-dimensional network structure of the present invention has a structure as described in JP-A-2006-200117. As shown in FIG. 1, a continuous linear body of 300 dtex or more mainly composed of the resin composition part of the present invention is twisted to form a large number of loops, and each loop is brought into contact with each other in a molten state. The portions are fused together to form a three-dimensional network structure composed of three-dimensional random loops. As a result, even if a large deformation is applied with a very large stress, the entire three-dimensional network structure composed of the fused three-dimensional random loop is deformed and absorbs the stress. The body can recover to its original form over time.
Accordingly, when a three-dimensional network structure composed of a continuous linear body made of a known thermoplastic resin is used as a cushioning material, the fineness of the continuous linear body is large or the apparent density of the three-dimensional network structure is high. When it is high, the three-dimensional network structure does not have cushioning properties, and even if it has, plastic deformation or destruction occurs, and such recovery does not occur.
本発明の立体網目状構造体を形成する連続線状体の繊度は、特に限定されないが、３００デシテックス以下では強度が低くなり反発力が低下することがある。好ましくは４００デシテックス以上１００，０００デシテックス以下であり、より好ましくは５００〜５０，０００デシテックスである。１００，０００デシテックス以上では線状体の構成本数が少なくなり圧縮特性が悪くなる傾向がある。立体網目状構造体を形成する連続線状体の断面形状は特に限定されないが、細い繊度の連続線状体とする場合、異形断面や中空断面は反発力が向上するので好ましい。 The fineness of the continuous linear body forming the three-dimensional network structure of the present invention is not particularly limited. However, the strength may be lowered and the repulsive force may be decreased below 300 dtex. Preferably it is 400 dtex or more and 100,000 dtex or less, More preferably, it is 500-50,000 dtex. If the decitex is 100,000 or more, the number of linear members tends to decrease, and the compression characteristics tend to deteriorate. The cross-sectional shape of the continuous linear body forming the three-dimensional network structure is not particularly limited. However, when the continuous linear body has a fine fineness, a modified cross-section or a hollow cross-section is preferable because the repulsive force is improved.
本発明の立体網目状構造体は、要求性能に応じて、ループの形状、太さ及び数、見掛け密度等、適宜選択することができる。 The three-dimensional network structure of the present invention can be appropriately selected according to required performance, such as the shape, thickness and number of loops, and apparent density.
１１．立体網目状構造体の用途
本発明によれば、通常幅約１ｍ、厚さ約５０ｃｍ、見掛け密度０．０７〜０．１４ｇ／ｃｍ３の一般的な立体網目状構造体が得られるが、この大きさに限定されるものでない。本発明の立体網目状構造体は、家具、ベッド等の寝具、車両用座席、船舶用座席等のクッション材として好適に用いられる。また、本発明の立体網目状構造体は、必要に応じて他の材料との積層体として用いることもできる。
本発明により得られた製品は、優れたクッション性を有するため、発泡ウレタンに比べ反発力が高いこと、開放空隙を有するため洗浄が可能でアレルギーを引き起こすダニ、埃を除去できること、また耐熱性を有することより開放空隙構造を利用し温風過熱が可能なこと、更には例え外部応力により構造体が変化しても、架橋時の形状を記憶しているため加温することにより完全な形状復帰が可能になるなど優れた効果を発現する。
11. Use of three-dimensional network structure According to the present invention, a general three-dimensional network structure having a width of about 1 m, a thickness of about 50 cm, and an apparent density of 0.07 to 0.14 g / cm 3 can be obtained. It is not limited to size. The three-dimensional mesh-like structure of the present invention is suitably used as a cushioning material for furniture, bedding such as beds, vehicle seats, and ship seats. In addition, the three-dimensional network structure of the present invention can be used as a laminate with other materials as necessary.
Since the product obtained by the present invention has excellent cushioning properties, it has a higher repulsive force than foamed urethane, it has an open gap, it can be cleaned and can remove allergens and dust that cause allergies, and it has heat resistance. It is possible to overheat hot air using an open air gap structure, and even if the structure changes due to external stress, the shape at the time of cross-linking is memorized, so the shape is restored by heating. It is possible to produce excellent effects.
以下に実施例及び比較例よりなる実験例を記載し、本発明を更に具体的に説明する。なお、実施例及び比較例における物性の測定と評価は、以下に示す方法によって実施した。 Experimental examples consisting of examples and comparative examples will be described below to explain the present invention more specifically. In addition, the measurement and evaluation of the physical property in an Example and a comparative example were implemented by the method shown below.
（１）エチレン・α−オレフィン共重合体の物性測定
（１−１）ＭＦＲ：ＪＩＳ Ｋ６９２２−２：１９９７に準拠（温度１９０℃、荷重２．１６ｋｇ）して測定した。
（１−２）密度：ＪＩＳ Ｋ６９２２−１，２：１９９７に準拠して測定した。
（１−３）重量平均分子量／数平均分子量：ＧＰＣ（ゲルパーミエーション）装置のサイズ排除クロマトグラフィーを用いて、以下に示す条件で測定し、重量平均分子量と数平均分子量の比を求めた。単分散ポリスチレンで、ユニバーサルな検量線を作成し、直鎖のポリエチレンの分子量として計算した。
機種：Ｗａｔｅｒｓ Ｍｏｄｅｌ １５０Ｃ ＧＰＣ
溶媒：ｏ−ジクロロベンゼン
流速：１ｍｌ／分
温度：１４０℃
測定濃度：２ｍｇ／ｍｌ
注入量：２００μｌ
カラム：昭和電工社製 ＡＤ８０Ｍ／Ｓ ３本
(1) Measurement of physical properties of ethylene / α-olefin copolymer (1-1) MFR: Measured according to JIS K6922-2: 1997 (temperature 190 ° C., load 2.16 kg).
(1-2) Density: Measured according to JIS K6922-1, 2: 1997.
(1-3) Weight average molecular weight / number average molecular weight: Using a size exclusion chromatography of a GPC (gel permeation) apparatus, measurement was performed under the following conditions to determine the ratio of the weight average molecular weight to the number average molecular weight. A universal calibration curve was created with monodisperse polystyrene and calculated as the molecular weight of linear polyethylene.
Model: Waters Model 150C GPC
Solvent: o-dichlorobenzene Flow rate: 1 ml / min Temperature: 140 ° C
Measurement concentration: 2 mg / ml
Injection volume: 200 μl
Column: 3 AD80M / S manufactured by Showa Denko
（２）立体網目状構造体の成形品の評価方法
（２−１）ゲル分率
ＩＳＯ １０１４７−１９９４に準拠して、成形品試料をソックスレー抽出器にてキシレン沸点温度で１０時間還流抽出、真空乾燥し、抽出前の試料重量に対して抽出・乾燥後の試料重量の割合を１００分率で求めた。
（２−２）圧縮強度
長さ１００ｍｍ×幅１００ｍｍ×厚み約８０ｍｍの試料をインストロン型万能引張・圧縮試験機で厚み方向に６０ｍｍ圧縮したときの強度として測定した。
（２−３）圧縮残留ひずみ
長さ５０ｍｍ×幅５０ｍｍ×厚み２５ｍｍに切り取り採取した試料を用い、ＪＩＳ Ｋ６４００−４：２００４の圧縮残留ひずみに準拠し測定した。なお、この試験は温度７０℃での圧縮ひずみ試験であるので、立体網目状構造体の耐熱性判断の指標として利用できる。
(2) Evaluation method of molded product of three-dimensional network structure (2-1) Gel fraction In accordance with ISO 10147-1994, a molded product sample was reflux extracted at a xylene boiling point temperature for 10 hours using a Soxhlet extractor, vacuum It dried and the ratio of the sample weight after extraction and drying with respect to the sample weight before extraction was calculated | required in 100 minutes.
(2-2) Compressive strength A sample having a length of 100 mm, a width of 100 mm, and a thickness of about 80 mm was measured as the strength when compressed by 60 mm in the thickness direction using an Instron universal tension / compression tester.
(2-3) Compressive residual strain Using a sample cut out and collected in a length of 50 mm, a width of 50 mm, and a thickness of 25 mm, the compressive residual strain was measured in accordance with the compressive residual strain of JIS K6400-4: 2004. Since this test is a compressive strain test at a temperature of 70 ° C., it can be used as an index for determining the heat resistance of the three-dimensional network structure.
［実施例１］
１）エチレン・α−オレフィン共重合体の製造
まず、特開昭６１−１３０３１４号公報の実施例に記載された方法に準拠して触媒の調製を行なった。即ち、錯体であるエチレン−ビス（４，５，６，７−テトラヒドロインデニル）ジルコニウムジクロライド２．０ミリモルに、メチルアルモキサンを上記錯体に対し１，０００モル倍加え、トルエンで１０リットルに希釈し、触媒溶液を調製した。重合体は、以下の方法で製造した。
内容積１．５リットルの撹拌式オートクレーブ型連続反応器にエチレンと１−ヘキセンとの混合物を１−ヘキセンの組成が６５重量％となるように供給し、反応器内の圧力を１，６００ｋｇ／ｃｍ２に保ち、１６０℃で反応を行ないペレタイズした。反応終了後、ＭＦＲが１２ｇ／１０分、密度が０．９０７ｇ／ｃｍ３、重量平均分子量と数平均分子量の比が２．４のエチレン・α−オレフィン共重合体（１−ヘキセン含量１８重量％）を得た。
[Example 1]
1) Production of ethylene / α-olefin copolymer First, a catalyst was prepared according to the method described in Examples of JP-A No. 61-130314. That is, methylalumoxane is added 1,000 mole times the above complex to 2.0 mmol of ethylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, which is a complex, and diluted to 10 liters with toluene. Then, a catalyst solution was prepared. The polymer was produced by the following method.
A mixture of ethylene and 1-hexene was supplied to a stirred autoclave type continuous reactor having an internal volume of 1.5 liter so that the composition of 1-hexene was 65% by weight, and the pressure in the reactor was 1,600 kg / The reaction was carried out at 160 ° C. while being kept at cm 2 and pelletized. After completion of the reaction, an ethylene / α-olefin copolymer having an MFR of 12 g / 10 min, a density of 0.907 g / cm 3 , and a ratio of the weight average molecular weight to the number average molecular weight of 2.4 (1-hexene content 18% by weight) )
２）シラン化合物のグラフト反応
上記１）で得られたエチレン・１−ヘキセン共重合体ペレット１００重量部にビニルトリメトキシシランを１．９６重量部、ジクミルパーオキサイドを０．０４重量部加え、含浸ペレットを得た。この含浸ペレットをスクリュー径４０ｍｍφ、Ｌ／Ｄ＝２６の単軸混練造粒機を用い、造粒温度１５０℃にてシラン化合物をグラフトしたペレットを得た。
2) Graft reaction of silane compound 1.96 parts by weight of vinyltrimethoxysilane and 0.04 parts by weight of dicumyl peroxide were added to 100 parts by weight of the ethylene / 1-hexene copolymer pellets obtained in 1) above. Impregnated pellets were obtained. The impregnated pellets were obtained by grafting a silane compound at a granulation temperature of 150 ° C. using a uniaxial kneading granulator having a screw diameter of 40 mmφ and L / D = 26.
３）シラノール縮合触媒と安定剤のマスターバッチ作製
上記１）のエチレン・１−ヘキセン共重合体ペレット１００重量部に、シラノール縮合触媒のジオクチルスズジラウレートを１重量部、安定剤のペンタエリストールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］（商品名ＩＲＧＡＮＯＸ １０１０）を５重量部配合し、スクリュー径３０ｍｍφの二軸混練造粒機を用い、造粒温度１５０℃にてシラノール縮合触媒含有マスターバッチペレットを得た。
3) Preparation of master batch of silanol condensation catalyst and stabilizer To 100 parts by weight of the ethylene / 1-hexene copolymer pellets of 1) above, 1 part by weight of dioctyltin dilaurate as a silanol condensation catalyst and pentaerythritol tetrakis as a stabilizer [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010) is blended, and using a biaxial kneading granulator with a screw diameter of 30 mmφ, a granulation temperature of 150 A master batch pellet containing a silanol condensation catalyst was obtained at ° C.
４）立体網目状構造体の成形
スクリュー径４０ｍｍφ、Ｌ／Ｄ＝２６の単軸押出機の先端に、ダイス及び冷却装置を具備させた成形機を用いた。ダイスは、直径０．５ｍｍφの円形の穴を、縦方向１３０ｍｍの間に１３列、横方向２００ｍｍの間に２０列、合計２６０個の円形穴を有するものを用い、単軸押出機の先端に設置した。冷却装置は、押出し品の挟み幅を任意に調整できる引取用キャタピラーを内蔵した水槽を使用し、ダイスの直下に設置した。
次に、上記２）のシラン化合物をグラフトしたペレット１００重量部、及び上記３）のシラノール縮合触媒含有マスターバッチペレット５重量部を投入し、成形温度２００℃にて厚み８０ｍｍの立体網目状構造体を成形した。
4) Molding of three-dimensional network structure A molding machine equipped with a die and a cooling device at the tip of a single screw extruder having a screw diameter of 40 mmφ and L / D = 26 was used. The die is a circular hole with a diameter of 0.5 mmφ with 13 rows in the longitudinal direction of 130 mm and 20 rows in the transverse direction of 200 mm, for a total of 260 round holes, at the tip of the single screw extruder. installed. As the cooling device, a water tank containing a caterpillar for take-up that can arbitrarily adjust the sandwiching width of the extruded product was used, and was installed directly under the die.
Next, 100 parts by weight of the pellets grafted with the silane compound of the above 2) and 5 parts by weight of the master batch pellets containing the silanol condensation catalyst of the above 3) are charged, and a three-dimensional network structure having a thickness of 80 mm at a molding temperature of 200 ° C. Was molded.
５）立体網目状構造体の架橋処理
上記４）の立体網目状構造体成形品を、４０℃の温水を霧状に散水する部屋中に１週間保管し、架橋処理した。
5) Crosslinking treatment of three-dimensional network structure The three-dimensional network structure molded product of 4) above was stored in a room in which warm water at 40 ° C. was sprayed in a mist for one week and subjected to crosslinking treatment.
６）立体網目状構造体の性能評価
上記５）の架橋処理した成形品の両サイドをカットし、長さ１００ｍｍ×幅１００ｍｍ×厚み約８０ｍｍの直方体状のブロック品を得た。このブロック品を用いて、平均厚み、見掛け密度、目視による表面外観、熱接着強度、ゲル分率、圧縮強度、柔軟性感触、圧縮残留ひずみを評価した。なお、圧縮残留ひずみについては、ブロック品の中心部から長さ５０ｍｍ×幅５０ｍｍ×厚み２５ｍｍに切り取り採取して測定評価した。
6) Performance evaluation of solid network structure Both sides of the cross-linked molded product of 5) above were cut to obtain a rectangular parallelepiped block product having a length of 100 mm, a width of 100 mm, and a thickness of about 80 mm. Using this block product, the average thickness, the apparent density, the visual surface appearance, the thermal adhesive strength, the gel fraction, the compressive strength, the soft touch, and the compressive residual strain were evaluated. The compressive residual strain was measured and evaluated by cutting out from the center of the block product into a length of 50 mm, a width of 50 mm and a thickness of 25 mm.
なお、上記熱接着強度については、以下の基準で判定した。
「充分融着」：融着部分の両端ストランドを手で引張っても剥離しない。
「融着不充分」：融着部分の両端ストランドを手で引張ると容易に融着部分が剥離する。
「融着せず」：融着していない。
一方、柔軟性感触については、以下の基準で判定した。
「非常に良好」：製品（ブロック品）を手で押し込みながら上下させゴム的な感触が充分に得られる。
「かなり良好」：製品（ブロック品）を手で押し込みながら上下させゴム的な感触がかなり得られる。
「良好」：製品（ブロック品）を手で押し込みながら上下させゴム的な感触が得られる。
「悪い」：製品（ブロック品）を手で押し込みながら上下させゴム的な感触が得られず。
これらの評価結果を表１に示した。
The thermal bond strength was determined according to the following criteria.
“Sufficient fusion”: Even if the strands at both ends of the fusion part are pulled by hand, they do not peel off.
“Insufficient fusion”: When the both end strands of the fusion part are pulled by hand, the fusion part easily peels off.
“Not fused”: Not fused.
On the other hand, the soft touch was determined according to the following criteria.
“Very good”: The product (block product) is pushed up and down while being pushed by hand, and a rubber-like feel is sufficiently obtained.
“Remarkably good”: The product (block product) is pushed up and down while being pushed by hand, and a rubber-like feel can be obtained considerably.
“Good”: The product (block product) is pushed up and down by hand to obtain a rubbery feel.
"Bad": The product (block product) is pushed up and down while being pushed by hand, and the rubbery feel cannot be obtained.
The evaluation results are shown in Table 1.
［実施例２］
実施例１のエチレン・α−オレフィン共重合体の重合条件を変えて、ＭＦＲが１６．５ｇ／１０分、密度が０．８９８ｇ／ｃｍ３、重量平均分子量と数平均分子量の比が２．４のエチレン・α−オレフィン共重合体を製造した。このエチレン・α−オレフィン共重合体を用いた以外は実施例１と同様にして立体網目状構造体を成形し評価した。評価結果を表１に示した。
[Example 2]
By changing the polymerization conditions of the ethylene / α-olefin copolymer of Example 1, the MFR was 16.5 g / 10 minutes, the density was 0.898 g / cm 3 , and the ratio of the weight average molecular weight to the number average molecular weight was 2.4. An ethylene / α-olefin copolymer was prepared. A three-dimensional network structure was molded and evaluated in the same manner as in Example 1 except that this ethylene / α-olefin copolymer was used. The evaluation results are shown in Table 1.
［実施例３］
実施例１のエチレン・α−オレフィン共重合体の重合条件を変えて、ＭＦＲが３０ｇ／１０分、密度が０．８８０ｇ／ｃｍ３、重量平均分子量と数平均分子量の比が２．４のエチレン・α−オレフィン共重合体を製造した。このエチレン・α−オレフィン共重合体を用いた以外は実施例１と同様にして立体網目状構造体を成形し評価した。評価結果を表１に示した。
[Example 3]
By changing the polymerization conditions of the ethylene / α-olefin copolymer of Example 1, an MFR of 30 g / 10 min, a density of 0.880 g / cm 3 , and a ratio of weight average molecular weight to number average molecular weight of 2.4 -The alpha-olefin copolymer was manufactured. A three-dimensional network structure was molded and evaluated in the same manner as in Example 1 except that this ethylene / α-olefin copolymer was used. The evaluation results are shown in Table 1.
［実施例４］
実施例１のエチレン・α−オレフィン共重合体の重合条件を変えて、ＭＦＲが５ｇ／１０分、密度が０．９０６ｇ／ｃｍ３、重量平均分子量と数平均分子量の比が２．４のエチレン・α−オレフィン共重合体を製造した。このエチレン・α−オレフィン共重合体を用いた以外は実施例１と同様にして立体網目状構造体を成形し評価した。評価結果を表１に示した。
[Example 4]
By changing the polymerization conditions of the ethylene / α-olefin copolymer of Example 1, the MFR is 5 g / 10 min, the density is 0.906 g / cm 3 , and the ratio of the weight average molecular weight to the number average molecular weight is 2.4. -The alpha-olefin copolymer was manufactured. A three-dimensional network structure was molded and evaluated in the same manner as in Example 1 except that this ethylene / α-olefin copolymer was used. The evaluation results are shown in Table 1.
［実施例５］
実施例１のエチレン・α−オレフィン共重合体の重合条件を変えて、ＭＦＲが５０ｇ／１０分、密度が０．９０７ｇ／ｃｍ３、重量平均分子量と数平均分子量の比が２．４のエチレン・α−オレフィン共重合体を製造した。このエチレン・α−オレフィン共重合体を用いた以外は実施例１と同様にして立体網目状構造体を成形し評価した。評価結果を表１に示した。
[Example 5]
By changing the polymerization conditions of the ethylene / α-olefin copolymer of Example 1, ethylene having an MFR of 50 g / 10 min, a density of 0.907 g / cm 3 , and a ratio of the weight average molecular weight to the number average molecular weight of 2.4 -The alpha-olefin copolymer was manufactured. A three-dimensional network structure was molded and evaluated in the same manner as in Example 1 except that this ethylene / α-olefin copolymer was used. The evaluation results are shown in Table 1.
［比較例１］
エチレン・α−オレフィン共重合体に対してシラン化合物のグラフト反応を実施せず、シラノール縮合触媒含有マスターバッチペレットを使用しないこと以外は、実施例１と同様にして立体網目状構造体を成形し評価した。評価結果を表１に示した。この結果、耐熱性の目安となる圧縮残留ひずみが大幅に悪化していることが確認された。
[Comparative Example 1]
A three-dimensional network structure was formed in the same manner as in Example 1 except that the graft reaction of the silane compound was not performed on the ethylene / α-olefin copolymer and the master batch pellet containing the silanol condensation catalyst was not used. evaluated. The evaluation results are shown in Table 1. As a result, it was confirmed that the compressive residual strain, which is a measure of heat resistance, was greatly deteriorated.
［比較例２］
実施例１のエチレン・α−オレフィン共重合体の重合条件を変えて、ＭＦＲが１ｇ／１０分、密度が０．９０５ｇ／ｃｍ３、重量平均分子量と数平均分子量の比が２．５のエチレン・α−オレフィン共重合体を製造した。このエチレン・α−オレフィン共重合体を用いた以外は実施例１と同様にして立体網目状構造体を成形し評価した。評価結果を表１に示した。
この結果、ストランドの表面が荒れ、融着も充分でなかった。
[Comparative Example 2]
By changing the polymerization conditions of the ethylene / α-olefin copolymer of Example 1, an MFR of 1 g / 10 min, a density of 0.905 g / cm 3 , and a ratio of the weight average molecular weight to the number average molecular weight of 2.5 -The alpha-olefin copolymer was manufactured. A three-dimensional network structure was molded and evaluated in the same manner as in Example 1 except that this ethylene / α-olefin copolymer was used. The evaluation results are shown in Table 1.
As a result, the surface of the strand was rough and the fusion was not sufficient.
［比較例３］
塩化チタン主成分とする固体触媒、トリエチルアルミニウム助触媒を用いたチーグラー触媒と分子量調整用の水素の存在下でエチレンと１−ヘキセンを重合して、ＭＦＲが１６ｇ／１０分、密度が０．９２１ｇ／ｃｍ３、重量平均分子量と数平均分子量の比が３．２のエチレン・α−オレフィン共重合体を製造した。このエチレン・α−オレフィン共重合体を用いた以外は実施例１と同様にして立体網状構造体を成形し評価した。評価結果を表１に示した。この結果、ストランドの熱接着が不十分であり、手で引っ張ると一部に融着部の剥れが生じた。
[Comparative Example 3]
Polymerization of ethylene and 1-hexene in the presence of a solid catalyst mainly composed of titanium chloride, Ziegler catalyst using triethylaluminum cocatalyst and hydrogen for molecular weight adjustment, MFR is 16 g / 10 min, density is 0.921 g An ethylene / α-olefin copolymer having a weight average molecular weight / number average molecular weight ratio of 3.2 / cm 3 was produced. A three-dimensional network structure was molded and evaluated in the same manner as in Example 1 except that this ethylene / α-olefin copolymer was used. The evaluation results are shown in Table 1. As a result, the thermal bonding of the strands was insufficient, and peeling of the fused part occurred in part when pulled by hand.
［比較例４］
実施例１のエチレン・α−オレフィン共重合体の重合条件を変えて、ＭＦＲが１１５ｇ／１０分、密度が０．９０６ｇ／ｃｍ３、重量平均分子量と数平均分子量の比が２．３のエチレン・α−オレフィン共重合体を製造した。このエチレン・α−オレフィン共重合体を用いた以外は実施例１と同様にして立体網目状構造体を成形し評価した。評価結果を表１に示した。この結果、樹脂が流れ過ぎてダイス出口が液状になりストランドが引き取れず成形ができなかった。
[Comparative Example 4]
By changing the polymerization conditions of the ethylene / α-olefin copolymer of Example 1, an MFR of 115 g / 10 min, a density of 0.906 g / cm 3 , and a ratio of the weight average molecular weight to the number average molecular weight of 2.3 -The alpha-olefin copolymer was manufactured. A three-dimensional network structure was molded and evaluated in the same manner as in Example 1 except that this ethylene / α-olefin copolymer was used. The evaluation results are shown in Table 1. As a result, the resin flowed too much and the die outlet became liquid, and the strand could not be taken out and could not be molded.
［比較例５］
実施例１のエチレン・α−オレフィン共重合体の重合条件を変えて、ＭＦＲが１５ｇ／１０分、密度が０．９２５ｇ／ｃｍ３、重量平均分子量と数平均分子量の比が２．４のエチレン・α−オレフィン共重合体を製造した。このエチレン・α−オレフィン共重合体を用いた以外は実施例１と同様にして立体網目状構造体を成形し評価した。評価結果を表１に示した。この結果、熱接着強度が低く、融着が不十分であり、柔軟性感触が悪かった。
[Comparative Example 5]
By changing the polymerization conditions of the ethylene / α-olefin copolymer of Example 1, ethylene having an MFR of 15 g / 10 min, a density of 0.925 g / cm 3 , and a ratio of weight average molecular weight to number average molecular weight of 2.4 -The alpha-olefin copolymer was manufactured. A three-dimensional network structure was molded and evaluated in the same manner as in Example 1 except that this ethylene / α-olefin copolymer was used. The evaluation results are shown in Table 1. As a result, the thermal adhesive strength was low, the fusion was insufficient, and the flexibility was poor.
［比較例６］
塩化チタン主成分とする固体触媒、トリエチルアルミニウム助触媒を用いたチーグラー触媒と分子量調整用の水素の存在下でエチレンと１−ヘキセンを重合して、ＭＦＲが１５ｇ／１０分、密度が０．９１９ｇ／ｃｍ３、重量平均分子量と数平均分子量の比が３．２のエチレン・α−オレフィン共重合体を製造した。このエチレン・α−オレフィン共重合体を用いた以外は実施例１と同様にして立体網状構造体を成形し評価した。評価結果を表１に示した。この結果、熱接着強度が低く、融着が不十分であり、柔軟性感触が悪かった。
[Comparative Example 6]
Polymerization of ethylene and 1-hexene in the presence of a solid catalyst based on titanium chloride, Ziegler catalyst using triethylaluminum cocatalyst and hydrogen for molecular weight adjustment, MFR is 15 g / 10 min, density is 0.919 g An ethylene / α-olefin copolymer having a weight average molecular weight / number average molecular weight ratio of 3.2 / cm 3 was produced. A three-dimensional network structure was molded and evaluated in the same manner as in Example 1 except that this ethylene / α-olefin copolymer was used. The evaluation results are shown in Table 1. As a result, the thermal adhesive strength was low, the fusion was insufficient, and the flexibility was poor.
上記の評価結果を示す表１から、実施例１〜５では、特定のエチレン・α−オレフィン共重合体とシラン化合物の配合及びグラフト反応により得られたエチレン系樹脂を用いているので、成形性と柔軟性に優れ、かつ、耐熱性にも優れた立体網目状構造体が得られることが分かる。
これに対して、比較例１では、エチレン・α−オレフィン共重合体のシラン化合物のグラフト反応を実施しなかったために、耐熱性の目安となる圧縮残留ひずみが大幅に悪化している。また、比較例２、４では、ＭＦＲが本発明から外れるエチレン・α−オレフィン共重合体を用いたために、ストランドの表面が荒れ、融着も充分でなかったか、樹脂が流れ過ぎてダイス出口が液状になりストランドが引き取れず成形ができなかった。一方、比較例３では、チーグラー触媒で製造されたエチレン・α−オレフィン共重合体を用いたために、ストランドの熱接着が不十分であり、手で引っ張ると一部に融着部の剥れが生じた。また、比較例５では、密度が本発明から外れるエチレン・α−オレフィン共重合体を用いたために、熱接着強度が低く、融着が不十分であり、柔軟性感触が悪かった。比較例６では、チーグラー触媒で重合されたエチレン・α−オレフィン共重合体を用いたために、熱接着強度が低く、融着が不十分であり、柔軟性感触が悪かった。
From Table 1 which shows said evaluation result, in Examples 1-5, since the ethylene-type resin obtained by the mixing | blending and graft reaction of a specific ethylene-alpha-olefin copolymer and a silane compound is used, a moldability is used. It can be seen that a three-dimensional network structure having excellent flexibility and heat resistance can be obtained.
On the other hand, in Comparative Example 1, since the graft reaction of the silane compound of the ethylene / α-olefin copolymer was not performed, the compressive residual strain, which is a measure of heat resistance, was greatly deteriorated. Moreover, in Comparative Examples 2 and 4, since the MFR used an ethylene / α-olefin copolymer deviating from the present invention, the surface of the strand was rough, the fusion was not sufficient, or the resin flowed too much and the die outlet was It became liquid and the strand could not be pulled out and could not be molded. On the other hand, in Comparative Example 3, since an ethylene / α-olefin copolymer produced with a Ziegler catalyst was used, the thermal adhesion of the strands was insufficient, and when it was pulled by hand, the fused part was partially peeled off. occured. Further, in Comparative Example 5, since an ethylene / α-olefin copolymer having a density deviating from the present invention was used, the thermal adhesive strength was low, the fusion was insufficient, and the flexibility was poor. In Comparative Example 6, since an ethylene / α-olefin copolymer polymerized with a Ziegler catalyst was used, the thermal adhesive strength was low, the fusion was insufficient, and the flexibility was poor.
Claims (5)
［化１］ Ｒ１ＳｉＲ２ ｎＹ３−ｎ・・・（Ｉ）
（一般式（Ｉ）において、Ｒ１はエチレン性不飽和炭化水素基（酸素原子を有していてもよい）であり、Ｒ２は炭素数１〜１２のアルキル基、Ｙは加水分解可能な有機基であり、相互に同一でも異なっていてもよく、ｎは０〜２である） An ethylene / α-olefin copolymer polymerized by a metallocene catalyst , having a melt flow rate (MFR) measured at a temperature of 190 ° C. and a load of 2.16 kg of 2 to 50 g / 10 min, and a density of 0 .850~0.920g / cm 3, and gel permeation chromatography (GPC) according to weight average molecular weight (Mw) and number average molecular weight (Mn) ethylene · alpha-olefin copolymer ratio is 3 or less (a ) 0.1 to 10 parts by weight of the ethylenically unsaturated silane compound (b) represented by the following general formula (I) with respect to 100 parts by weight of the radical generator (c) 0.001 to 5 parts by weight Polyethylene resin for a three-dimensional network structure comprising a graft reaction product (d) obtained by grafting in the presence of 0.001 to 5 parts by weight of a silanol condensation catalyst (e) Narubutsu.
[Chemical Formula 1] R 1 SiR 2 n Y 3-n (I)
(In General Formula (I), R 1 is an ethylenically unsaturated hydrocarbon group (which may have an oxygen atom), R 2 is an alkyl group having 1 to 12 carbon atoms, and Y is hydrolyzable. An organic group, which may be the same or different from each other, and n is 0 to 2)
［化２］ Ｈ２Ｃ＝Ｃ（Ｒ３）Ｓｉ（ＯＲ４）３・・・（ＩＩ）
（一般式（ＩＩ）において、Ｒ３は、Ｈ又はＣＨ３、Ｒ４は、相互に同一でも異なっていてもよい炭素数４以下の直鎖若しくは分岐アルキル基、又はフェニル基である） The polyethylene-based resin composition for a three-dimensional network structure according to claim 1, wherein the ethylenically unsaturated silane compound (b) is a compound represented by the following general formula (II).
[Chemical Formula 2] H 2 C═C (R 3 ) Si (OR 4 ) 3 (II)
(In general formula (II), R 3 is H or CH 3 , and R 4 is a linear or branched alkyl group having 4 or less carbon atoms, which may be the same or different from each other, or a phenyl group)
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| JP2002097339A (en) * | 2000-09-27 | 2002-04-02 | Kinugawa Rubber Ind Co Ltd | Flexible elastomer composition and method for producing the same |
| JP2003026875A (en) * | 2001-07-13 | 2003-01-29 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic elastomer composition |
| JP4709530B2 (en) * | 2004-11-04 | 2011-06-22 | リケンテクノス株式会社 | Flame retardant resin composition |
| JP4835150B2 (en) * | 2004-12-21 | 2011-12-14 | 東洋紡績株式会社 | Elastic network structure with soft resilience |
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