JP4379187B2 - Method for producing thermoplastic elastomer composition - Google Patents
Method for producing thermoplastic elastomer composition Download PDFInfo
- Publication number
- JP4379187B2 JP4379187B2 JP2004123693A JP2004123693A JP4379187B2 JP 4379187 B2 JP4379187 B2 JP 4379187B2 JP 2004123693 A JP2004123693 A JP 2004123693A JP 2004123693 A JP2004123693 A JP 2004123693A JP 4379187 B2 JP4379187 B2 JP 4379187B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- acrylate
- thermoplastic elastomer
- resin
- elastomer composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 78
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 229920001971 elastomer Polymers 0.000 claims description 52
- 239000005060 rubber Substances 0.000 claims description 49
- 239000003431 cross linking reagent Substances 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 229920005992 thermoplastic resin Polymers 0.000 claims description 19
- 229920000800 acrylic rubber Polymers 0.000 claims description 18
- 229920000058 polyacrylate Polymers 0.000 claims description 18
- 229920005672 polyolefin resin Polymers 0.000 claims description 17
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 10
- 239000011258 core-shell material Substances 0.000 claims description 9
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 5
- 229920006122 polyamide resin Polymers 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 2
- -1 compatibilizers Substances 0.000 description 41
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 33
- 238000004132 cross linking Methods 0.000 description 28
- 239000003921 oil Substances 0.000 description 28
- 235000019198 oils Nutrition 0.000 description 28
- 239000004014 plasticizer Substances 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 239000000178 monomer Substances 0.000 description 21
- 229920001577 copolymer Polymers 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 239000000945 filler Substances 0.000 description 15
- 238000004898 kneading Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000004606 Fillers/Extenders Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000011256 inorganic filler Substances 0.000 description 10
- 229910003475 inorganic filler Inorganic materials 0.000 description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 230000003712 anti-aging effect Effects 0.000 description 8
- 150000001451 organic peroxides Chemical class 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001741 organic sulfur group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920006124 polyolefin elastomer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- LBHPSYROQDMVBS-UHFFFAOYSA-N (1-methylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C)CCCCC1 LBHPSYROQDMVBS-UHFFFAOYSA-N 0.000 description 2
- OFZRSOGEOFHZKS-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br OFZRSOGEOFHZKS-UHFFFAOYSA-N 0.000 description 2
- AYYISYPLHCSQGL-UHFFFAOYSA-N (2,3,4,5,6-pentachlorophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl AYYISYPLHCSQGL-UHFFFAOYSA-N 0.000 description 2
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 2
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-N 0.000 description 2
- IWTINSUNRUQBBO-UHFFFAOYSA-N 1,2-diphenylethyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(OC(=O)C(=C)C)CC1=CC=CC=C1 IWTINSUNRUQBBO-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- BQMWZHUIGYNOAL-UHFFFAOYSA-N 1-phenylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)C1=CC=CC=C1 BQMWZHUIGYNOAL-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 2
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 2
- DDXZFLFMKZXQOT-UHFFFAOYSA-N 2-fluoroprop-2-enenitrile Chemical compound FC(=C)C#N DDXZFLFMKZXQOT-UHFFFAOYSA-N 0.000 description 2
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- MXTBGEVVUCLNMR-UHFFFAOYSA-N 3,3-dimethylbut-1-enyl prop-2-enoate Chemical compound CC(C)(C)C=COC(=O)C=C MXTBGEVVUCLNMR-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 101000757216 Homo sapiens Protein arginine N-methyltransferase 1 Proteins 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 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
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 102100022985 Protein arginine N-methyltransferase 1 Human genes 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- DQVUUGHMHQPVSI-UHFFFAOYSA-N [chloro(phenyl)methyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(Cl)C1=CC=CC=C1 DQVUUGHMHQPVSI-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- AVXYPAZKABBYHD-UHFFFAOYSA-N benzhydryl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(OC(=O)C(=C)C)C1=CC=CC=C1 AVXYPAZKABBYHD-UHFFFAOYSA-N 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 2
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- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
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- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
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- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
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- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、熱可塑性エラストマー組成物の製造方法に関し、詳しくは、従来の製造方法に比べてより簡潔で処理時間が短く、省エネルギーで製造することができる熱可塑性エラストマー組成物の製造方法に関する。 The present invention relates to a method for producing a thermoplastic elastomer composition, and more particularly, to a method for producing a thermoplastic elastomer composition that can be produced more simply, with a shorter processing time, and with less energy than conventional production methods.
従来から、耐油性熱可塑性エラストマー組成物として、オレフィン系樹脂、アクリルゴムを含有する混合物を、架橋剤の存在下に動的に熱処理して得られる熱可塑性エラストマー組成物が知られている(例えば、特許文献1参照)。特許文献1には、この熱可塑性エラストマー組成物の製造方法として2つの方法が挙げられている。 Conventionally, as an oil-resistant thermoplastic elastomer composition, a thermoplastic elastomer composition obtained by dynamically heat-treating a mixture containing an olefin resin and acrylic rubber in the presence of a crosslinking agent is known (for example, , See Patent Document 1). Patent Document 1 lists two methods as a method for producing this thermoplastic elastomer composition.
(1)これらの成分のうち、まずアクリルゴム、無機充填剤、更に必要に応じて相容化剤、可塑剤、伸展油、芳香族オリゴマー等をニーダー、バンバリミキサーなどの密閉式混練機に投入し加熱混練し、次いでオレフィン系樹脂を投入して溶融混練した後、押出機にてペレット状に成形する。次に、2軸混練押出機を用いて先に成形したペレット及び動的架橋のための架橋剤あるいはさらに架橋助剤を混練し、加熱溶融しながらアクリルゴムを動的架橋する。 (1) Among these components, first, acrylic rubber, inorganic filler and, if necessary, compatibilizer, plasticizer, extender oil, aromatic oligomer, etc. are charged into a closed kneader such as a kneader or a Banbury mixer. Then, the mixture is heated and kneaded, and then an olefin-based resin is added and melt-kneaded, and then formed into pellets with an extruder. Next, the previously molded pellets and a crosslinking agent for dynamic crosslinking or further a crosslinking aid are kneaded using a biaxial kneading extruder, and the acrylic rubber is dynamically crosslinked while being heated and melted.
(2)まず、2軸混練押出機の第1の投入口より、ペレット状に成形したオレフィン系樹脂を投入し、2軸スクリューによって混合して加熱・溶融する。アクリルゴム、無機充填剤、相溶化剤、可塑剤、伸展油、芳香族オリゴマーはバンバリミキサー等のゴム用混練機を用い、必要に応じて滑剤、補強剤、老化防止剤等を添加して混練した後、架橋系を含まない、いわゆるマスターバッチとし、ゴム用ペレタイザーでペレット化して調製しておく。前記のように、オレフィン系樹脂を2軸混練押出機で加熱・溶融した後、このようにあらかじめペレット化したアクリルゴム、無機充填剤、相溶化剤、可塑剤、伸展油、芳香族オリゴマーを含むゴム成分のペレットを2軸混練押出機の第2の投入口より投入し、オレフィン系樹脂中にゴム成分を分散させる。この後、2軸混練押出機の第3、さらには第4の投入口より架橋剤あるいはさらに架橋助剤を投入し、混練下にアクリルゴムを動的に架橋させる。 (2) First, an olefin-based resin formed into a pellet shape is charged from the first charging port of the twin-screw kneading extruder, mixed with a twin-screw, and heated and melted. Acrylic rubber, inorganic fillers, compatibilizers, plasticizers, extender oils, and aromatic oligomers are kneaded by using a rubber kneader such as a Banbury mixer, and if necessary, adding lubricants, reinforcing agents, anti-aging agents, etc. After that, a so-called master batch containing no crosslinking system is prepared and pelletized with a rubber pelletizer. As mentioned above, after the olefin resin is heated and melted with a twin-screw kneading extruder, it contains acrylic rubber, inorganic filler, compatibilizer, plasticizer, extender oil, aromatic oligomer previously pelletized. The rubber component pellets are charged from the second charging port of the twin-screw kneading extruder to disperse the rubber component in the olefin resin. Thereafter, a cross-linking agent or a cross-linking aid is added from the third and fourth input ports of the twin-screw kneading extruder, and the acrylic rubber is dynamically cross-linked while kneading.
このように、従来の乳化重合ゴムを原料とする熱可塑性エラストマー組成物の製造方法において、架橋剤を用いた動的熱処理の前に各成分を溶融混練後ペレット状へ成形するか、あるいはマスターバッチ化することが必要であった。これは、一般的にアクリルゴムというものがベール状(塊状)で仕上げられ、言い換えると、クラム化が困難又はクラムとしての保持が困難であるという理由による。
従って、従来の方法では、工程が複雑で処理時間がかかり、熱エネルギーおよびコストがかかるという問題がある。
Therefore, the conventional method has a problem that the process is complicated, processing time is required, and heat energy and cost are high.
以上に説明したように、乳化重合ゴムを原料とする熱可塑性エラストマー組成物の製造方法において、従来の製造方法に比べ、より簡潔で処理時間が短く、省エネルギーで低コストな製造方法が要請されている。 As described above, in a method for producing a thermoplastic elastomer composition using an emulsion-polymerized rubber as a raw material, there is a demand for a production method that is simpler, has a shorter processing time, saves energy, and is less expensive than conventional production methods. Yes.
本発明は、上述の課題を解決するべくなされたものであり、従来に比べて簡潔な処理工程で乳化重合ゴムを用いた熱可塑性エラストマー組成物を得ることができる製造方法を提供するものである。 The present invention has been made to solve the above-described problems, and provides a production method capable of obtaining a thermoplastic elastomer composition using an emulsion-polymerized rubber in a simpler process than in the past. .
本発明によれば、(A)熱可塑性樹脂、及び(B)粉末状およびクラム状の乳化重合ゴムを含有する原料組成物を、上流に連続式異方向回転二軸混練機、下流に同方向回転二軸押出機を直列に配設した押出装置の前記連続式異方向回転二軸混練機の原料導入部より供給し、前記連続式異方向回転二軸混練機により前記原料組成物を混合分散させ、前記連続式異方向回転二軸混練機の出口の混練物の温度を250℃以下に保持しながら、前記同方向回転二軸押出機により、架橋剤存在下に動的に熱処理する、熱可塑性エラストマー組成物の製造方法、が提供される。 According to the present invention, a raw material composition containing (A) a thermoplastic resin, and (B) a powdered and crumb-like emulsion polymerized rubber, a continuous different-direction rotating twin-screw kneader upstream, and the same direction downstream Supplied from the raw material introduction part of the continuous different-direction rotating twin-screw kneader of the extruder equipped with a rotating twin-screw extruder in series, and the raw material composition is mixed and dispersed by the continuous different-direction rotating twin-screw kneader. And heat-treating dynamically in the presence of a crosslinking agent by the same-direction rotating twin-screw extruder while maintaining the temperature of the kneaded product at the outlet of the continuous different-direction rotating twin-screw kneader at 250 ° C. or less. A method for producing a plastic elastomer composition is provided.
本発明においては、前記粉末状およびクラム状の乳化重合ゴムが、コアシェル構造(コア部が25℃以下のガラス転移温度(Tg)を有する軟質部、シェル部が25℃を超えるTgを有する硬質部)を有することが好ましく、また、前記粉末状およびクラム状の乳化重合ゴムが、アクリルゴム、アクリロニトリルブタジエンゴム、ブタジエンゴム、及びスチレンブタジエンゴムからなる群から選ばれる少なくとも一つであることが好ましい。さらに、本発明では、前記熱可塑性樹脂が、ポリオレフィン樹脂、ポリアミド樹脂、及びポリエステル樹脂からなる群から選ばれる少なくとも一つであることが好ましい。 In the present invention, the powdered and crumb-like emulsion-polymerized rubber comprises a core-shell structure (a core part having a soft part having a glass transition temperature (Tg) of 25 ° C. or lower, and a shell part having a Tg exceeding 25 ° C. The powdered and crumb emulsion polymerized rubber is preferably at least one selected from the group consisting of acrylic rubber, acrylonitrile butadiene rubber, butadiene rubber, and styrene butadiene rubber. Furthermore, in the present invention, it is preferable that the thermoplastic resin is at least one selected from the group consisting of a polyolefin resin, a polyamide resin, and a polyester resin.
本発明の熱可塑性エラストマー組成物の製造方法は、クラム化が困難でベール状(塊状)で仕上げられる乳化重合ゴムを用いた熱可塑性エラストマー組成物の製造に際して、従来方法に比し、処理工程を簡潔にでき、しかも省エネルギーであるという優れた効果を奏する。 The manufacturing method of the thermoplastic elastomer composition of the present invention is more difficult to crumb and has a processing step as compared with the conventional method in manufacturing a thermoplastic elastomer composition using an emulsion-polymerized rubber that is finished in a bale (lumb shape). It has the excellent effect of being concise and energy saving.
以下、本発明に係る熱可塑性エラストマー組成物の製造方法の実施形態について具体的に説明するが、本発明はこれらの実施形態に限定されるものではない。 Hereinafter, although the embodiment of the manufacturing method of the thermoplastic elastomer composition concerning the present invention is described concretely, the present invention is not limited to these embodiments.
本発明に係る熱可塑性エラストマー組成物の製造方法は、(A)熱可塑性樹脂、及び(B)粉末状またはクラム状の乳化重合ゴムを含有する原料組成物を準備し、この原料組成物を、好ましくは、連続式混練機及び/又は連続式押出機において架橋剤存在下に動的に熱処理することからなる。 The method for producing a thermoplastic elastomer composition according to the present invention comprises (A) a thermoplastic resin, and (B) a raw material composition containing a powdery or crumb-like emulsion-polymerized rubber. Preferably, the heat treatment is performed dynamically in the presence of a crosslinking agent in a continuous kneader and / or a continuous extruder.
まず、本発明に用いる原料組成物及び架橋剤の各成分について説明する。
(A)熱可塑性樹脂:
原料組成物として用いられる(A)熱可塑性樹脂としては、例えば、アミノアクリルアミド重合体、結晶性ポリオレフィン樹脂およびその無水マレイン酸グラフト重合体、非晶性ポリオレフィン樹脂およびその無水マレイン酸グラフト重合体、ポリイソブチレン、エチレン塩化ビニル重合体、エチレンビニルアルコール重合体およびそのアイオノマー、エチレン酢酸ビニル共重合体、ポリエチレンオキサイド、エチレンアクリル酸共重合体、ポリイソブチレンおよびその無水マレイン酸グラフト重合体、塩素化ポリプロピレン、4−メチルペンテン−1樹脂、ポリスチレン、ABS樹脂、ACS樹脂、AS樹脂、AES樹脂、ASA樹脂、MBS樹脂、アクリル樹脂、メタクリル樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、ポリアミド樹脂、ポリカーボネート、アクリル樹脂、メタクリル樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、ビニルアルコール樹脂、ビニルアセタール樹脂、メチルメタアクリレート樹脂、フッ素樹脂、ポリエステル樹脂(ポリエステルエラストマーを含む)、ポリエーテル樹脂、ポリエチレンテレフタレート、ポリアクリル酸エステル、ポリアミド樹脂などが挙げられる。このうち、好ましくは、結晶性ポリオレフィン樹脂、非晶性ポリオレフィン樹脂、ポリアミド樹脂、ポリエステル樹脂(ポリエステルエラストマーを含む)が挙げられる。
First, each component of the raw material composition and the crosslinking agent used in the present invention will be described.
(A) Thermoplastic resin:
Examples of the thermoplastic resin (A) used as the raw material composition include aminoacrylamide polymer, crystalline polyolefin resin and its maleic anhydride graft polymer, amorphous polyolefin resin and its maleic anhydride graft polymer, poly Isobutylene, ethylene vinyl chloride polymer, ethylene vinyl alcohol polymer and its ionomer, ethylene vinyl acetate copolymer, polyethylene oxide, ethylene acrylic acid copolymer, polyisobutylene and its maleic anhydride graft polymer, chlorinated polypropylene, 4 -Methylpentene-1 resin, polystyrene, ABS resin, ACS resin, AS resin, AES resin, ASA resin, MBS resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinylidene chloride resin, polyamide resin Polycarbonate, acrylic resin, methacrylic resin, vinyl chloride resin, vinylidene chloride resin, vinyl alcohol resin, vinyl acetal resin, methyl methacrylate resin, fluororesin, polyester resin (including polyester elastomer), polyether resin, polyethylene terephthalate, polyacryl Examples include acid esters and polyamide resins. Of these, crystalline polyolefin resins, amorphous polyolefin resins, polyamide resins, and polyester resins (including polyester elastomers) are preferable.
(B)粉末状またはクラム状の乳化重合ゴム:
また、原料組成物として用いられる(B)粉末状またはクラム状の乳化重合ゴムとしては、例えば、アクリルゴム、アクリロニトリルブタジエンゴム、ブタジエンゴム、スチレンブタジエンゴムなどが挙げられ、特に、アクリルゴムが好ましい。また、乳化重合で得られるラテックスとしては、コアシェルタイプのゴムが好ましい。アクリルゴムのコアシェルタイプの構造は、アクリル酸アルキルエステル、アクリル酸アルコキシアルキルエステル、共役ジエン系化合物を主成分とする軟質のコア部と、コア表面部分が熱可塑性樹脂を主成分とする硬質のシェル部からなっている。
(B) Powdered or crumb emulsion polymerized rubber:
Examples of the (B) powdered or crumb emulsion polymerization rubber used as the raw material composition include acrylic rubber, acrylonitrile butadiene rubber, butadiene rubber, and styrene butadiene rubber, with acrylic rubber being particularly preferred. The latex obtained by emulsion polymerization is preferably a core-shell type rubber. The core-shell type structure of acrylic rubber consists of a soft core mainly composed of alkyl acrylate ester, alkoxyalkyl acrylate and conjugated diene compound, and a hard shell whose core surface portion is mainly composed of thermoplastic resin. It consists of parts.
前記のようなコアシェル構造にすることで、粉末状あるいはクラム状のゴムが互いに粘着・凝集し合うことなく、その性状を保持したまま、保管、製造時の添加剤ブレンド作業、連続式混練機による生産をすることができ、生産性・経済性に優れた製造方法で熱可塑性エラストマー組成物を得ることができる。 By using the core-shell structure as described above, the powdered or crumb rubbers do not stick and agglomerate with each other, and while maintaining their properties, the additive blending operation during storage and production, using a continuous kneader Production is possible, and a thermoplastic elastomer composition can be obtained by a production method excellent in productivity and economy.
クラムとは、乳化重合したラテックスを凝固、乾燥して得られるクラム状又は粒状のゴムである。クラムサイズとしては、数平均粒子径が5cm以下、より好ましくは4cm以下、更に好ましくは3cm以下である。また、数平均粒子径が通常0.01mm以上、好ましくは0.1mm以上、より好ましくは1mm以上である。数平均粒子径が5cmを超えるクラムでは、熱可塑性エラストマー組成物を製造時に安定的・定量的に連続式混練機及び/又は連続式押出機へ供給することができない恐れがある。
また、粉末状ゴムとは、乳化重合したラテックスを凝固、乾燥したままで得られる状態のものでもよいし、クラムまたはクラムを固めたベールゴムを機械的に砕いたものであってもよい。
A crumb is a crumb-like or granular rubber obtained by coagulating and drying emulsion-polymerized latex. As the crumb size, the number average particle diameter is 5 cm or less, more preferably 4 cm or less, and still more preferably 3 cm or less. The number average particle diameter is usually 0.01 mm or more, preferably 0.1 mm or more, more preferably 1 mm or more. When the number average particle diameter exceeds 5 cm, there is a possibility that the thermoplastic elastomer composition cannot be stably and quantitatively supplied to the continuous kneader and / or the continuous extruder during production.
The powdered rubber may be a state obtained by coagulating and drying an emulsion-polymerized latex, or may be a crumb or a crushed bale rubber mechanically crushed.
以下、乳化重合法によるコアシェル構造を有する乳化重合アクリルゴムについて詳述する。
コア部に用いられる単量体としては、アクリル酸アルキルエステル、アクリル酸アルコキシアルキルエステル、共役ジエン系化合物などが挙げられる。アクリル酸アルキルエステルとしては、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸n−プロピル、アクリル酸イソプロピル、アクリル酸n−ブチル、アクリル酸イソブチル、アクリル酸ベンチル、アクリル酸ヘキシル、アクリル酸ヘプチル、アクリル酸2−エチルヘキシル、アクリル酸オクチル、アクリル酸ノニル、アクリル酸デシルなどを挙げることができ、これらは単独でまたは2種以上組み合わせて用いることができる。この中で、特にアクリル酸エチル、アクリル酸n−ブチルが好ましい。
Hereinafter, the emulsion-polymerized acrylic rubber having a core-shell structure by the emulsion polymerization method will be described in detail.
Examples of the monomer used for the core include acrylic acid alkyl esters, acrylic acid alkoxyalkyl esters, and conjugated diene compounds. Examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, benzyl acrylate, hexyl acrylate, heptyl acrylate and acrylic acid. Examples thereof include 2-ethylhexyl, octyl acrylate, nonyl acrylate, decyl acrylate, and the like, and these can be used alone or in combination of two or more. Among these, ethyl acrylate and n-butyl acrylate are particularly preferable.
アクリル酸アルコキシアルキルエステルとしては、例えばアクリル酸メトキシメチル、アクリル酸メトキシエチル、アクリル酸メトキシプロピル、アクリル酸エトキシメチル、アクリル酸エトキシエチル、アクリル酸エトキシプロピル、アクリル酸ブトキシエチルなどを挙げることができ、これらは単独でまたは2種以上組み合わせて用いることができる。この中で、特にアクリル酸メトキシメチル、アクリル酸メトキシエチル、アクリル酸エトキシメチル、アクリル酸エトキシエチルが好ましい。 Examples of the alkoxyalkyl acrylate include methoxymethyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, ethoxymethyl acrylate, ethoxyethyl acrylate, ethoxypropyl acrylate, butoxyethyl acrylate, and the like. These can be used alone or in combination of two or more. Of these, methoxymethyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, and ethoxyethyl acrylate are particularly preferable.
共役ジエン系化合物としては、例えば1,3−ブタジエン、2−メチル−1,3−ブタジエン(イソプレン)、2,3−ジメチル−1,3−ブタジエン、1,3−ペンタジエン、1,3−ヘキサジエン、ミルセンが挙げられる。 Examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. And myrcene.
さらに必要であれば、これらの単量体と重合可能なその他単量体を共重合してもよい。その他単量体としては、例えばアクリル酸ジヒドロジシクロペンテニル、メタクリル酸ジヒドロジシクロペンテニル、イタコン酸ジヒドロジシクロペンテニル、マレイン酸ジヒドロジシクロペンテニル、フマル酸ジヒドロジシクロペンテニル、アクリル酸ジヒドロジシクロペンテニルオキシエチル(DCPEA)、メタクリル酸ジヒドロジシクロペンテニルオキシエチル、イタコン酸ジヒドロジシクロペンテニルオキシエチル、マレイン酸ジヒドロジシクロペンテニルオキシエチル、フマル酸ジヒドロジシクロペンテニルオキシエチル、メタクリル酸ビニル(CAS No.4245−38−8)、アクリル酸ビニル(CAS No.2177−18−6)、メタクリル酸1,1−ジメチルプロペニル、アクリル酸1,1−ジメチルプロペニル、メタクリル酸3,3−ジメチルブテニル、アクリル酸3,3−ジメチルブテニル、イタコン酸ジビニル、マレイン酸ジビニル、フマル酸ジビニル、ジシクロペンタジエン、メチルジシクロペンタジエン、エチリデンノルボルネン、1,1−ジメチルプロペニルメタクリレート、1,1−ジメチルプロペニルアクリレート、3,3−ジメチルブテニルメタクリレート、3,3−ジメチルブテニルアクリレート、ビニル1,1−ジメチルプロペニルエーテル、ビニル3,3−ジメチルブテニルエーテル、1−アクリロイルオキシ−1−フェニルエテン、1−アクリロイルオキシ−2−フェニルエテン、1−メタクリロイルオキシ−1−フェニルエテン、1−メタクリロイルオキシ−2−フェニルエテンなどを挙げることができる。 If necessary, these monomers and other polymerizable monomers may be copolymerized. Examples of other monomers include dihydrodicyclopentenyl acrylate, dihydrodicyclopentenyl methacrylate, dihydrodicyclopentenyl itaconate, dihydrodicyclopentenyl maleate, dihydrodicyclopentenyl fumarate, dihydrodicyclopentenyl acrylate. Ethyl (DCPEA), dihydrodicyclopentenyloxyethyl methacrylate, dihydrodicyclopentenyloxyethyl itaconate, dihydrodicyclopentenyloxyethyl maleate, dihydrodicyclopentenyloxyethyl fumarate, vinyl methacrylate (CAS No. 4245-) 38-8), vinyl acrylate (CAS No. 2177-18-6), 1,1-dimethylpropenyl methacrylate, 1,1-dimethylpropenyl acrylate 3,3-dimethylbutenyl methacrylate, 3,3-dimethylbutenyl acrylate, divinyl itaconate, divinyl maleate, divinyl fumarate, dicyclopentadiene, methyl dicyclopentadiene, ethylidene norbornene, 1,1-dimethyl Propenyl methacrylate, 1,1-dimethylpropenyl acrylate, 3,3-dimethylbutenyl methacrylate, 3,3-dimethylbutenyl acrylate, vinyl 1,1-dimethylpropenyl ether, vinyl 3,3-dimethylbutenyl ether, 1- Examples include acryloyloxy-1-phenylethene, 1-acryloyloxy-2-phenylethene, 1-methacryloyloxy-1-phenylethene, 1-methacryloyloxy-2-phenylethene, and the like.
また、その他単量体としては、例えばアクリロニトリル、メタクリロニトリル、エタクリロニトリル、α−クロロアクリロニトリル、α−フルオロアクリロニトリルなどを挙げることができる。 Examples of other monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like.
さらに、その他単量体としては、例えばメチルメタクリレート、ベンジルメタクリレート、フェニルメタクリレート、1−メチルシクロヘキシルメタクリレート、シクロヘキシルメタクリレート、クロロベンジルメタクリレート、1−フェニルエチルメタクリレート、1,2−ジフェニルエチルメタクリレート、ジフェニルメチルメタクリレート、フルフリルメタクリレート、1−フェニルシクロヘキシルメタクリレート、ペンタクロロフェニルメタクリレート、ペンタブロモフェニルメタクリレートなどの単官能メタクリレート類;スチレン、ビニルトルエン、ビニルピリジン、α−メチルスチレン、ビニルナフタレン、ハロゲン化スチレン、アクリルアミド、メタクリルアミド、N−メチロールアクリルアミド、酢酸ビニル、塩化ビニル、塩化ビニリデン、脂環式アルコールの(メタ)アクリル酸エステル(例えばアクリル酸シクロヘキシル)、芳香族アルコールの(メタ)アクリル酸エステル(例えばアクリル酸ベンジル)などを挙げることができる。さらにまた、エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、1,4ブタンジオールジ(メタ)アクリレート、1,6ヘキサンジオール−ジ(メタ)アクリレート、トリメチロールプロパン−ジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジビニルベンゼン、ジイソプロペニルベンゼン、トリビニルベンゼン、ヘキサメチレンジ(メタ)アクリレート等の多官能不飽和単量体が挙げられる。 Furthermore, as other monomers, for example, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 1-methylcyclohexyl methacrylate, cyclohexyl methacrylate, chlorobenzyl methacrylate, 1-phenylethyl methacrylate, 1,2-diphenylethyl methacrylate, diphenylmethyl methacrylate, Monofunctional methacrylates such as furfuryl methacrylate, 1-phenylcyclohexyl methacrylate, pentachlorophenyl methacrylate, pentabromophenyl methacrylate; styrene, vinyl toluene, vinyl pyridine, α-methyl styrene, vinyl naphthalene, halogenated styrene, acrylamide, methacrylamide, N-methylolacrylamide, vinyl acetate, vinyl chloride Mention may be made of vinylidene chloride, (meth) acrylic acid esters of alicyclic alcohols (such as cyclohexyl acrylate), and (meth) acrylic acid esters of aromatic alcohols (e.g. benzyl acrylate). Furthermore, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4 butanediol di (meth) acrylate, 1,6 hexanediol-di (meth) acrylate, trimethylolpropane-di (meth) Examples thereof include polyfunctional unsaturated monomers such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, divinylbenzene, diisopropenylbenzene, trivinylbenzene, hexamethylene di (meth) acrylate and the like.
一方、シェル部に用いられる単量体としては、例えば、アクリロニトリル、メタクリロニトリル、エタクリロニトリル、α−クロロアクリロニトリル、α−フルオロアクリロニトリルなどが挙げられる。また、メチルメタクリレート、ベンジルメタクリレート、フェニルメタクリレート、1−メチルシクロヘキシルメタクリレート、シクロヘキシルメタクリレート、クロロベンジルメタクリレート、1−フェニルエチルメタクリレート、1,2−ジフェニルエチルメタクリレート、ジフェニルメチルメタクリレート、フルフリルメタクリレート、1−フェニルシクロヘキシルメタクリレート、ペンタクロロフェニルメタクリレート、ペンタブロモフェニルメタクリレートなどの単官能メタクリレート類;スチレン、ビニルトルエン、ビニルピリジン、α−メチルスチレン、ビニルナフタレン、ハロゲン化スチレン、アクリルアミド、メタクリルアミド、N−メチロールアクリルアミド、酢酸ビニル、塩化ビニル、塩化ビニリデン、脂環式アルコールの(メタ)アクリル酸エステル(例えばアクリル酸シクロヘキシル)、芳香族アルコールの(メタ)アクリル酸エステル(例えばアクリル酸ベンジル)などを挙げることができる。さらにまた、エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、1,4ブタンジオールジ(メタ)アクリレート、1,6ヘキサンジオール−ジ(メタ)アクリレート、トリメチロールプロパン−ジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジビニルベンゼン、ジイソプロペニルベンゼン、トリビニルベンゼン、ヘキサメチレンジ(メタ)アクリレート等の多官能不飽和単量体が挙げられる。これらの成分は単独あるいは2種以上を組み合わせて用いることができる。 On the other hand, examples of the monomer used for the shell portion include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. Further, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 1-methylcyclohexyl methacrylate, cyclohexyl methacrylate, chlorobenzyl methacrylate, 1-phenylethyl methacrylate, 1,2-diphenylethyl methacrylate, diphenylmethyl methacrylate, furfuryl methacrylate, 1-phenylcyclohexyl Monofunctional methacrylates such as methacrylate, pentachlorophenyl methacrylate, pentabromophenyl methacrylate; styrene, vinyl toluene, vinyl pyridine, α-methyl styrene, vinyl naphthalene, halogenated styrene, acrylamide, methacrylamide, N-methylol acrylamide, vinyl acetate, Vinyl chloride, vinylidene chloride, alicyclic alcohol (Meth) acrylic acid ester of Le (e.g. cyclohexyl acrylate), aromatic alcohols (meth) can be mentioned acrylic acid esters (e.g. benzyl acrylate). Furthermore, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4 butanediol di (meth) acrylate, 1,6 hexanediol-di (meth) acrylate, trimethylolpropane-di (meth) Examples thereof include polyfunctional unsaturated monomers such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, divinylbenzene, diisopropenylbenzene, trivinylbenzene, hexamethylene di (meth) acrylate and the like. These components can be used alone or in combination of two or more.
コアシェル構造を有するゴムは、コア部を先に重合し、重合転化率が一定以上になった時点で、シェル部の単量体を途中添加する方法で得ることができる。
なお、上記の重合転化率は50%以上が好ましく、より好ましくは55%以上、更に好ましくは60%以上である。重合転化率が50%未満ではうまくコアシェル構造が形成されない傾向にある。
The rubber having the core-shell structure can be obtained by a method in which the core part is polymerized first and the monomer of the shell part is added halfway when the polymerization conversion rate becomes a certain level or more.
The polymerization conversion rate is preferably 50% or more, more preferably 55% or more, and still more preferably 60% or more. If the polymerization conversion is less than 50%, the core-shell structure tends not to be formed well.
(B)粉末状またはクラム状の乳化重合ゴムにおけるコア部とシェル部の割合については、コア部の(B)成分全体(ゴム全体)に占める割合として、重合時に使用する単量体の重量比で50〜95重量%が好ましく、55〜90重量%がさらに好ましい。その割合が50重量%未満では、得られる熱可塑性エラストマー組成物のゴム弾性が劣る傾向にある。一方、95重量%を超えると、乳化重合後に凝固した粉末あるいはクラム状のゴムが粘着・凝集する傾向にある。 (B) About the ratio of the core part and shell part in powder-form or crumb-form emulsion polymerization rubber, as a ratio which occupies the whole (B) component (all rubber | gum) of a core part, the weight ratio of the monomer used at the time of superposition | polymerization Is preferably 50 to 95% by weight, more preferably 55 to 90% by weight. If the proportion is less than 50% by weight, the rubber elasticity of the resulting thermoplastic elastomer composition tends to be inferior. On the other hand, if it exceeds 95% by weight, the powder or crumb-like rubber solidified after emulsion polymerization tends to adhere and aggregate.
コア部のTgは25℃以下、好ましくは20℃以下、更に好ましくは15℃以下である。コア部のTgが25℃を超えるとゴム弾性に劣る傾向にあり好ましくない。シェル部のTgは25℃を超え、好ましくは30℃以上、更に好ましくは35℃以上である。一方、シェル部のTgが25℃以下では、クラムが粘着して熱可塑性エラストマーの生産性が悪化する傾向にある。 The Tg of the core part is 25 ° C. or lower, preferably 20 ° C. or lower, more preferably 15 ° C. or lower. If the Tg of the core exceeds 25 ° C, the rubber elasticity tends to be inferior, which is not preferable. The Tg of the shell portion exceeds 25 ° C., preferably 30 ° C. or higher, more preferably 35 ° C. or higher. On the other hand, when the Tg of the shell part is 25 ° C. or less, the crumbs adhere and the productivity of the thermoplastic elastomer tends to deteriorate.
上記した(A)成分の熱可塑性樹脂と(B)成分である乳化重合ゴムとの配合割合は、(A)成分と(B)成分の合計量を100重量%とした場合、(B)成分が好ましくは30〜95重量%、さらに好ましくは40〜93重量%、特に好ましくは50〜90重量%である。(B)成分である乳化重合ゴムの配合割合が30重量%未満の場合にはゴム弾性が劣る傾向にあり、一方、(B)成分の乳化重合ゴムの配合割合が95重量%を超えると、成形加工性が劣る傾向にある。 The blending ratio of the thermoplastic resin of the component (A) and the emulsion polymerized rubber as the component (B) is as follows when the total amount of the component (A) and the component (B) is 100% by weight. Is preferably 30 to 95% by weight, more preferably 40 to 93% by weight, and particularly preferably 50 to 90% by weight. When the blending ratio of the emulsion polymerized rubber as the component (B) is less than 30% by weight, the rubber elasticity tends to be inferior. On the other hand, when the blending ratio of the emulsion polymerized rubber as the component (B) exceeds 95% by weight, Molding processability tends to be inferior.
架橋剤:
本発明において使用される架橋剤は、上記熱可塑性樹脂の融点以上の温度における動的熱処理により、組成物中の少なくとも1種の(B)成分である乳化重合ゴムを架橋し得る化合物である。このような架橋物としては、分子中に2重結合を有する高分子化合物を架橋することができる架橋剤であれば特に制限はないが、例えば、硫黄、有機含硫黄化合物、有機過酸化物、樹脂、キノン誘導体、ポリハロゲン化物、ビス(ジオキソトリアゾリン)誘導体、アルデヒド、エポキシ化合物、アミン−ボランコンプレックス、双極性化合物が挙げられる。さらに、白金触媒の存在下、ヒドロシリル化反応による白金架橋に使用されるメチルハイドロジェンシロキサンが挙げられる。これらの架橋剤の中で、硫黄、有機含硫黄化合物、有機過酸化物、メチルハイドロジェンシロキサンが好ましく、有機過酸化物がさらに好ましい。架橋剤は、単独でまたは2種以上を混合して使用することができる。これらの架橋剤の使用量は、通常、本発明の(B)成分である乳化重合ゴム100重量部に対して0.1〜20重量部、好ましくは1〜10重量部である。
Cross-linking agent:
The cross-linking agent used in the present invention is a compound capable of cross-linking the emulsion-polymerized rubber that is at least one component (B) in the composition by dynamic heat treatment at a temperature equal to or higher than the melting point of the thermoplastic resin. Such a crosslinked product is not particularly limited as long as it is a crosslinking agent capable of crosslinking a polymer compound having a double bond in the molecule. For example, sulfur, an organic sulfur-containing compound, an organic peroxide, Examples include resins, quinone derivatives, polyhalides, bis (dioxotriazoline) derivatives, aldehydes, epoxy compounds, amine-borane complexes, and bipolar compounds. Furthermore, methyl hydrogen siloxane used for platinum bridge | crosslinking by hydrosilylation reaction in presence of a platinum catalyst is mentioned. Among these crosslinking agents, sulfur, organic sulfur-containing compounds, organic peroxides, and methylhydrogensiloxane are preferable, and organic peroxides are more preferable. A crosslinking agent can be used individually or in mixture of 2 or more types. The amount of these crosslinking agents to be used is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the emulsion polymerization rubber which is the component (B) of the present invention.
有機過酸化物としては、1分半減期(半減期が1分間)を得るための分解温度が150℃以上のものが好ましい。具体的には、1,1−ビス(t−ブチルパーオキシ)シクロヘキサン、2,2−ビス(4,4−ジ−t−ブチルパーオキシシクロヘキシル)プロパン、1,1−ビス(t−ブチルパーオキシ)シクロドデカン、t−ヘキシルパーオキシイソプロピルモノカーボネート、t−ブチルパーオキシマレイン酸、t−ブチルパーオキシ−3,5,5−トリメチルヘキサノエイト、t−ブチルパーオキシラウレイト、2,5−ジメチル−2,5−ジ(m−トルオイルパーオキシ)ヘキサン、t−ブチルパーオキシイソプロピルモノカーボネート、t−ブチルパーオキシ2−エチルヘキシルモノカーボネート、t−ヘキシルパーオキシベンゾエイト、2,5−ジメチル−2,5−ジ(ベンゾイルパーオキシ)ヘキサン、t−ブチルパーオキシアセテイト、2,2−ビス(t−ブチルパーオキシ)ブタン、t−ブチルパーオキシベンゾエイト、n−ブチル−4.4−ビス(t−ブチルパーオキシ)バレレイト、ジ−t−ブチルパーオキシイソフタレイト、α,α′ビス(t−ブチルパーオキシ)ジイソプロピルベンゼン、ジクミルパーオキサイド、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン、t−ブチルクミルパーオキサイド、ジ−t−ブチルパーオキサイド、p−メンタンヒドロパーオキサイド、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキシン−3、ジイソプロピルベンゼンヒドロパーオキサイド、t−ブチルトリメチルシリルパーオキサイド、1,1,3,3−テトラメチルブチルヒドロパーオキサイド、クメンヒドロパーオキサイド、t−ヘキシルヒドロパーオキサイド、t−ブチルヒドロパーオキサイド等が挙げられる。有機過酸化物の添加量は、本発明の(B)成分である乳化重合ゴム100重量部に対して0.3〜15重量部、好ましくは0.5〜10重量部である。有機過酸化物の添加量が0.3重量部未満の場合には、架橋時間が極めて長くなる上、架橋が不十分になる傾向がある。添加量が15重量部を超える場合には、架橋物が硬くなり、脆くなる傾向にある。 As the organic peroxide, those having a decomposition temperature of 150 ° C. or higher for obtaining a half-life of 1 minute (half-life of 1 minute) are preferable. Specifically, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) Oxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5 -Dimethyl-2,5-di (m-toluoyl peroxy) hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5- Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, , 2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4.4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t -Butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1 , 3,3-Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl Mud peroxide, t- butyl hydroperoxide, and the like. The addition amount of the organic peroxide is 0.3 to 15 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the emulsion polymerized rubber as the component (B) of the present invention. When the addition amount of the organic peroxide is less than 0.3 parts by weight, the crosslinking time becomes extremely long and the crosslinking tends to be insufficient. When the addition amount exceeds 15 parts by weight, the cross-linked product tends to be hard and brittle.
上記有機過酸化物は、単独でまたは2種以上を混合して使用することができる。本発明においては、上記有機過酸化物を適当な架橋助剤と併用することにより、均一かつ穏やかな架橋反応を行うことができる。このような架橋助剤としては、例えば粉末硫黄、コロイド硫黄、沈降硫黄、不溶性硫黄、表面処理硫黄、ジペンタメチレンチウラムテトラスルフィドなどの硫黄あるいは硫黄化合物;p−キノンオキシム、p,p′−ジベンゾイルキノンオキシム等のオキシム化合物;エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジアリルフタレート、テトラアリルオキシエタン、トリアリルシアヌレート、N,N′−m−フェニレンビスマレイミド、N,N′−トルイレンビスマレイミド、無水マレイン酸、ジビニルベンゼン、ジ(メタ)アクリル酸亜鉛等の多官能性モノマー類等を挙げることができる。これらの架橋助剤のうち、p,p′−ジベンゾイルキノンオキシム、N,N′−m−フェニレンビスマレイミド、ジビニルベンゼンが好ましい。なお、N,N′−m−フェニレンビスマレイミドは、単独でも架橋剤として作用しうるものである。上記架橋助剤は、単独でまたは2種以上を混合して使用することができる。架橋助剤の使用量は、(B)成分100重量部に対して0〜20重量部、好ましくは1〜10重量部である。架橋剤として硫黄を使用する場合には、メルカプトベンゾチアゾールなどのチアゾール類、テトラメチルチウラムジスルフィドなどのチウラム類、ジフェニルグアニジンなどのグアニジン類、ジメチルジチオカルバミン酸亜鉛などのジチオカルバミン酸塩などが架橋促進剤として有効に使用できる。架橋剤として有機含硫黄化合物を使用する場合には、例えばチウラム系促進剤であるテトラメチルチウラムジスルフィドや4,4′−ジチオモルホリンなどが架橋促進剤として有効に使用できる。これらの架橋促進剤の使用量は、通常、(B)成分100重量部に対して0.1〜20重量部、好ましくは1〜10重量部である。 The said organic peroxide can be used individually or in mixture of 2 or more types. In the present invention, a uniform and gentle crosslinking reaction can be performed by using the organic peroxide in combination with an appropriate crosslinking aid. Examples of such a crosslinking aid include sulfur or sulfur compounds such as powdered sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur, dipentamethylene thiuram tetrasulfide; p-quinone oxime, p, p'-di Oxime compounds such as benzoylquinone oxime; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, N, N'-m-phenylene bismaleimide, N, N'-toluylene bismaleimide, anhydrous Can be mentioned in acid, divinylbenzene, di (meth) polyfunctional monomers such as zinc acrylate and the like. Of these crosslinking aids, p, p'-dibenzoylquinone oxime, N, N'-m-phenylenebismaleimide, and divinylbenzene are preferred. N, N′-m-phenylenebismaleimide alone can act as a crosslinking agent. The crosslinking aids can be used alone or in admixture of two or more. The usage-amount of a crosslinking adjuvant is 0-20 weight part with respect to 100 weight part of (B) component, Preferably it is 1-10 weight part. When sulfur is used as a crosslinking agent, thiazoles such as mercaptobenzothiazole, thiurams such as tetramethylthiuram disulfide, guanidines such as diphenylguanidine, dithiocarbamates such as zinc dimethyldithiocarbamate, etc. are used as crosslinking accelerators. Can be used effectively. When an organic sulfur-containing compound is used as the crosslinking agent, for example, tetramethylthiuram disulfide or 4,4′-dithiomorpholine, which is a thiuram accelerator, can be effectively used as the crosslinking accelerator. The amount of these crosslinking accelerators used is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight per 100 parts by weight of component (B).
他の配合成分:
尚、本発明の熱可塑性エラストマー組成物の製造方法においては、上記(A)成分及び(B)成分のほかに、相溶化剤、可塑剤、フィラー(無機充填剤)、伸展油等が配合される。さらに、その他の添加剤として、芳香族オリゴマー、加工助剤、補強剤、伸展油以外の軟化剤、老化防止剤などを、熱可塑性エラストマー組成物の性能を阻害しない範囲内で適量配合することができる。
Other ingredients:
In addition, in the manufacturing method of the thermoplastic elastomer composition of the present invention, a compatibilizer, a plasticizer, a filler (inorganic filler), an extender oil and the like are blended in addition to the component (A) and the component (B). The Furthermore, as other additives, an appropriate amount of aromatic oligomer, processing aid, reinforcing agent, softening agent other than extender oil, anti-aging agent, etc. may be blended within a range that does not impair the performance of the thermoplastic elastomer composition. it can.
相容化剤:
(A)成分の熱可塑性樹脂及び(B)成分の乳化重合ゴムとは本来難相容系あるいは非相容系であることがあり、その場合、この両成分と似通った構造を持つ相容化剤を配合することが好ましい。本発明における相容化剤としては、溶解度パラメータ(SP値)が(A)成分の熱可塑性樹脂(SP値:7〜8)と(B)成分の乳化重合ゴム(SP値:9〜10)との中間にある重合体、具体的には、溶解度パラメータ(SP値)が7.2〜9.5の範囲にある重合体が好ましく用いられる。なお、ここで用いるSP値は、ポリマーハンドブック第2版(Polymer Handbook;Second Edition;BRADRUP編)の第339頁に記載のHOYの方法で計算したものである。
非極性の熱可塑性樹脂と極性のゴム、あるいは極性の熱可塑性樹脂と非極性のゴムの組み合わせの場合、相容化剤を用いることが好ましい。
相容化剤としては、例えば、エチレン−アクリル酸エステル共重合体、官能基含有ポリオレフィン、ポリオレフィン−グリコール(メタ)アクリレート、低ニトリル含有アクリロニトリル−ブタジエンゴムまたはその水添物、スチレン−ブタジエンブロック共重合体又はその水添物、スチレン−イソプレンブロック共重合体又はその水添物、スチレン−ブタジエンゴム、ブタジエンゴム、イソプレンゴム、エピクロルヒドリンゴム、クロロプレンゴム、塩素化エチレン・α−オレフィン共重合体、エチレン・ビニルエステル共重合体、クロロスルホン化ポリエチレンや、特開2003−277571号公報に記載されているグラフト重合体などが挙げられる。この中で、特にエチレン−アクリル酸エステル共重合体、官能基含有ポリオレフィンおよびポリオレフィン−グリコール(メタ)アクリレートからなる群から選ばれる少なくとも1種が好ましい。
Compatibilizer:
The thermoplastic resin of component (A) and the emulsion polymerized rubber of component (B) may be inherently incompatible or non-compatible, and in that case, they have a structure similar to these components. It is preferable to mix an agent. As a compatibilizing agent in the present invention, a thermoplastic resin (SP value: 7 to 8) having a solubility parameter (SP value) of component (A) and an emulsion polymerization rubber of component (B) (SP value: 9 to 10) And a polymer having a solubility parameter (SP value) in the range of 7.2 to 9.5 is preferably used. The SP value used here is calculated by the HOY method described on page 339 of Polymer Handbook 2nd edition (Polymer Handbook; Second Edition; BRADRUP).
In the case of a combination of a nonpolar thermoplastic resin and a polar rubber, or a combination of a polar thermoplastic resin and a nonpolar rubber, it is preferable to use a compatibilizing agent.
Examples of the compatibilizer include ethylene-acrylic acid ester copolymer, functional group-containing polyolefin, polyolefin-glycol (meth) acrylate, low nitrile-containing acrylonitrile-butadiene rubber or hydrogenated product thereof, and styrene-butadiene block copolymer. Copolymer or hydrogenated product thereof, styrene-isoprene block copolymer or hydrogenated product thereof, styrene-butadiene rubber, butadiene rubber, isoprene rubber, epichlorohydrin rubber, chloroprene rubber, chlorinated ethylene / α-olefin copolymer, ethylene Examples thereof include vinyl ester copolymers, chlorosulfonated polyethylene, and graft polymers described in JP-A No. 2003-277571. Among these, at least one selected from the group consisting of ethylene-acrylic acid ester copolymers, functional group-containing polyolefins, and polyolefin-glycol (meth) acrylates is particularly preferable.
エチレン−アクリル酸エステル共重合体としては、エチレンを必須成分とし、炭素原子数が1〜8のアルキル基を有するアルキルアクリレート、炭素原子数が1〜4のアルコキシ基および炭素原子数が1〜4のアルキレン基を有するアルコキシアルキルアクリレートからなる群より選ばれる少なくとも1種のアクリル酸エステル単量体からなる共重合体が挙げられる。また、エチレンとアクリル酸エステルおよび酢酸ビニルを主骨格とした共重合体、またはエチレンとアクリル酸エステルおよび架橋点としてのカルボキシル基含有単量体および/またはエポキシ基含有単量体との共重合体が挙げられる。この共重合体には前記の単量体と共重合しうる他の共重合性単量体、例えばアクリロニトリル等が共重合されたものでもよい。 As an ethylene-acrylic acid ester copolymer, ethylene is an essential component, an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. And a copolymer comprising at least one acrylate monomer selected from the group consisting of alkoxyalkyl acrylates having the following alkylene groups. Also, a copolymer of ethylene and an acrylic ester and vinyl acetate as a main skeleton, or a copolymer of ethylene and an acrylic ester and a carboxyl group-containing monomer and / or an epoxy group-containing monomer as a crosslinking point Is mentioned. This copolymer may be copolymerized with another copolymerizable monomer that can be copolymerized with the above monomer, such as acrylonitrile.
その具体例は、エチレン−アクリル酸メチル共重合体、エチレン−アクリル酸メチル−アクリル酸共重合体、エチレン−アクリル酸メチル−メタアクリル酸共重合体等のカルボキシル基含有単量体との共重合体、エチレン−アクリル酸メチル−グリシジルメタアクリレート共重合体、エチレン−アクリル酸メチル−グリシジルアクリレート共重合体、エチレン−アクリル酸メチル−アリルグリシジルエーテル共重合体等のエポキシ基含有単量体との共重合体、エチレン−アルキルアクリレート−酢酸ビニル共重合体、エチレン−アルキルアクリレート−酢酸ビニル−グリシジルメタアクリレート共重合体、エチレン−アルキルアクリレート−酢酸ビニル−グリシジルアクリレート共重合体、エチレン−アルキルアクリレート−酢酸ビニル−アリルグリシジルエーテル共重合体等のエポキシ基含有単量体との共重合体などが挙げられる。共重合体の分子量は、数平均分子量で3,000〜500,000が望ましい。さらに好ましくは、ムーニー粘度[ML1+4(100℃)]で10〜150のものを用いると良い。これらのエチレン−アクリル酸エステル共重合体は単独あるいは2種以上を用いることができる。 Specific examples thereof include copolymerization with a carboxyl group-containing monomer such as ethylene-methyl acrylate copolymer, ethylene-methyl acrylate-acrylic acid copolymer, ethylene-methyl acrylate-methacrylic acid copolymer, etc. Copolymers, copolymers with epoxy group-containing monomers such as ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl acrylate copolymer, ethylene-methyl acrylate-allyl glycidyl ether copolymer, etc. Polymer, ethylene-alkyl acrylate-vinyl acetate copolymer, ethylene-alkyl acrylate-vinyl acetate-glycidyl methacrylate copolymer, ethylene-alkyl acrylate-vinyl acetate-glycidyl acrylate copolymer, ethylene-alkyl acrylate-vinyl acetate -A And a copolymer of glycidyl ether copolymer and epoxy group-containing monomers can be mentioned. The molecular weight of the copolymer is preferably 3,000 to 500,000 in terms of number average molecular weight. More preferably, a Mooney viscosity [ML 1 + 4 (100 ° C.)] of 10 to 150 is used. These ethylene-acrylic acid ester copolymers can be used alone or in combination of two or more.
官能基含有ポリオレフィンとは、ポリオレフィン系樹脂又はポリオレフィン系ゴムを、官能基によって変性したポリマーを意味する。ポリオレフィン系樹脂又はポリオレフィン系ゴムは、α−オレフィンを主体として重合された樹脂又はゴムである。α−オレフィンとしては、エチレン、プロピレン、1−ブテン、4−メチル−1−ブテン、4−メチル−1−ペンテンなどが挙げられ、好ましくはエチレン、プロピレンである。これらのα−オレフィンは単独でまたは2種以上を組み合わせて使用することができる。また、ポリオレフィン系ゴムとしては、エチレン−プロピレンゴム、エチレン−プロピレン−ジエンゴムが挙げられる。官能基としては、好ましくはエポキシ基、カルボキシル基、酸無水物、および水酸基からなる群から選ばれる少なくとも1種が挙げられる。例えば、グリシジルメタアクリレート、グリシジルアクリレート、ビニルグリシジルエーテル、アリルグリシジルエーテル等の不飽和エポキシド等でグラフト変性した官能基含有ポリオレフィンが挙げられる。また、変性に用いられる官能基含有化合物の具体例としては、マレイン酸、フマル酸、イタコン酸、シトラコン酸、アリルコハク酸、無水マレイン酸、無水フマル酸、無水イタコン酸などであり、好ましくは無水マレイン酸である。変性方法としては、ポリオレフィン樹脂又はポリオレフィン系ゴムを、アルキル芳香族炭化水素溶媒中、115℃以上の温度でラジカル開始剤を用い、上記官能基含有化合物をグラフトさせる方法、あるいは極小量のアルキル過酸化物、好ましくは脂肪族の2官能性過酸化物、官能基含有化合物、ならびにポリオレフィン樹脂及び/又はポリオレフィン系ゴムを、200℃以上の温度で混練りする方法などが挙げられる。官能基含有ポリオレフィンの具体例としては、無水マレイン酸変性LDPE(低密度ポリエチレン)、無水マレイン酸変性HDPE(高密度ポリエチレン)、無水マレイン酸変性LLDPE(直鎖低密度ポリエチレン)、無水マレイン酸変性EVA(エチレン−酢酸ビニル共重合体)、無水マレイン酸変性PP(ポリプロピレン)などであり、好ましくは無水マレイン酸変性LLDPEである。 The functional group-containing polyolefin means a polymer obtained by modifying a polyolefin resin or polyolefin rubber with a functional group. The polyolefin-based resin or the polyolefin-based rubber is a resin or rubber polymerized mainly with α-olefin. Examples of the α-olefin include ethylene, propylene, 1-butene, 4-methyl-1-butene, 4-methyl-1-pentene, and preferably ethylene and propylene. These α-olefins can be used alone or in combination of two or more. Examples of the polyolefin rubber include ethylene-propylene rubber and ethylene-propylene-diene rubber. The functional group is preferably at least one selected from the group consisting of an epoxy group, a carboxyl group, an acid anhydride, and a hydroxyl group. Examples thereof include functional group-containing polyolefins graft-modified with unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, and allyl glycidyl ether. Specific examples of the functional group-containing compound used for the modification include maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, maleic anhydride, fumaric anhydride, itaconic anhydride, preferably maleic anhydride. It is an acid. As a modification method, a polyolefin resin or a polyolefin-based rubber is grafted onto the functional group-containing compound using a radical initiator at a temperature of 115 ° C. or higher in an alkyl aromatic hydrocarbon solvent, or a minimal amount of alkyl peroxidation. And a method of kneading a product, preferably an aliphatic bifunctional peroxide, a functional group-containing compound, and a polyolefin resin and / or polyolefin rubber at a temperature of 200 ° C. or higher. Specific examples of the functional group-containing polyolefin include maleic anhydride modified LDPE (low density polyethylene), maleic anhydride modified HDPE (high density polyethylene), maleic anhydride modified LLDPE (linear low density polyethylene), maleic anhydride modified EVA. (Ethylene-vinyl acetate copolymer), maleic anhydride-modified PP (polypropylene), etc., preferably maleic anhydride-modified LLDPE.
ポリオレフィン−グリコール(メタ)アクリレートとしては、ポリプロピレングリコールモノ(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリエチレングリコールポリプロピレングリコールモノ(メタ)アクリレート、メトキシポリエチレングリコールモノ(メタ)アクリレート、エトキシポリエチレングリコールモノ(メタ)アクリレート、メトキシポリプロピレングリコールモノ(メタ)アクリレート、エトキシポリプロピレングリコールモノ(メタ)アクリレート等を挙げることができる。これらは単独あるいは2種以上用いることができる。なお、ポリオレフィングリコールの重合度は2〜10である。 Polyolefin-glycol (meth) acrylates include polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, ethoxypolyethylene glycol mono ( Examples include meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, and ethoxypolypropylene glycol mono (meth) acrylate. These may be used alone or in combination of two or more. In addition, the polymerization degree of polyolefin glycol is 2-10.
相容化剤の添加量は、(A)成分と(B)成分の合計量100重量部に対して、0〜20重量部、好ましくは0.5〜18重量部、さらに好ましくは1〜15重量部である。相容化剤の添加量が20重量部を超えると、得られる熱可塑性エラストマー組成物の柔軟性の指標である圧縮永久歪が悪化する傾向にある。 The addition amount of the compatibilizer is 0 to 20 parts by weight, preferably 0.5 to 18 parts by weight, more preferably 1 to 15 parts per 100 parts by weight of the total amount of the components (A) and (B). Parts by weight. When the addition amount of the compatibilizer exceeds 20 parts by weight, compression set, which is an index of flexibility of the obtained thermoplastic elastomer composition, tends to deteriorate.
可塑剤:
可塑剤としては、ゴム組成物の通常の可塑剤が使用できるが、耐熱性に優れた可塑剤が好ましく、例えば耐熱性に優れたエーテル系、エーテルエステル系、トリメリット酸系可塑剤が挙げられる。エーテル系可塑剤としては、脂肪族ジカルボン酸にアルコキシポリオキシエチレンアルコールを縮合させたものが挙げられる。具体的には、旭電化工業社製のアデカサイザーRS−705、大日本インキ化学工業社製のモノサイザーW−264等が該当する。エーテルエステル系可塑剤としては、その製造方法としては特に限定されるものではないが、2−エチルヘキシル酸とエーテルグリコールとをモル比2:1で反応させることにより容易に得られるものであり、例えば、ペンタエチレングリコール、ヘキサエチレングリコールあるいはヘプタエチレングリコールなどを所定量含む混合エーテルグリコールと2−エチルヘキシル酸とを常法により反応させて得ることができるが、ペンタエチレングリコール、ヘキサエチレングリコールあるいはヘプタエチレングリコール等をそれぞれ別々に2−エチルヘキシル酸と常法により反応させて得られたジエステルを用いたポリエチレングリコール平均重合度が5〜10となるように混合することによっても製造できる。具体的には、旭電化工業社製のアデカサイザーRS−107、RS−1000、RS−735、RS−700等が該当する。トリメリット酸系可塑剤としては、トリメリット酸の3つのカルボン酸がそれぞれアルコールと縮合してなるトリメリット酸エステルが挙げられる。例えば、トリメリット酸トリメチル、トリメリット酸トリエチル、トリメリット酸トリプロピル、トリメリット酸トリブチル、トリメリット酸トリアミル、トリメリット酸トリヘキシル、トリメリット酸トリヘプチル、トリメリット酸トリn−オクチル、トリメリット酸トリ−2−エチルヘキシル、トリメリット酸トリノニル、トリメリット酸トリス(デシル)、トリメリット酸トリス(ドデシル)、トリメリット酸トリス(テトラデシル)、トリメリット酸トリス(C8〜C12混合アルキル)、トリメリット酸トリス(C7〜C9混合アルキル)、トリメリット酸トリラウリル等が挙げられる。具体的には、旭電化工業社製のアデカサイザーC−8、C−880、C−79、C−810、C−9N、C−10等が該当する。これらの可塑剤の分子量は好ましくは400〜1000である。可塑剤の分子量が400未満では耐熱性が不十分であり、1000を超えると耐寒性、圧縮永久歪が劣り、好ましくない。可塑剤は単独または2種以上を併用することができる。この可塑剤は、熱可塑性エラストマー組成物製造時に(A)成分と(B)成分に添加しても良いし、予め(B)成分に添加しても良い。可塑剤の配合量は、(A)成分と(B)成分の合計量100重量部あたり、0〜100重量部とすることができ、好ましくは5〜70重量部、より好ましくは10〜50重量部である。可塑剤の配合量が100重量部を超えると、最終的に得られる熱可塑性エラストマー組成物から可塑剤がブリードアウトし、機械的強度及びゴム弾性が低下する傾向にある。
Plasticizer:
As the plasticizer, a normal plasticizer of a rubber composition can be used, but a plasticizer excellent in heat resistance is preferable, and examples thereof include ether-based, ether ester-based, trimellitic acid-based plasticizers excellent in heat resistance. . Examples of the ether plasticizer include those obtained by condensing an alkoxy dioxyethylene alcohol with an aliphatic dicarboxylic acid. Specifically, Adeka Sizer RS-705 manufactured by Asahi Denka Kogyo Co., Ltd. and Monosizer W-264 manufactured by Dainippon Ink & Chemicals, Inc. are applicable. The ether ester plasticizer is not particularly limited as its production method, but can be easily obtained by reacting 2-ethylhexyl acid and ether glycol in a molar ratio of 2: 1. , Pentaethylene glycol, hexaethylene glycol or heptaethylene glycol can be obtained by reacting a mixed ether glycol containing a predetermined amount of 2-ethylenehexyl acid with 2-ethylhexylic acid by a conventional method. Etc., respectively, can be produced by mixing them so that the average polymerization degree of polyethylene glycol is 5 to 10 using diesters obtained by reacting each of them with 2-ethylhexylic acid by a conventional method. Specifically, Adekasizer RS-107, RS-1000, RS-735, RS-700, etc. manufactured by Asahi Denka Kogyo Co., Ltd. are applicable. Examples of trimellitic acid plasticizers include trimellitic acid esters obtained by condensing three carboxylic acids of trimellitic acid with alcohols. For example, trimethyl trimellitic acid, triethyl trimellitic acid, tripropyl trimellitic acid, tributyl trimellitic acid, triamyl trimellitic acid, trihexyl trimellitic acid, triheptyl trimellitic acid, tri-n-octyl trimellitic acid, trimellitic acid trimethyl 2-ethylhexyl, trinonyl trimellitic acid, tris trimellitic acid (decyl), tris trimellitic acid (dodecyl), tris trimellitic acid (tetradecyl), tris trimellitic acid (C8-C12 mixed alkyl), tris trimellitic acid (C7-C9 mixed alkyl), trilauryl trimellitic acid and the like. Specifically, Adekasizer C-8, C-880, C-79, C-810, C-9N, C-10, etc. manufactured by Asahi Denka Kogyo Co., Ltd. are applicable. The molecular weight of these plasticizers is preferably 400 to 1000. When the molecular weight of the plasticizer is less than 400, the heat resistance is insufficient, and when it exceeds 1000, the cold resistance and compression set are inferior. The plasticizers can be used alone or in combination of two or more. This plasticizer may be added to the component (A) and the component (B) during the production of the thermoplastic elastomer composition, or may be added to the component (B) in advance. The compounding amount of the plasticizer can be 0 to 100 parts by weight, preferably 5 to 70 parts by weight, more preferably 10 to 50 parts by weight per 100 parts by weight of the total amount of the component (A) and the component (B). Part. When the blending amount of the plasticizer exceeds 100 parts by weight, the plasticizer bleeds out from the finally obtained thermoplastic elastomer composition, and the mechanical strength and rubber elasticity tend to decrease.
フィラー(無機充填剤):
本発明で用いるフィラー(無機充填剤)としては、通常のゴム組成物の無機充填剤を使用することができ、例えば、シリカ、重質炭酸カルシウム、胡粉、軽微性炭酸カルシウム、極微細活性化炭酸カルシウム、特殊炭酸カルシウム、塩基性炭酸マグネシウム、カオリンクレー、焼成クレー、パイロフライトクレー、シラン処理クレー、合成ケイ酸カルシウム、合成ケイ酸マグネシウム、合成ケイ酸アルミニウム、炭酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム、酸化マグネシウム、カオリン、セリサイト、タルク、微粉タルク、ウォラスナイト、ゼオライト、ベントナイト、マイカ、アスベスト、PMF(Processed Mineral Fiber)、セピオライト、チタン酸カリウム、エレスタダイト、石膏繊維、ガラスバルン、シリカバルン、ハイドロタルサイト、フライアシュバルン、シラスバルン、カーボン系バルン、アルミナ、硫酸バリウム、硫酸アルミニウム、硫酸カルシウム、二硫化モリブデン等GA挙げられる。これらは単独でまたは2種以上を併用して使用することができる。この中で、吸油性が高いことから特にシリカが好ましい。
Filler (inorganic filler):
As the filler (inorganic filler) used in the present invention, an inorganic filler of a normal rubber composition can be used. For example, silica, heavy calcium carbonate, hum powder, light calcium carbonate, ultrafine activated carbonic acid Calcium, special calcium carbonate, basic magnesium carbonate, kaolin clay, calcined clay, pyroflight clay, silanized clay, synthetic calcium silicate, synthetic magnesium silicate, synthetic aluminum silicate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide , Magnesium oxide, kaolin, sericite, talc, fine talc, wollastonite, zeolite, bentonite, mica, asbestos, PMF (Processed Mineral Fiber), sepiolite, potassium titanate, elastadite, gypsum fiber, gauze Subarun, Shirikabarun, hydrotalcite, fly ash balloon, Shirasubarun, carbon-based balloon, alumina, barium sulfate, aluminum sulfate, calcium sulfate, and GA molybdenum disulfide. These can be used alone or in combination of two or more. Of these, silica is particularly preferred because of its high oil absorption.
フィラー(無機充填剤)の添加量は、(A)成分と(B)成分の合計量100重量部に対して、0〜100重量部、好ましくは0.5〜90重量部、さらに好ましくは1〜80重量部である。フィラーの添加量が100重量部を超えると、粘度が過度に高くなり、あるいは得られる熱可塑性エラストマー組成物の柔軟性の指標である圧縮永久歪が大きくなり好ましくない。 The addition amount of the filler (inorganic filler) is 0 to 100 parts by weight, preferably 0.5 to 90 parts by weight, more preferably 1 with respect to 100 parts by weight of the total amount of the components (A) and (B). ~ 80 parts by weight. When the added amount of the filler exceeds 100 parts by weight, the viscosity becomes excessively high, or the compression set, which is an index of flexibility of the obtained thermoplastic elastomer composition, becomes unfavorable.
伸展油:
伸展油としては、通常ゴム組成物に使用される伸展油を用いることができるが、アロマティック系およびナフテン系伸展油が好ましい。特に、ASTM D3238−95(2000年再承認)記載のn−d−M法による環分析のアロマ炭素(CA%)、ナフテン炭素(CN%)、パラフィン炭素(CP%)がそれぞれ3〜60、20〜50、0〜60(但しCA+CN+CP=100)であることがより好ましい。CPが60%を超えると、熱可塑性エラストマー組成物の機械的強度及び熱可塑性エラストマー組成物を用いた成形品の表面肌が不良になることがある。伸展油の配合量は、(A)成分と(B)成分の合計量100重量部あたり、0〜100重量部、好ましくは1〜90重量部である。伸展油の添加量が100重量部を超えると、得られる熱可塑性エラストマー組成物の柔軟性の指標である圧縮永久歪が大きくなり好ましくない。
Extension oil:
As the extender oil, an extender oil usually used in a rubber composition can be used, and aromatic and naphthenic extender oils are preferable. In particular, aroma carbon (CA%), naphthene carbon (CN%), and paraffin carbon (CP%) of ring analysis by ndM method described in ASTM D3238-95 (reapproved in 2000) are 3 to 60, respectively. It is more preferable that it is 20-50, 0-60 (however, CA + CN + CP = 100). When CP exceeds 60%, the mechanical strength of the thermoplastic elastomer composition and the surface skin of the molded article using the thermoplastic elastomer composition may be poor. The amount of the extender oil is 0 to 100 parts by weight, preferably 1 to 90 parts by weight, per 100 parts by weight of the total amount of the component (A) and the component (B). When the amount of the extender oil exceeds 100 parts by weight, the compression set, which is an index of the flexibility of the thermoplastic elastomer composition obtained, is undesirably increased.
その他の添加剤:
芳香族オリゴマーとしては、重量平均分子量(GPC法、ポリスチレン換算)が200から10,000程度のものであればよく、例えば芳香族環骨格主体の樹脂が挙げられ、その具体例としては、クマロンインデン樹脂、キシレン樹脂、フェノールノボラック樹脂、スチレン化フェノール樹脂、ナフタレン樹脂などが挙げられ、この中で、クマロンインデン樹脂、ナフタレン樹脂が好ましい。芳香族オリゴマーの重量平均分子量が200未満では、成形品の機械的強度が不足し、10,000を超えると混練性が悪化する。芳香族オリゴマーの配合量は、(A)成分と(B)成分の合計量100重量部あたり、0〜20重量部、好ましくは1〜10重量部である。配合量が20重量部を超えると、粘着性が強くなり混練性が悪化することがある。
Other additives:
As the aromatic oligomer, it is sufficient that the weight average molecular weight (GPC method, polystyrene conversion) is about 200 to 10,000. Examples include aromatic ring skeleton-based resins, and specific examples thereof include coumarone. Indene resin, xylene resin, phenol novolac resin, styrenated phenol resin, naphthalene resin and the like can be mentioned. Among these, coumarone indene resin and naphthalene resin are preferable. If the weight average molecular weight of the aromatic oligomer is less than 200, the mechanical strength of the molded product is insufficient, and if it exceeds 10,000, the kneadability deteriorates. The compounding amount of the aromatic oligomer is 0 to 20 parts by weight, preferably 1 to 10 parts by weight per 100 parts by weight of the total amount of the component (A) and the component (B). When the blending amount exceeds 20 parts by weight, the tackiness becomes strong and the kneading property may be deteriorated.
加工助剤としては、例えば滑剤、金属酸化物、アミン類、脂肪酸とその誘導体などが挙げられる。滑剤としては、例えば、ステアリン酸、オレイン酸、ラウリル酸、ジブチルアンモニウム・オレート、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸カリウム、ステアリン酸ナトリウム、ステアリルアミン等を挙げることができる。これらは単独でまたは2種以上を混合して使用することができる。 Examples of processing aids include lubricants, metal oxides, amines, fatty acids and derivatives thereof. Examples of the lubricant include stearic acid, oleic acid, lauric acid, dibutylammonium oleate, zinc stearate, calcium stearate, potassium stearate, sodium stearate, stearylamine and the like. These can be used alone or in admixture of two or more.
金属酸化物としては、例えば、亜鉛華、活性亜鉛華、表面処理亜鉛華、炭酸亜鉛、複合亜鉛華、複合活性亜鉛華、表面処理酸化マグネシウム、酸化マグネシウム、水酸化カルシウム、極微細水酸化カルシウム、一酸化鉛、鉛丹、鉛白等を挙げることができる。これらは単独でまたは2種以上を混合して使用することができる。 Examples of the metal oxide include zinc white, activated zinc white, surface-treated zinc white, zinc carbonate, composite zinc white, composite active zinc white, surface-treated magnesium oxide, magnesium oxide, calcium hydroxide, ultrafine calcium hydroxide, Examples thereof include lead monoxide, red lead, and white lead. These can be used alone or in admixture of two or more.
軟化剤としては、上記した伸展油以外の石油系軟化剤、植物油系軟化剤、サブを挙げることができる。植物系軟化剤は、ひまし油、綿実油、あまに油、なたね油、大豆油、パーム油、やし油、落花生油、木ろう等を挙げることができる。サブとしては、黒サブ、白サブ、飴サブ等を挙げることができる。 Examples of the softener include petroleum softeners other than the above-described extender oil, vegetable oil softeners, and sub. Examples of plant softeners include castor oil, cottonseed oil, sesame oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, and wax. Examples of the sub include a black sub, a white sub, and a dark blue sub.
老化防止剤としては、ナフチルアミン系、ジフェニルアミン系、p−フェニレンジアミン系、キノリン系、ヒドロキノン誘導体系、モノ、ビス、トリス、ポリフェノール系、チオビスフェノール系、ヒンダートフェノール系、亜リン酸エステル系、イミダゾール系、ジチオカルバミン酸ニッケル塩系、リン酸系の老化防止剤等を挙げることができる。これらは単独あるいは2種以上を混合して用いることができる。 Antiaging agents include naphthylamine, diphenylamine, p-phenylenediamine, quinoline, hydroquinone derivative, mono, bis, tris, polyphenol, thiobisphenol, hindered phenol, phosphite, imidazole And anti-aging agents such as nickel, dithiocarbamic acid nickel salt and phosphoric acid. These can be used alone or in admixture of two or more.
補強剤としては、例えばカーボンブラックがあり、具体的にはSAFカーボンブラック、ISAFカーボンブラック、HAFカーボンブラック、FEFカーボンブラック、GPFカーボンブラック、SRFカーボンブラック、FTカーボンブラック、MTカーボンブラック、アセチレンカーボンブラック、ケッチェンブラック等を挙げることができる。これらは単独あるいは2種以上を混合して用いることができる。 Examples of the reinforcing agent include carbon black, specifically, SAF carbon black, ISAF carbon black, HAF carbon black, FEF carbon black, GPF carbon black, SRF carbon black, FT carbon black, MT carbon black, acetylene carbon black. And ketjen black. These can be used alone or in admixture of two or more.
熱可塑性エラストマー組成物の製造方法:
本発明に係る熱可塑性エラストマー組成物の製造方法は、以上に説明してきた(A)熱可塑性樹脂、及び(B)乳化重合ゴムを少なくとも含み、好ましくはさらに相容化剤、可塑剤、フィラー、伸展油及びその他の添加剤などを含有する原料組成物を、好ましくは、連続式混練機に導入して混練りした後、架橋剤存在下に動的に熱処理することから構成されている。すなわち、原料組成物を連続式混練機及び/又は連続式押出機において混合分散する混合分散工程と、この混合分散工程で得られる混練物を架橋剤存在下に動的に架橋する(動的に熱処理する)架橋工程を連続して行うものである。
ここで、上記「動的熱処理」とは、剪断力を加えること及び加熱することの両方を行うことをいう。この動的熱処理は、例えば、溶融混練装置である連続式混練機及び/又は連続式押出機を用いて行うことができる。
Method for producing thermoplastic elastomer composition:
The method for producing a thermoplastic elastomer composition according to the present invention comprises at least (A) a thermoplastic resin and (B) an emulsion-polymerized rubber as described above, and preferably further comprises a compatibilizer, a plasticizer, a filler, The raw material composition containing the extending oil and other additives is preferably introduced into a continuous kneader and kneaded, and then dynamically heat-treated in the presence of a crosslinking agent. That is, a mixing and dispersing step in which the raw material composition is mixed and dispersed in a continuous kneader and / or a continuous extruder, and the kneaded product obtained in this mixing and dispersing step is dynamically crosslinked in the presence of a crosslinking agent (dynamically A heat treatment) is performed continuously.
Here, the “dynamic heat treatment” refers to both applying a shearing force and heating. This dynamic heat treatment can be performed using, for example, a continuous kneader and / or a continuous extruder that is a melt kneader.
本発明に係る熱可塑性エラストマー組成物の製造方法のより好ましい方法としては、(A)熱可塑性樹脂、(B)粉末状およびクラム状の乳化重合ゴム、及び好ましくは相溶化剤、可塑剤、フィラー、伸展油及びその他の添加剤などを含有する原料組成物を、上流に連続式異方向回転二軸混練機、下流に同方向回転二軸押出機を直列に配設した押出装置の前記連続式異方向回転二軸混練機の原料導入部より供給し、前記連続式異方向回転二軸混練機により前記原料組成物を混合分散させ、前記連続式異方向回転二軸混練機の出口の混練物の温度を250℃以下に保持しながら、前記同方向回転二軸押出機により、架橋剤存在下に動的に熱処理することが挙げられる。 As a more preferable method for producing the thermoplastic elastomer composition according to the present invention, (A) a thermoplastic resin, (B) a powdery and crumb-like emulsion polymerized rubber, and preferably a compatibilizer, a plasticizer, and a filler The continuous type of extrusion apparatus in which a raw material composition containing an extending oil and other additives is arranged in series with a continuous different-direction rotating twin-screw kneader upstream and a same-direction rotating twin-screw extruder downstream. Supply from the raw material introduction part of the different-direction rotating twin-screw kneader, mix and disperse the raw material composition with the continuous different-direction rotating twin-screw kneader, and kneaded at the outlet of the continuous different-direction rotating twin-screw kneader It is possible to dynamically heat-treat in the presence of a cross-linking agent by the same-direction rotating twin-screw extruder while maintaining the temperature at 250 ° C. or lower.
この製造方法においては、押出装置の上流側に配設された連続式異方向回転二軸混練機中で、供給された原料組成物の溶融混練り、及び架橋剤の混合分散を行い、一定温度以下に制御した混練物を同方向回転二軸押出機に供給し、動的架橋反応を完了させるものである。連続式異方向回転二軸混練機の出口における混練物の温度は、用いる熱可塑性樹脂及び架橋剤によって異なるが、連続式異方向回転二軸混練機中で架橋反応の進行を抑制した状態で原料組成物の溶融混練りを行える温度に制御する必要があるため、また、原料組成物中の(A)熱可塑性樹脂及び(B)乳化重合ゴムの劣化を防ぐために、250℃以下に保持することが好ましく、240℃以下に保持することがさらに好ましい。 In this production method, in a continuous different-direction rotating twin-screw kneader disposed upstream of the extrusion apparatus, the supplied raw material composition is melt-kneaded and the crosslinking agent is mixed and dispersed at a constant temperature. The kneaded material controlled below is supplied to the same direction rotating twin screw extruder to complete the dynamic crosslinking reaction. The temperature of the kneaded material at the outlet of the continuous different-direction rotating biaxial kneader varies depending on the thermoplastic resin and the crosslinking agent used, but the raw material is kept in a state where the progress of the crosslinking reaction is suppressed in the continuous different-direction rotating biaxial kneader. Since it is necessary to control the temperature at which the composition can be melt-kneaded, and in order to prevent deterioration of the (A) thermoplastic resin and (B) emulsion-polymerized rubber in the raw material composition, the temperature should be kept at 250 ° C. or lower. Is preferable, and it is more preferable to hold at 240 ° C. or lower.
本発明で用いる押出装置の上流側に配設する連続式異方向回転二軸混練機としては特に限定されないが、例えば、日本製鋼所社製CIM、神戸製鋼所社製ミクストロンFCM/NCM/LCM/ACM(いずれも商標)等を挙げることができる。 Although it does not specifically limit as a continuous different direction rotation biaxial kneading machine arrange | positioned in the upstream of the extrusion apparatus used by this invention, For example, Nippon Steel Works CIM, Kobe Steel Works Mixtron FCM / NCM / LCM / ACM (both are trademarks) and the like.
また、本発明で用いる押出装置の上流側に配設する同方向回転二軸押出機としては特に限定されないが、L/D(スクリュー有効長Lと外径Dとの比)が好ましくは30以上、より好ましくは36〜60である二軸押出機を用いることが好ましい。
二軸押出機としては、例えば2本のスクリューが噛み合うもの、噛み合わないもの等、任意の二軸押出機を使用することができる。このような二軸押出機としては池貝社製GT、同PCM、神戸製鋼所社製KTX、日本製鋼所社製TEX、東芝機械社製TEM、ワーナー社製ZSK(いずれも商標)等が挙げられる。
The co-rotating twin-screw extruder disposed on the upstream side of the extrusion apparatus used in the present invention is not particularly limited, but L / D (ratio of effective screw length L to outer diameter D) is preferably 30 or more. It is preferable to use a twin screw extruder that is more preferably 36-60.
As the twin-screw extruder, for example, an arbitrary twin-screw extruder such as one in which two screws mesh or not mesh can be used. Examples of such a twin-screw extruder include GT manufactured by Ikegai Co., Ltd., PCM, KTX manufactured by Kobe Steel Co., Ltd., TEX manufactured by Nippon Steel Co., Ltd., TEM manufactured by Toshiba Machine Co., Ltd., and ZSK manufactured by Warner Co., Ltd. (both are trademarks). .
本発明において、(A)成分及び(B)成分(及び相溶化剤)以外の架橋剤、フィラー、可塑剤、軟化剤等の供給方法としては特に限定されず、上記原料組成物中及び/又は上記混合分散工程の途中において配合させることができ、具体的には、(i)ブレンドミキサーを用いて架橋反応に供される上記原料組成物と予め混合して上記連続式異方向回転二軸混練機に供給する方法、(ii)上記連続式異方向回転二軸混練機のフィードホッパーから供給する方法などがある。また、(iii)上記連続式異方向回転二軸混練機のフィードホッパーと混練機の出口との間に設けられたバレル開口部から供給してもよい。 In the present invention, the supply method of the crosslinking agent, filler, plasticizer, softener and the like other than the components (A) and (B) (and the compatibilizer) is not particularly limited, and / or in the raw material composition and / or Specifically, it can be blended in the middle of the mixing and dispersing step. Specifically, (i) the continuous different-direction rotating biaxial kneading is previously mixed with the raw material composition to be subjected to the crosslinking reaction using a blend mixer. And (ii) a method of supplying from a feed hopper of the continuous different-direction rotating twin-screw kneader. Moreover, (iii) You may supply from the barrel opening part provided between the feed hopper of the said continuous type opposite direction rotation biaxial kneader and the exit of a kneader.
上記のような連続式異方向回転二軸混練機と同方向回転二軸押出機とを連結した装置で、熱可塑性エラストマー組成物を製造する場合、軟化剤、フィラー(充填剤)等の供給方法としては特に限定されず、(i)ブレンドミキサーを用いて架橋反応に供される乳化重合ゴム及び熱可塑性樹脂と予め混合して連続式異方向回転二軸混練機に供給する方法、(ii)連続式異方向回転二軸混練機、同方向回転二軸押出機、あるいは両方のフィードホッパーから供給する方法、(iii)連続式異方向回転二軸混練機、同方向回転二軸押出機、あるいは両方のフィードホッパーとダイとの間に設けられたバレル開口部から供給する方法、(iv)サイドフィーダーを用いて同方向回転二軸押出機に供給する方法等が挙げられる。 When a thermoplastic elastomer composition is produced with an apparatus in which a continuous different-direction rotating twin-screw kneader and a same-direction rotating twin-screw extruder are connected as described above, a method of supplying a softener, filler (filler), etc. (I) A method of pre-mixing with an emulsion polymerization rubber and a thermoplastic resin to be subjected to a crosslinking reaction using a blend mixer and supplying the mixture to a continuous different-direction rotating twin-screw kneader, (ii) A method of feeding from a continuous different-direction rotating twin-screw kneader, a same-direction rotating twin-screw extruder, or both feed hoppers, (iii) a continuous different-direction rotating twin-screw kneader, a same-direction rotating twin-screw extruder, or Examples thereof include a method of supplying from a barrel opening provided between both feed hoppers and a die, and (iv) a method of supplying to a co-rotating twin screw extruder using a side feeder.
以下、実施例によって本発明をさらに具体的に説明するが、本発明はこれらの実施例によって何ら制限を受けるものではない。
なお、実施例、比較例中の部及び%は、特に断らない限り重量基準である。また、実施例、比較例中の各種測定は、下記の方法に拠った。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
In addition, the part and% in an Example and a comparative example are a basis of weight unless there is particular notice. Various measurements in the examples and comparative examples were based on the following methods.
(熱可塑性エラストマー組成物の調製)
以下に示すオレフィン樹脂、アクリルゴム、無機充填剤、可塑剤、架橋剤、伸展油,その他添加剤を用いた。
(Preparation of thermoplastic elastomer composition)
The following olefin resin, acrylic rubber, inorganic filler, plasticizer, crosslinking agent, extender oil, and other additives were used.
(A)ポリオレフィン樹脂
ポリプロピレン重合体「PP1」:密度0.90g/cm3、MFR(温度230℃、荷重21N)3g/10min、日本ポリケム社製、品名「ノバテックPP MA4」
(A) Polyolefin resin Polypropylene polymer “PP1”: density 0.90 g / cm 3 , MFR (temperature 230 ° C., load 21 N) 3 g / 10 min, manufactured by Nippon Polychem Co., Ltd., product name “Novatech PP MA4”
(B)乳化重合コアシェル型アクリルゴム
以下の記載の方法によりアクリルゴムを合成した。
(B−1)ANM1
窒素置換されたオートクレーブ内に、イオン交換水200部を入れ、さらにアクリル酸エチル(EA)33.4部、メトキシエチルアクリレート(MEA)33.4部、アクリロニトリル(AN)10部、アクリル酸ジヒドロジシクロペンテニルオキシエチル(DCPEA)3.2部からなる単量体混合物80部と、ラウリル酸ナトリウム4部と、p−メンタンハイドロパーオキサイド0.04部と、硫酸第一鉄0.01部と、エチレンジアミン四酢酸ナトリウム0.025部と、ソジウムホルムアルデヒドスルホキシレート0.04部とを仕込み、反応温度15℃で乳化重合させた。重合転化率が90%になったところで、メチルメタクリレート(MMA)13部、AN6.2部、DCPEA0.8部を仕込み、引き続き重合させた。重合転化率がほぼ100%に達したところで、N,N−ジエチルヒドロキシルアミン0.5部を反応系に添加して共重合反応を停止させた(反応時間7時間)。次いで、反応生成物(ラテックス)を取り出し、反応生成物に塩化カルシウム水溶液(0.25%)を添加して不飽和基含有アクリルゴムを凝固させた。この凝固物を十分に水洗した後、約90℃で3〜4時間乾燥させることにより、ムーニー粘度[ML1+4(100℃)]45のクラム状の不飽和基含有アクリルゴム(これをANM1とする)を得た。
(B) Emulsion polymerization core-shell type acrylic rubber Acrylic rubber was synthesized by the following method.
(B-1) ANM1
In a nitrogen-substituted autoclave, 200 parts of ion-exchanged water are added, and 33.4 parts of ethyl acrylate (EA), 33.4 parts of methoxyethyl acrylate (MEA), 10 parts of acrylonitrile (AN), dihydrodiacrylate 80 parts of a monomer mixture consisting of 3.2 parts of cyclopentenyloxyethyl (DCPEA), 4 parts of sodium laurate, 0.04 parts of p-menthane hydroperoxide, 0.01 parts of ferrous sulfate, 0.025 part of sodium ethylenediaminetetraacetate and 0.04 part of sodium formaldehyde sulfoxylate were charged and emulsion polymerization was carried out at a reaction temperature of 15 ° C. When the polymerization conversion reached 90%, 13 parts of methyl methacrylate (MMA), 6.2 parts of AN, and 0.8 part of DCPEA were charged, followed by polymerization. When the polymerization conversion reached almost 100%, 0.5 part of N, N-diethylhydroxylamine was added to the reaction system to stop the copolymerization reaction (reaction time 7 hours). Next, the reaction product (latex) was taken out, and an aqueous calcium chloride solution (0.25%) was added to the reaction product to coagulate the unsaturated group-containing acrylic rubber. The coagulated product was thoroughly washed with water and then dried at about 90 ° C. for 3 to 4 hours to obtain a crumb-like unsaturated group-containing acrylic rubber having a Mooney viscosity [ML 1 + 4 (100 ° C.)] 45 (this was ANM1 And).
(C)無機充填剤
シリカ:東ソー・シリカ社製、品名「ニプシールNS」
(D)架橋剤
2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン:日本油脂社製、品名「パーヘキサ25B−40」
(E)可塑剤
エーテルエステル系可塑剤:旭電化工業社製、品名「アデカサイザーRS1000」
(F)伸展油:富士興産社製、品名「フッコールFLEX#2050N」
n−d−M法による分析値はCA6%、CN39%、CP55%。
(C) Inorganic filler Silica: manufactured by Tosoh Silica Co., Ltd., product name “Nipsil NS”
(D) Crosslinking agent 2,5-dimethyl-2,5-di (t-butylperoxy) hexane: manufactured by NOF Corporation, product name “Perhexa 25B-40”
(E) Plasticizer Ether ester plasticizer: Asahi Denka Kogyo Co., Ltd., product name “Adeka Sizer RS1000”
(F) Extension oil: manufactured by Fuji Kosan Co., Ltd., product name “Fukkor FLEX # 2050N”
The analytical values by the ndM method are CA 6%, CN 39%, CP 55%.
その他添加剤
架橋助剤(1):三共化成社製、品名「ジビニルベンゼン(純度56%)」
老化防止剤(1):4,4′−ビス(α,α−ジメチルベンジル)ジフェニルアミン、大内新興化学工業社製、品名「ノクラックCD」
加工助剤(1):花王社製、品名「ステアリン酸」
シランカップリング剤:GE東芝シリコーン社製、品名「TSL8370」
Other additives Crosslinking aid (1): Sankyo Chemical Co., Ltd., product name “divinylbenzene (purity 56%)”
Anti-aging agent (1): 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., product name “NOCRACK CD”
Processing aid (1): Product name “Stearic acid” manufactured by Kao Corporation
Silane coupling agent: GE Toshiba Silicone, product name “TSL8370”
実施例1
ANMクラム、架橋剤、架橋助剤、加工助剤及び老化防止剤をヘンシェルミキサーを用いて30秒間混合して添加剤混合ANMクラムを得た。また、フィラー、シランカップリング剤、可塑剤および伸展油をヘンシェルミキサーを用いて30秒間混合して液体添加剤混合フィラーを得た。連続式異方向回転二軸混練機(異方向噛み合い型2ローター、L/D=10、商品名「ミクストロンLCM」、神戸製鋼所社製)の後に同方向回転二軸押出機(同方向非噛み合い型スクリュー、L/D=42、商品名「TEX44αII」、日本製鋼所社製)を連結した装置に表2に示す配合割合で、3台(1台は添加剤混合ANMクラム用、1台は液体添加剤混合フィラー用、1台はポリオレフィン樹脂用)の重量式フィーダー(商品名「KF−C88」、クボタ社製)を用いて吐出量40kg/hで上記連続式異方向二軸混練機の原料導入口より供給し、シリンダー温度80℃、ローター回転数500rpm、ゲート開度30%、オリフィス開度100%で溶融混練りを行った。次いで、溶融状態の組成物を上記連続式異方向回転二軸混練機に直結された同方向二軸押出機に供給し、シリンダー温度設定200℃、スクリュー回転数400rpmで動的熱処理による架橋反応を施して、熱可塑性エラストマー組成物を得た。
実施例1は、40kgの熱可塑性エラストマー組成物を得るのに、連続式異方向回転二軸混練機と連続式同方向二軸押出機を直結した装置で溶融混練り作業に1時間を要した。
Example 1
The ANM crumb, the crosslinking agent, the crosslinking aid, the processing aid and the anti-aging agent were mixed for 30 seconds using a Henschel mixer to obtain an additive mixed ANM crumb. Further, a filler, a silane coupling agent, a plasticizer and an extending oil were mixed for 30 seconds using a Henschel mixer to obtain a liquid additive mixed filler. Continuous-direction bi-axial kneader (Di-directional meshing type 2-rotor, L / D = 10, trade name “Mixtron LCM”, manufactured by Kobe Steel, Ltd.) followed by co-rotating twin-screw extruder (co-directional non-meshing) 3 units (1 unit is for additive-mixed ANM crumbs) with the mixing ratio shown in Table 2 to the device connected with the mold screw, L / D = 42, trade name “TEX44αII”, manufactured by Nippon Steel Works Co., Ltd. For the liquid additive mixed filler, one of the above-described continuous different-direction twin-screw kneaders with a discharge rate of 40 kg / h using a weight type feeder (product name “KF-C88”, manufactured by Kubota Corp.) It was supplied from the raw material inlet and melt-kneaded at a cylinder temperature of 80 ° C., a rotor rotation speed of 500 rpm, a gate opening of 30%, and an orifice opening of 100%. Next, the molten composition is supplied to the same-direction twin screw extruder directly connected to the above-described continuous different-direction rotating twin-screw kneader, and subjected to a crosslinking reaction by dynamic heat treatment at a cylinder temperature setting of 200 ° C. and a screw rotation speed of 400 rpm. To obtain a thermoplastic elastomer composition.
In Example 1, it took 1 hour for the melt-kneading work in an apparatus in which a continuous different-direction rotating twin-screw kneader and a continuous same-direction twin-screw extruder were directly connected to obtain 40 kg of the thermoplastic elastomer composition. .
実施例2
ANMクラム、粉末NBR(相容化材)、架橋剤、架橋助剤、加工助剤及び老化防止剤をヘンシェルミキサーを用いて30秒間混合して添加剤混合ANMクラムを得た。二軸押出機(同方向非噛み合い型スクリュー、L/D=38.5、商品名「TEX44αII」、日本製鋼所社製)に表2に示す配合割合で、3台(1台は添加剤混合ANMクラム用、1台は液体添加剤混合フィラー用、1台はポリオレフィン系樹脂用)の重量式フィーダー(商品名「KF−C88」、クボタ社製)を用いて、吐出量40kg/hで供給し、シリンダー温度設定200℃、スクリュー回転数400rpmで動的熱処理を施しながら押出を行い、熱可塑性エラストマー組成物を得た。
実施例2は、40kgの熱可塑性エラストマー組成物を得るのに、連続式同方向二軸押出機で溶融混練り作業に1時間を要した。
Example 2
ANM crumb, powder NBR (compatibilizer), crosslinking agent, crosslinking aid, processing aid and anti-aging agent were mixed for 30 seconds using a Henschel mixer to obtain an additive-mixed ANM crumb. In the twin screw extruder (same direction non-meshing screw, L / D = 38.5, trade name “TEX44αII”, manufactured by Nippon Steel Works), 3 units (1 unit is additive mixed) Supplied at a discharge rate of 40 kg / h using a weight type feeder (trade name “KF-C88”, manufactured by Kubota) for ANM crumb, one for liquid additive mixed filler and one for polyolefin resin Then, extrusion was performed while performing dynamic heat treatment at a cylinder temperature setting of 200 ° C. and a screw rotation speed of 400 rpm, to obtain a thermoplastic elastomer composition.
In Example 2, it took 1 hour for the melt-kneading operation with a continuous co-directional twin-screw extruder to obtain 40 kg of the thermoplastic elastomer composition.
比較例1
バッチ式ミキサーおよび連続式混練機の多段工程を用いて熱可塑性エラストマー組成物を製造した。具体的には、表2に示す配合割合に従い、ANMクラム、ポリオレフィン樹脂、フィラー、可塑剤、伸展油、シランカップリング剤、加工助剤、老化防止剤を160℃に加熱した10リッター双腕型加圧ニーダー(モリヤマ社製)に7kgの上記した全配合を表2の比率で投入し、40rpmで15分間混練りした。その後、溶融状態の組成物を180℃、40rpmに設定したフィーダールーダー(モリヤマ社製)にて15分間かけてペレット化した。
Comparative Example 1
A thermoplastic elastomer composition was produced using a multistage process of a batch mixer and a continuous kneader. Specifically, according to the mixing ratio shown in Table 2, a 10-liter double-arm type in which ANM crumb, polyolefin resin, filler, plasticizer, extender oil, silane coupling agent, processing aid, and anti-aging agent were heated to 160 ° C. In a pressure kneader (manufactured by Moriyama Co., Ltd.), 7 kg of the above total formulation was charged at the ratio shown in Table 2, and kneaded at 40 rpm for 15 minutes. Thereafter, the molten composition was pelletized with a feeder ruder (manufactured by Moriyama Corporation) set at 180 ° C. and 40 rpm for 15 minutes.
更に、得られたペレット物に、架橋剤として、「パーヘキサ25B−40」を1重量部、架橋助剤としてジビニルベンゼン(純度56%)2重量部(ジビニルベンゼンとして5重量部)を配合し、ヘンシェルミキサーにて30秒混合し、二軸押出機(同方向非噛み合い型スクリュー、L/D=38.5、商品名「TEX44αII」、日本製鋼所社製)に表2に示す配合割合で、1台の重量式フィーダー(商品名「KF−C88」、クボタ社製)を用いて、吐出量40kg/hrで供給し、シリンダー温度設定200℃、スクリュー回転数400rpmで動的熱処理を施しながら押出を行い、熱可塑性エラストマー組成物を得た。
比較例1は、40kgの熱可塑性エラストマー組成物を得るのに、10リッター双腕型加圧ニーダーとフィーダールーダー作業に3時間、連続式同方向二軸押出機で溶融混練り作業に1時間、合計4時間を要した。また、実施例1,2と比較して、比較例1は混練作業が困難であり、時間単位当たりの消費エネルギー量が多く、作業全体では数倍以上のエネルギーを要した。
Furthermore, 1 part by weight of “Perhexa 25B-40” as a crosslinking agent and 2 parts by weight of divinylbenzene (purity 56%) as a crosslinking aid (5 parts by weight as divinylbenzene) are blended in the obtained pellets. Mixing for 30 seconds with a Henschel mixer, the mixing ratio shown in Table 2 in a twin-screw extruder (same direction non-meshing screw, L / D = 38.5, trade name “TEX44αII”, manufactured by Nippon Steel) Using a single heavy-weight feeder (trade name “KF-C88”, manufactured by Kubota), supply at a discharge rate of 40 kg / hr, and extrude while performing dynamic heat treatment at a cylinder temperature setting of 200 ° C. and a screw rotation speed of 400 rpm. To obtain a thermoplastic elastomer composition.
In Comparative Example 1, to obtain a 40 kg thermoplastic elastomer composition, 3 hours for a 10 liter double arm type pressure kneader and feeder ruder work, 1 hour for melt kneading work with a continuous co-directional twin screw extruder, It took 4 hours in total. Further, compared with Examples 1 and 2, in Comparative Example 1, the kneading work was difficult, the amount of energy consumed per unit of time was large, and the entire work required several times more energy.
熱可塑性エラストマーの試験片作製
得られた熱可塑性エラストマーのペレットを射出成形機(商品名N−100、日本製鋼所社製)を用いて射出成形を行い、厚み2mm、長さ120mm、幅120mmのシートを作製し各種評価に供した。
Test piece preparation of thermoplastic elastomer The obtained thermoplastic elastomer pellets were injection molded using an injection molding machine (trade name N-100, manufactured by Nippon Steel Co., Ltd.), and had a thickness of 2 mm, a length of 120 mm, and a width of 120 mm. Sheets were prepared and subjected to various evaluations.
熱可塑性エラストマーの評価
得られた熱可塑性エラストマーの成形シートを用いて、硬度、機械的物性(引張破断強度、引張破断伸び)、及び耐油性を下記方法により各々評価し、表2に記した。
(1)硬度:柔軟性の指標としてJIS−K6253に準拠して測定した。
(2)引張破断強度及び引張破断伸び:JIS−K6251に準拠して測定した。
(3)耐油性:JIS−K6258に準拠し、FuelC試験油を用い23℃、70時間浸漬試験による体積変化率(ΔV)を求めた。
(4)耐熱性:JIS−K6257に準拠し、ギヤーオーブン中に150℃、70時間放置後、引張試験を行い、引張破断強度の変化率(Ac(TB))及び引張破断伸びの変化率(Ac(EB))を測定した。
(5)圧縮永久歪:JIS−K6262に準拠し、120℃、22時間、25%圧縮後の値を測定した。
(6)低温試験:JIS−K6261に準拠し、−20℃の条件下で衝撃脆化試験を行い、異常の有無を調べた。
(7)耐候性:JIS−K6259に準拠し、オゾン濃度500pphm、40℃、200時間、静的40%伸張の条件で評価し、亀裂の有無を調べた。
Evaluation of Thermoplastic Elastomer Using the obtained thermoplastic elastomer molded sheet, hardness, mechanical properties (tensile rupture strength, tensile rupture elongation), and oil resistance were evaluated by the following methods, respectively.
(1) Hardness: Measured according to JIS-K6253 as an index of flexibility.
(2) Tensile breaking strength and tensile breaking elongation: measured in accordance with JIS-K6251.
(3) Oil resistance: Based on JIS-K6258, the volume change rate (ΔV) was determined by immersion test at 23 ° C. for 70 hours using Fuel C test oil.
(4) Heat resistance: In accordance with JIS-K6257, after leaving in a gear oven at 150 ° C. for 70 hours, a tensile test was performed, and the rate of change in tensile strength (Ac (T B )) and the rate of change in tensile elongation at break (Ac (E B )) was measured.
(5) Compression set: Based on JIS-K6262, the value after compression at 120 ° C. for 22 hours and 25% was measured.
(6) Low temperature test: In accordance with JIS-K6261, an impact embrittlement test was conducted under the condition of −20 ° C. to examine the presence or absence of abnormality.
(7) Weather resistance: In accordance with JIS-K6259, evaluation was made under conditions of ozone concentration 500 pphm, 40 ° C., 200 hours, static 40% elongation, and the presence or absence of cracks was examined.
得られた熱可塑性エラストマー組成物の評価結果を表2に示す。 Table 2 shows the evaluation results of the obtained thermoplastic elastomer composition.
本発明の製造方法により得られる熱可塑性エラストマー組成物は、耐熱老化性、耐候性、耐油性に優れるため、耐油性、耐候性を必要とする、例えば、燃料油、潤滑油系耐油性ホース、オイルクーラーホース、エアーダストホース、パワーステアリングホース、コントロールホース、インタークーラーホース、トルコンホース、オイルリターンホース、バキュームセンシングホース、耐熱ホースなどの各種ホース材に好適に用いることができる。 The thermoplastic elastomer composition obtained by the production method of the present invention is excellent in heat aging resistance, weather resistance, and oil resistance, and therefore requires oil resistance and weather resistance, for example, fuel oil, lubricating oil-based oil resistant hose, It can be suitably used for various hose materials such as oil cooler hose, air dust hose, power steering hose, control hose, intercooler hose, torque converter hose, oil return hose, vacuum sensing hose, heat resistant hose and the like.
Claims (4)
(B)粉末状およびクラム状の乳化重合ゴム
を含有する原料組成物を、上流に連続式異方向回転二軸混練機、下流に同方向回転二軸押出機を直列に配設した押出装置の前記連続式異方向回転二軸混練機の原料導入部より供給し、前記連続式異方向回転二軸混練機により前記原料組成物を混合分散させ、前記連続式異方向回転二軸混練機の出口の混練物の温度を250℃以下に保持しながら、前記同方向回転二軸押出機により、架橋剤存在下に動的に熱処理する、熱可塑性エラストマー組成物の製造方法。 A raw material composition containing (A) a thermoplastic resin, and (B) a powdery and crumb-like emulsion-polymerized rubber, a continuous different direction rotating twin screw kneader upstream, and a same direction rotating twin screw extruder downstream. The raw material composition is supplied from the raw material introduction part of the continuous different-direction rotating twin-screw kneader of the extruder arranged in series, and the raw material composition is mixed and dispersed by the continuous different-direction rotating twin-screw kneader. Production of a thermoplastic elastomer composition that is dynamically heat-treated in the presence of a crosslinking agent by the same-direction rotating twin-screw extruder while maintaining the temperature of the kneaded product at the outlet of the direction-rotating twin-screw kneader at 250 ° C. or lower. Method.
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JPWO2006003972A1 (en) * | 2004-06-30 | 2008-04-17 | 日本ゼオン株式会社 | Thermoplastic elastomer composition and molded article thereof |
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JP2010202784A (en) * | 2009-03-04 | 2010-09-16 | Yokohama Rubber Co Ltd:The | Rubber composition capable of forming two or more crosslinkable groups |
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JP6232980B2 (en) * | 2013-12-02 | 2017-11-22 | 日油株式会社 | Thermoplastic elastomer |
JP6361399B2 (en) * | 2014-09-17 | 2018-07-25 | 日油株式会社 | Thermoplastic elastomer |
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JP7452262B2 (en) | 2019-07-19 | 2024-03-19 | 日本ゼオン株式会社 | Acrylic rubber veil with excellent storage stability |
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