JP6684434B2 - ABS resin composition and resin molded product - Google Patents
ABS resin composition and resin molded product Download PDFInfo
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- JP6684434B2 JP6684434B2 JP2015190772A JP2015190772A JP6684434B2 JP 6684434 B2 JP6684434 B2 JP 6684434B2 JP 2015190772 A JP2015190772 A JP 2015190772A JP 2015190772 A JP2015190772 A JP 2015190772A JP 6684434 B2 JP6684434 B2 JP 6684434B2
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- Prior art keywords
- abs resin
- vinyl acetate
- ethylene
- copolymer
- resin composition
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims description 86
- 239000011342 resin composition Substances 0.000 title claims description 59
- 229920005989 resin Polymers 0.000 title description 8
- 239000011347 resin Substances 0.000 title description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 66
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 66
- 229920000578 graft copolymer Polymers 0.000 claims description 58
- 150000001451 organic peroxides Chemical class 0.000 claims description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 29
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 16
- 229920006163 vinyl copolymer Polymers 0.000 claims description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 42
- 239000000463 material Substances 0.000 description 38
- 238000011156 evaluation Methods 0.000 description 23
- 238000012360 testing method Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000013011 mating Effects 0.000 description 15
- 239000003505 polymerization initiator Substances 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 12
- 229910000975 Carbon steel Inorganic materials 0.000 description 11
- 239000010962 carbon steel Substances 0.000 description 11
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- BMPPHGZRHQWRFX-UHFFFAOYSA-N (1-tert-butylperoxy-2-carboxyoxyethyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(COC(O)=O)OOC(C)(C)C BMPPHGZRHQWRFX-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 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 4
- 239000000654 additive Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- JXCAHDJDIAQCJO-UHFFFAOYSA-N (1-tert-butylperoxy-2-ethylhexyl) hydrogen carbonate Chemical compound CCCCC(CC)C(OC(O)=O)OOC(C)(C)C JXCAHDJDIAQCJO-UHFFFAOYSA-N 0.000 description 2
- 101100272412 Arabidopsis thaliana BIA1 gene Proteins 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 229930182556 Polyacetal Natural products 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 150000001723 carbon free-radicals Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- VCEFKTXEJZXVFE-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 4,4-dimethylpentaneperoxoate Chemical compound CC(C)(C)CCC(=O)OOOC(C)(C)C VCEFKTXEJZXVFE-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- CTPYJEXTTINDEM-UHFFFAOYSA-N 1,2-bis(1-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOCC(C)C1=CC=CC=C1C(C)COOC(C)(C)C CTPYJEXTTINDEM-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- YAQDPWONDFRAHF-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-ylperoxy)pentane Chemical compound CCCC(C)(C)OOC(C)(C)CCC YAQDPWONDFRAHF-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- WXDJDZIIPSOZAH-UHFFFAOYSA-N 2-methylpentan-2-yl benzenecarboperoxoate Chemical compound CCCC(C)(C)OOC(=O)C1=CC=CC=C1 WXDJDZIIPSOZAH-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004184 polymer manufacturing process Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、摺動部材として利用可能なＡＢＳ樹脂組成物、及び樹脂成形品に関する。 The present invention relates to an ABS resin composition that can be used as a sliding member, and a resin molded product.
アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ）樹脂は、耐衝撃性や耐熱性、加工性等に優れる。 Acrylonitrile-butadiene-styrene copolymer (ABS) resin is excellent in impact resistance, heat resistance, processability and the like.
このため、ＡＢＳ樹脂は、例えば、自動車部品、ＯＡ機器等の幅広い分野で用いられている。一方で、ＡＢＳ樹脂は、上記のような優れた性質から軸受けなどの摺動部材への応用が期待されるが、ポリアセタールやポリエチレンなどの結晶性樹脂と比較して耐摩耗性や動摩擦係数などの摺動性について改良の余地がある。また、部品同士が擦れ合った際に軋み音が発生する場合がある。 Therefore, the ABS resin is used in a wide range of fields such as automobile parts and office automation equipment. On the other hand, ABS resin is expected to be applied to sliding members such as bearings because of its excellent properties as described above. However, ABS resin has better wear resistance and dynamic friction coefficient than crystalline resins such as polyacetal and polyethylene. There is room for improvement in slidability. In addition, a squeaking noise may occur when the parts rub against each other.
熱可塑性樹脂の摺動性を向上させるための一般的な技術が特許文献１や特許文献２に開示されている。
特許文献１には、最終成形された熱可塑性樹脂の表面上に紫外線硬化型アクリル系ハードコート剤を塗布、硬化させ、ハードコート層を形成する技術が開示されている。
また、特許文献２には、軋み音の発生を抑制ないし低減させるために、表面処理剤としてフッ素系やシリコーン系のコーティング組成物をＡＢＳ樹脂の表面上に塗布する技術が開示されている。
A general technique for improving the slidability of a thermoplastic resin is disclosed in Patent Document 1 and Patent Document 2.
Patent Document 1 discloses a technique for forming a hard coat layer by coating and curing an ultraviolet-curable acrylic hard coat agent on the surface of a finally molded thermoplastic resin.
Patent Document 2 discloses a technique of applying a fluorine-based or silicone-based coating composition as a surface treatment agent onto the surface of an ABS resin in order to suppress or reduce the generation of squeaking noise.
しかしながら、特許文献１や特許文献２に記載の技術では、コーティング工程を行う必要があるため、作業時間やコスト負担が増加してしまう。この点、ＡＢＳ樹脂組成物自体の摺動性を向上させることができれば、コーティング工程を行うことなく優れた摺動性が得られる。 However, in the techniques described in Patent Document 1 and Patent Document 2, it is necessary to perform the coating process, and thus work time and cost burden increase. In this respect, if the slidability of the ABS resin composition itself can be improved, excellent slidability can be obtained without performing a coating step.
以上のような事情に鑑み、本発明の目的は、優れた摺動性が得られるＡＢＳ樹脂組成物、及び樹脂成形品を提供することにある。 In view of the circumstances as described above, an object of the present invention is to provide an ABS resin composition and a resin molded article that can obtain excellent slidability.
上記目的を達成するため、本発明に係るＡＢＳ樹脂組成物は、（Ｘ）ＡＢＳ樹脂と、（Ｙ）グラフト共重合体と、を含有する。
上記（Ｙ）グラフト共重合体の主鎖が、（Ａ）エチレン−酢酸ビニル共重合体から成る。
上記（Ｙ）グラフト共重合体の側鎖が、（ｂ−１）スチレンと、（ｂ−２）アクリロニトリル及びメタクリル酸グリシジルの少なくとも１つと、を含有する（Ｂ）ビニル共重合体から成る。
上記（Ｙ）グラフト共重合体の主鎖同士が架橋されている。
前記（Ａ）エチレン−酢酸ビニル共重合体において、酢酸ビニルの含有量が1重量％以上、２０重量％以下である。
この構成により、優れた摺動性が得られるＡＢＳ樹脂組成物を提供することができる。
In order to achieve the above object, the ABS resin composition according to the present invention contains (X) ABS resin and (Y) graft copolymer.
The main chain of the (Y) graft copolymer is composed of (A) ethylene-vinyl acetate copolymer.
The side chain of the (Y) graft copolymer is composed of (B) a vinyl copolymer containing (b-1) styrene and (b-2) at least one of acrylonitrile and glycidyl methacrylate.
The main chains of the (Y) graft copolymer are crosslinked.
In the ethylene-vinyl acetate copolymer (A), the content of vinyl acetate is 1% by weight or more and 20% by weight or less.
With this configuration, it is possible to provide an ABS resin composition that provides excellent slidability.
本発明では、更に前記（Ｙ）グラフト共重合体の主鎖同士が、前記（Ａ）エチレン−酢酸ビニル共重合体１００重量部に対して０．１〜３重量部の（Ｃ）有機過酸化物によって架橋されている。
この構成により、（Ａ）エチレン−酢酸ビニル共重合体の主鎖同士が選択的に架橋され、（Ｘ）ＡＢＳ樹脂に対する（Ｙ）グラフト共重合体の分散性が良好となる。
In the present invention, the main chains of the (Y) graft copolymer are further 0.1 to 3 parts by weight of (C) organic peroxide with respect to 100 parts by weight of the ( A) ethylene-vinyl acetate copolymer. It is cross-linked by objects.
With this configuration, the main chains of the ethylene-vinyl acetate copolymer (A) are selectively crosslinked, and the dispersibility of the (Y) graft copolymer in the (X) ABS resin is improved.
更に、上記（Ｘ）ＡＢＳ樹脂の含有量を１００重量部とすると、上記（Ｙ）グラフト共重合体の含有量を１〜２５重量部とする。
この構成により、ＡＢＳ樹脂組成物の摺動性や外観品質が更に向上し、摺動時の軋み音の発生も更に抑制できる。
Further, when the content of the (X) ABS resin is 100 parts by weight, the content of the (Y) graft copolymer is 1 to 25 parts by weight.
With this configuration, the slidability and appearance quality of the ABS resin composition are further improved, and the generation of squeaking noise during sliding can be further suppressed.
上記（Ａ）エチレン−酢酸ビニル共重合体と、上記（ｂ−１）スチレンと、上記（ｂ−２）アクリロニトリル及びメタクリル酸グリシジルの少なくとも１つと、の含有量の合計を１００重量部とすると、上記（Ａ）エチレン−酢酸ビニル共重合体の含有量が５０〜９０重量部であってもよい。
この構成により、特に良好な摺動性を有するＡＢＳ樹脂組成物が得られる。
When the total content of the (A) ethylene-vinyl acetate copolymer, the (b-1) styrene, and (b-2) at least one of acrylonitrile and glycidyl methacrylate is 100 parts by weight, The content of the above-mentioned (A) ethylene-vinyl acetate copolymer may be 50 to 90 parts by weight.
With this configuration, an ABS resin composition having particularly good slidability can be obtained.
本発明の一形態に係る樹脂成形品は、上記ＡＢＳ樹脂組成物を成形して得られる。 The resin molded product according to one aspect of the present invention is obtained by molding the ABS resin composition.
優れた摺動性が得られるＡＢＳ樹脂組成物、及び樹脂成形品を提供することができる。 It is possible to provide an ABS resin composition having excellent slidability and a resin molded article.
以下、本発明の一実施形態を説明する。 An embodiment of the present invention will be described below.
＜ＡＢＳ樹脂組成物＞
本実施形態に係るＡＢＳ樹脂組成物は、（Ｘ）ＡＢＳ樹脂と、（Ｙ）グラフト共重合体と、を含有する。
<ABS resin composition>
The ABS resin composition according to the present embodiment contains (X) ABS resin and (Y) graft copolymer.
このＡＢＳ樹脂組成物で用いる（Ｙ）グラフト共重合体は、特定の主鎖と側鎖からなり、更に有機過酸化物によって選択的に主鎖同士を架橋させて得られる。このような（Ｙ）グラフト共重合体を用いることにより、（Ｙ）グラフト共重合体が（Ｘ）ＡＢＳ樹脂に対して良好に分散する。これにより、（Ｘ）ＡＢＳ樹脂本来の優れた機械物性が維持されるとともに、優れた摺動性を有するＡＢＳ樹脂組成物が得られる。 The (Y) graft copolymer used in this ABS resin composition has a specific main chain and side chains, and is obtained by selectively crosslinking the main chains with an organic peroxide. By using such a (Y) graft copolymer, the (Y) graft copolymer is favorably dispersed in the (X) ABS resin. This makes it possible to obtain an ABS resin composition having excellent slidability while maintaining the original excellent mechanical properties of the (X) ABS resin.
＜（Ｘ）ＡＢＳ樹脂＞
本実施形態に係る（Ｘ）ＡＢＳ樹脂は、アクリロニトリル、ブタジエン、スチレンの３成分を主体とした共重合体を主成分とするものであり、特定の種類に限定されず、公知の方法で製造されたものを使用することができる。例えば、ブタジエン存在下でアクリロニトリルとスチレンをラジカル共重合して得られるもの等が挙げられる。（Ｘ）ＡＢＳ樹脂における、アクリロニトリル、ブタジエン、スチレンのそれぞれの含有量は特に限定されない。
<(X) ABS resin>
The (X) ABS resin according to the present embodiment is mainly composed of a copolymer mainly composed of acrylonitrile, butadiene, and styrene, and is not limited to a particular type, and is manufactured by a known method. It can be used. Examples thereof include those obtained by radically copolymerizing acrylonitrile and styrene in the presence of butadiene. The contents of acrylonitrile, butadiene, and styrene in the (X) ABS resin are not particularly limited.
＜（Ｙ）グラフト共重合体＞
本実施形態に係る（Ｙ）グラフト共重合体の主鎖は、（Ａ）エチレン−酢酸ビニル共重合体から成る。（Ｙ）グラフト共重合体の側鎖は、（ｂ−１）スチレンと、（ｂ−２）アクリロニトリル及びメタクリル酸グリシジルの少なくとも１つと、のビニル共重合体から成る。
<(Y) Graft Copolymer>
The main chain of the (Y) graft copolymer according to this embodiment is composed of (A) ethylene-vinyl acetate copolymer. The side chain of the (Y) graft copolymer is composed of a vinyl copolymer of (b-1) styrene and (b-2) at least one of acrylonitrile and glycidyl methacrylate.
本実施形態に係る（Ｙ）グラフト共重合体は、主鎖同士の炭素−炭素結合により架橋されている。この主鎖同士の炭素−炭素結合は、例えば、後述の（Ｃ）有機過酸化物の作用によって得られる。 The (Y) graft copolymer according to this embodiment is crosslinked by carbon-carbon bonds between main chains. The carbon-carbon bond between the main chains is obtained, for example, by the action of (C) organic peroxide described later.
より詳細には、（Ｙ）グラフト共重合体が生成される際に、（Ｃ）有機過酸化物が分解して生じたラジカルが、（Ａ）エチレン−酢酸ビニル共重合体から水素を引き抜く。これにより、（Ａ）エチレン−酢酸ビニル共重合体に含まれる炭素ラジカルが生成される。（Ａ）エチレン−酢酸ビニル共重合体からの水素の引き抜き反応は、一般的に、−ＯＣＯＣＨ３＞（−ＣＨ２−ｏｒ−ＣＨ―）の順に反応する。この炭素ラジカル同士が再結合反応することにより、（Ｙ）グラフト共重合体の主鎖同士の炭素−炭素結合が形成される。 More specifically, when the (Y) graft copolymer is produced, the radicals generated by the decomposition of the (C) organic peroxide abstract hydrogen from the (A) ethylene-vinyl acetate copolymer. As a result, carbon radicals contained in the (A) ethylene-vinyl acetate copolymer are generated. (A) an ethylene - abstraction reaction of hydrogen from the vinyl acetate copolymer is generally, -OCOCH 3> (- CH 2 -or-CH-) reacting the order. The carbon-carbon bonds between the main chains of the (Y) graft copolymer are formed by the recombination reaction of the carbon radicals.
（Ｙ）グラフト共重合体の含有量は、（Ｘ）ＡＢＳ樹脂の含有量を１００重量部とすると、１〜２５重量部とするが、１〜１５重量部であることが更に好ましい。
The content of the (Y) graft copolymer is 1 to 25 parts by weight when the content of the (X) ABS resin is 100 parts by weight, and more preferably 1 to 15 parts by weight.
（Ｙ）グラフト共重合体の含有量を１重量部以上とすることによりＡＢＳ樹脂組成物の摺動性が向上し、（Ｙ）グラフト共重合体の含有量を３重量部以上とすることによりＡＢＳ樹脂組成物の摺動性が更に向上する。 By adjusting the content of the (Y) graft copolymer to 1 part by weight or more, the slidability of the ABS resin composition is improved, and by adjusting the content of the (Y) graft copolymer to 3 parts by weight or more. The slidability of the ABS resin composition is further improved.
この一方で、（Ｙ）グラフト共重合体の含有量を２５重量部以下に留めることによりＡＢＳ樹脂組成物の機械物性や外観品質が向上し、（Ｙ）グラフト共重合体の含有量を１５重量部以下に留めることによりＡＢＳ樹脂組成物の機械物性や外観品質が更に向上する。 On the other hand, by keeping the content of the (Y) graft copolymer at 25 parts by weight or less, the mechanical properties and appearance quality of the ABS resin composition are improved, and the content of the (Y) graft copolymer is 15 parts by weight. By limiting the amount to less than the range, mechanical properties and appearance quality of the ABS resin composition are further improved.
本実施形態に係る（Ｙ）グラフト共重合体は、以下に説明するエチレン−酢酸ビニル共重合体樹脂組成物を溶融混練することにより得られる。 The (Y) graft copolymer according to the present embodiment is obtained by melt-kneading the ethylene-vinyl acetate copolymer resin composition described below.
＜エチレン−酢酸ビニル共重合体樹脂組成物＞
本実施形態に係るエチレン−酢酸ビニル共重合体樹脂組成物は、（Ａ）エチレン−酢酸ビニル共重合体（ＥＶＡ）と、（Ｂ）ビニル共重合体と、（Ｃ）有機過酸化物と、を含有する。（Ｂ）ビニル共重合体及び（Ｃ）有機過酸化物は、（Ａ）エチレン−酢酸ビニル共重合体に含浸されている。
<Ethylene-vinyl acetate copolymer resin composition>
The ethylene-vinyl acetate copolymer resin composition according to the present embodiment includes (A) an ethylene-vinyl acetate copolymer (EVA), (B) a vinyl copolymer, and (C) an organic peroxide. Contains. The (B) vinyl copolymer and the (C) organic peroxide are impregnated in the (A) ethylene-vinyl acetate copolymer.
［（Ａ）エチレン−酢酸ビニル共重合体（ＥＶＡ）］
本実施形態に係る（Ａ）エチレン−酢酸ビニル共重合体では、構造単位での酢酸ビニルの含有量が、１〜２０重量％であることが好ましく、３〜１０重量％であることが更に好ましい。
[(A) Ethylene-vinyl acetate copolymer (EVA)]
In the ethylene-vinyl acetate copolymer (A) according to the present embodiment, the content of vinyl acetate in the structural unit is preferably 1 to 20% by weight, more preferably 3 to 10% by weight. .
（Ａ）エチレン−酢酸ビニル共重合体において、酢酸ビニルの含有量を２０重量％以下に留めることにより、ＡＢＳ樹脂組成物の摺動性が向上し、酢酸ビニルの含有量を１０重量％以下に留めることにより、ＡＢＳ樹脂組成物の摺動性が更に向上する。更に、これらの場合に、（Ｙ）グラフト重合体の耐熱性が向上する。 In the ethylene-vinyl acetate copolymer (A), by keeping the content of vinyl acetate at 20% by weight or less, the slidability of the ABS resin composition is improved, and the content of vinyl acetate is reduced to 10% by weight or less. By stopping, the slidability of the ABS resin composition is further improved. Furthermore, in these cases, the heat resistance of the (Y) graft polymer is improved.
この一方で、（Ａ）エチレン−酢酸ビニル共重合体において、酢酸ビニルの含有量を１重量％以上とすることにより、（Ｃ）有機過酸化物による架橋反応が進行しやすくなり、（Ａ）エチレン−酢酸ビニル共重合体における酢酸ビニルの含有量を３重量％以上とすることにより、（Ｃ）有機過酸化物による架橋反応が更に進行しやすくなる。 On the other hand, in the ethylene-vinyl acetate copolymer (A), when the content of vinyl acetate is 1% by weight or more, the crosslinking reaction by the organic peroxide (C) easily proceeds, and (A) By setting the content of vinyl acetate in the ethylene-vinyl acetate copolymer to 3% by weight or more, the crosslinking reaction by the organic peroxide (C) is further facilitated.
また、（Ａ）エチレン−酢酸ビニル共重合体としては、その流動性を指標として任意に選択可能である。例えば、（Ａ）エチレン−酢酸ビニル共重合体のメルトフローレート（ＭＦＲ）は、ＪＩＳ Ｋ ７２１０に準拠した測定方法で、１９０℃において、０．１〜２５（ｇ／１０ｍｉｎ）であることが好ましく、１．０〜１０（ｇ／１０ｍｉｎ）であることが更に好ましい。 The (A) ethylene-vinyl acetate copolymer can be arbitrarily selected with its fluidity as an index. For example, the melt flow rate (MFR) of the ethylene-vinyl acetate copolymer (A) is preferably 0.1 to 25 (g / 10 min) at 190 ° C. by a measurement method according to JIS K 7210. , 1.0 to 10 (g / 10 min) is more preferable.
（Ａ）エチレン−酢酸ビニル共重合体において、ＭＦＲを２５（ｇ／１０ｍｉｎ）以下に、更にＭＦＲを１０（ｇ／１０ｍｉｎ）以下に留めることにより、ＡＢＳ樹脂組成物の摺動性が向上する。この一方で、（Ａ）エチレン−酢酸ビニル共重合体において、ＭＦＲを０．１（ｇ／１０ｍｉｎ）以上とし、更にＭＦＲを１．０（ｇ／１０ｍｉｎ）以上とすることにより、（Ｙ）グラフト重合体の製造プロセスにおける作業性が向上する。 In the ethylene-vinyl acetate copolymer (A), the sliding property of the ABS resin composition is improved by keeping the MFR at 25 (g / 10 min) or less and the MFR at 10 (g / 10 min) or less. On the other hand, in the ethylene-vinyl acetate copolymer (A), the MFR is set to 0.1 (g / 10 min) or more, and further, the MFR is set to 1.0 (g / 10 min) or more, whereby the (Y) graft Workability in the polymer manufacturing process is improved.
［（Ｂ）ビニル共重合体］
本実施形態に係る（Ｂ）ビニル共重合体は、（ｂ−１）スチレンと、（ｂ−２）アクリロニトリル及びメタクリル酸グリシジルの少なくとも１つと、（ｂ−３）ｔ−ブチルペルオキシメタクリロイロキシエチルカーボネートと、（ｂ−４）重合開始剤と、から成るビニル単量体組成物により構成される。
[(B) Vinyl Copolymer]
The (B) vinyl copolymer according to the present embodiment includes (b-1) styrene, (b-2) at least one of acrylonitrile and glycidyl methacrylate, and (b-3) t-butylperoxymethacryloyloxyethyl. It is composed of a vinyl monomer composition comprising carbonate and (b-4) a polymerization initiator.
（Ｂ）ビニル共重合体における各単量体（ｂ−１），（ｂ−２），（ｂ−３），（ｂ−４）の含有量は適宜決定可能である。しかし、（ｂ−１）スチレンと、（ｂ−２）アクリロニトリル及びメタクリル酸グリシジルの少なくとも１つと、の含有量の合計を１００重量部とすると、（ｂ−１）スチレンの含有量が５０〜９９重量部であることが好ましい。これにより、摺動性及び機械物性に特に優れたＡＢＳ樹脂組成物が得られる。 The content of each monomer (b-1), (b-2), (b-3), (b-4) in the (B) vinyl copolymer can be appropriately determined. However, when the total content of (b-1) styrene and (b-2) at least one of acrylonitrile and glycidyl methacrylate is 100 parts by weight, the content of (b-1) styrene is 50 to 99. It is preferably part by weight. As a result, an ABS resin composition having particularly excellent slidability and mechanical properties can be obtained.
また、（Ａ）エチレン−酢酸ビニル共重合体と、（ｂ−１）スチレンと、（ｂ−２）アクリロニトリル及びメタクリル酸グリシジルの少なくとも１つと、の含有量の合計を１００重量部とすると、（Ａ）エチレン−酢酸ビニル共重合体の含有量が５０〜９０重量部であることが好ましい。この場合に、ＡＢＳ樹脂組成物における特に良好な摺動性が得られる。 When the total content of (A) ethylene-vinyl acetate copolymer, (b-1) styrene, and (b-2) at least one of acrylonitrile and glycidyl methacrylate is 100 parts by weight, ( The content of A) ethylene-vinyl acetate copolymer is preferably 50 to 90 parts by weight. In this case, particularly good slidability of the ABS resin composition can be obtained.
（Ｂ）ビニル共重合体における（ｂ−３）ｔ−ブチルペルオキシメタクリロイロキシエチルカーボネートは、下記化学式（１）で表される化合物である。本実施形態に係るエチレン−酢酸ビニル共重合体樹脂組成物を溶融混練すると、（ｂ−３）ｔ−ブチルペルオキシメタクリロイロキシエチルカーボネートの過酸化結合が熱分解してラジカルを発生させることにより、（Ｙ）グラフト共重合体が得られる。
（Ｂ）ビニル共重合体における（ｂ−４）重合開始剤は、特定の種類に限定されず、有機過酸化物やアゾ開始剤などといった公知のものを利用可能である。しかし、（ｂ−４）重合開始剤の１０時間半減期温度は５０〜７５℃であることが好ましい。 The (b-4) polymerization initiator in the vinyl copolymer (B) is not limited to a particular type, and known ones such as organic peroxides and azo initiators can be used. However, the 10-hour half-life temperature of the (b-4) polymerization initiator is preferably 50 to 75 ° C.
ここで、１０時間半減期温度（以下、「Ｔ１０」との略称も用いる。）とは、（ｂ−４）重合開始剤又は（Ｃ）有機過酸化物に含まれる過酸化結合濃度又はアゾ結合濃度を０．１モル／リットルとなるようにベンゼンに溶解させた溶液を熱分解させた際に、当該（ｂ−４）重合開始剤又は（Ｃ）有機過酸化物が１０時間で半減期を迎える温度のことである。 Here, the 10-hour half-life temperature (hereinafter, also referred to as “T10”) is used to mean (b-4) polymerization initiator or (C) peroxide bond concentration or azo bond contained in the organic peroxide. When a solution prepared by dissolving benzene in a concentration of 0.1 mol / liter was pyrolyzed, the (b-4) polymerization initiator or (C) organic peroxide had a half-life of 10 hours. It is the temperature to reach.
（ｂ−４）重合開始剤の１０時間半減期温度を５０℃以上とすることにより、（ｂ−４）重合開始剤の急激な分解が抑制され、重合温度を制御しやすくなる。この一方で、（ｂ−４）重合開始剤の１０時間半減期温度を７５℃以下とすることにより、（ｂ−４）重合開始剤の良好な分解が得られ、（Ｙ）グラフト共重合体に（ｂ−４）重合開始剤自体や他の単量体が残存しにくくなる。 By setting the 10-hour half-life temperature of the polymerization initiator (b-4) to 50 ° C. or higher, the rapid decomposition of the polymerization initiator (b-4) is suppressed and the polymerization temperature is easily controlled. On the other hand, by setting the 10-hour half-life temperature of the (b-4) polymerization initiator to 75 ° C. or lower, good decomposition of the (b-4) polymerization initiator is obtained, and the (Y) graft copolymer is obtained. In addition, (b-4) the polymerization initiator itself and other monomers are less likely to remain.
なお、（Ａ）エチレン−酢酸ビニル共重合体に（ｂ−４）重合開始剤自体や他の単量体を残存しにくくするために、（Ｂ）ビニル共重合体を得るための重合温度を高くすることも考えられる。 In addition, in order to prevent the (b-4) polymerization initiator itself and other monomers from remaining in the (A) ethylene-vinyl acetate copolymer, the polymerization temperature for obtaining the (B) vinyl copolymer is set to It is also possible to raise it.
しかし、重合温度を高くすると、重合温度と（Ｃ）有機過酸化物の１０時間半減期温度との差が小さくなるため、（Ｂ）ビニル共重合体を得るための重合反応時に（Ｃ）有機過酸化物が分解しやすくなる。したがって、溶融混練時に（Ｃ）有機過酸化物が不足し、（Ａ）エチレン−酢酸ビニル共重合体が十分に架橋反応を行うことができなくなる場合がある。このため、（Ｂ）ビニル共重合体を得るための重合温度を高くすることは好ましくない。 However, when the polymerization temperature is increased, the difference between the polymerization temperature and the 10-hour half-life temperature of the (C) organic peroxide is reduced, and therefore, the (C) organic compound is used during the polymerization reaction to obtain the (B) vinyl copolymer. Peroxide becomes easy to decompose. Therefore, the (C) organic peroxide may be insufficient during melt-kneading, and the (A) ethylene-vinyl acetate copolymer may not be able to sufficiently perform the crosslinking reaction. Therefore, it is not preferable to increase the polymerization temperature for obtaining the vinyl copolymer (B).
（ｂ−４）重合開始剤として利用可能な有機過酸化物として、例えば、下記のものが挙げられる。各物質について、括弧内に１０時間半減期温度を示す。
ｔ−ブチルパーオキシネオヘプタノエート（Ｔ１０＝５１℃）
ｔ−ヘキシルパーオキシピバレート（Ｔ１０＝５３℃）
ｔ−ブチルパーオキシピバレート（Ｔ１０＝５５℃）
ジ（３，５，５−トリメチルヘキサノイル）パーオキサイド（Ｔ１０＝５９℃）
ジラウロイルパーオキサイド（Ｔ１０＝６２℃）
１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエート（Ｔ１０＝６５℃）
２，５−ジメチル−２，５−ジ（２−エチルヘキサノイルパーオキシ）ヘキサン（Ｔ１０＝６６℃）
ｔ−ヘキシルパーオキシ−２−エチルヘキシルヘキサノエート（Ｔ１０＝７０℃）
ジ（４−メチルベンゾイル）パーオキサイド（Ｔ１０＝７１℃）
ｔ−ブチルパーオキシ−２−エチルヘキサノエート（Ｔ１０＝７２℃）
ジベンゾイルパーオキサイド（Ｔ１０＝７４℃）
Examples of the organic peroxide that can be used as the (b-4) polymerization initiator include the following. The 10-hour half-life temperature is shown in parentheses for each substance.
t-Butylperoxy neoheptanoate (T10 = 51 ° C)
t-hexyl peroxypivalate (T10 = 53 ° C)
t-Butyl peroxypivalate (T10 = 55 ° C)
Di (3,5,5-trimethylhexanoyl) peroxide (T10 = 59 ° C)
Dilauroyl peroxide (T10 = 62 ° C)
1,1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate (T10 = 65 ° C)
2,5-Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane (T10 = 66 ° C)
t-hexyl peroxy-2-ethylhexyl hexanoate (T10 = 70 ° C.)
Di (4-methylbenzoyl) peroxide (T10 = 71 ° C)
t-Butylperoxy-2-ethylhexanoate (T10 = 72 ° C)
Dibenzoyl peroxide (T10 = 74 ° C)
（ｂ−４）重合開始剤として利用可能なアゾ化合物として、例えば、下記のものが挙げられる。各物質について、括弧内に１０時間半減期温度を示す。
２，２−アゾビス（２，４−ジメチルバレロニトリル）（Ｔ１０＝５１℃）
２，２−アゾビス（イソブチロニトリル）（Ｔ１０＝６５℃）
２，２−アゾビス（２−メチルブチロニトリル）（Ｔ１０＝６７℃）
Examples of the azo compound that can be used as the polymerization initiator (b-4) include the following. The 10-hour half-life temperature is shown in parentheses for each substance.
2,2-Azobis (2,4-dimethylvaleronitrile) (T10 = 51 ° C)
2,2-Azobis (isobutyronitrile) (T10 = 65 ° C)
2,2-Azobis (2-methylbutyronitrile) (T10 = 67 ° C)
［（Ｃ）有機過酸化物］
本実施形態に係る（Ｃ）有機過酸化物は、溶融混練時に熱分解してラジカルを発生させることにより、（Ａ）エチレン−酢酸ビニル共重合体を架橋することができる。
（Ｃ）有機過酸化物は、特定の種類に限定されず、公知のものを利用可能である。しかし、（Ｃ）有機過酸化物の１０時間半減期温度は９５〜１３０℃であることが好ましい。
[(C) Organic peroxide]
The (C) organic peroxide according to the present embodiment can crosslink the (A) ethylene-vinyl acetate copolymer by thermally decomposing and generating radicals during melt-kneading.
The (C) organic peroxide is not limited to a particular type, and known ones can be used. However, the 10-hour half-life temperature of the organic peroxide (C) is preferably 95 to 130 ° C.
（Ｃ）有機過酸化物の１０時間半減期温度を９５℃以上とすることにより、（Ｂ）ビニル共重合体を得るための重合反応時に（Ｃ）有機過酸化物が分解しにくくなる。したがって、（Ｂ）ビニル共重合体を得るための重合反応時に（Ｃ）有機過酸化物が減少しにくいため、溶融混練時に（Ａ）エチレン−酢酸ビニル共重合体の架橋反応が不足することを防止できる。 By setting the 10-hour half-life temperature of the organic peroxide (C) to 95 ° C. or higher, the organic peroxide (C) is less likely to decompose during the polymerization reaction for obtaining the vinyl copolymer (B). Therefore, since the (C) organic peroxide is less likely to decrease during the polymerization reaction for obtaining the (B) vinyl copolymer, the crosslinking reaction of the (A) ethylene-vinyl acetate copolymer may be insufficient during melt kneading. It can be prevented.
この一方で、（Ｃ）有機過酸化物の１０時間半減期温度を１３０℃以下とすることにより、溶融混練時に（Ｃ）有機過酸化物が良好に分解する。これにより、（Ａ）エチレン−酢酸ビニル共重合体の架橋反応が良好に進行するようになる。 On the other hand, by setting the 10-hour half-life temperature of the (C) organic peroxide to 130 ° C. or less, the (C) organic peroxide is satisfactorily decomposed during melt kneading. This allows the crosslinking reaction of the ethylene-vinyl acetate copolymer (A) to proceed favorably.
本実施形態に利用可能な（Ｃ）有機過酸化物としては、例えば、下記のものが挙げられる。各物質について、括弧内に１０時間半減期温度を示す。
ｔ−ヘキシルパーオキシイソプロピルモノカーボネート（Ｔ１０＝９５℃）
ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート（Ｔ１０＝９７℃）
ｔ−ブチルパーオキシラウレート（Ｔ１０＝９８℃）
ｔ−ブチルパーオキシイソプロピルモノカーボネート（Ｔ１０＝９９℃）
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（Ｔ１０＝９９℃）
ｔ−ヘキシルパーオキシベンゾエート（Ｔ１０＝９９℃）
２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン（Ｔ１０＝１００℃）
ｔ−ブチルパーオキシアセテート（Ｔ１０＝１０２℃）
２，２−ジ（ｔ−ブチルパーオキシ）ブタン（Ｔ１０＝１０３℃）
ｔ−ブチルパーオキシベンゾエート（Ｔ１０＝１０４℃）
ｎ−ブチル−４，４−ジ（ｔ−ブチルパーオキシ）バレレート（Ｔ１０＝１０５℃）
ジ（２−ｔ−ブチルパーオキシイソプロピル）ベンゼン（Ｔ１０＝１１９℃）
ジクミルパーオキサイド（Ｔ１０＝１１６℃）
ジ−ｔ−ヘキシルパーオキサイド（Ｔ１０＝１１６℃）
２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン（Ｔ１０＝１１８℃）
ｔ−ブチルクミルパーオキサイド（Ｔ１０＝１２０℃）
ジ−ｔ−ブチルパーオキサイド（Ｔ１０＝１２４℃）
Examples of the (C) organic peroxide that can be used in the present embodiment include the following. The 10-hour half-life temperature is shown in parentheses for each substance.
t-hexyl peroxyisopropyl monocarbonate (T10 = 95 ° C)
t-Butylperoxy-3,5,5-trimethylhexanoate (T10 = 97 ° C)
t-Butyl peroxylaurate (T10 = 98 ° C)
t-Butyl peroxyisopropyl monocarbonate (T10 = 99 ° C)
t-Butylperoxy-2-ethylhexyl monocarbonate (T10 = 99 ° C)
t-hexyl peroxybenzoate (T10 = 99 ° C)
2,5-Dimethyl-2,5-di (benzoylperoxy) hexane (T10 = 100 ° C)
t-butyl peroxyacetate (T10 = 102 ° C)
2,2-di (t-butylperoxy) butane (T10 = 103 ° C)
t-butyl peroxybenzoate (T10 = 104 ° C)
n-Butyl-4,4-di (t-butylperoxy) valerate (T10 = 105 ° C.)
Di (2-t-butylperoxyisopropyl) benzene (T10 = 119 ° C)
Dicumyl peroxide (T10 = 116 ℃)
Di-t-hexyl peroxide (T10 = 116 ° C)
2,5-Dimethyl-2,5-di (t-butylperoxy) hexane (T10 = 118 ° C)
t-Butyl cumyl peroxide (T10 = 120 ° C)
Di-t-butyl peroxide (T10 = 124 ° C)
本発明に係る（Ｃ）有機過酸化物の含有量は、（Ａ）エチレン−酢酸ビニル共重合体の含有量を１００重量部とすると、０．１〜３重量部とする。（Ｃ）有機過酸化物の含有量を０．１重量部以上とすることにより、（Ａ）エチレン−酢酸ビニル共重合体の架橋反応が不足することを防止できる。この一方で、（Ｃ）有機過酸化物の含有量を３重量部以下に留めることにより、溶融混練により得られる（Ｙ）グラフト共重合体において良好な流動性が得られる。 The content of the according (C) an organic peroxide present invention, (A) an ethylene - When 100 parts by weight content of vinyl acetate copolymer, and 0.1 to 3 parts by weight. When the content of the organic peroxide (C) is 0.1 part by weight or more, the insufficient crosslinking reaction of the ethylene-vinyl acetate copolymer (A) can be prevented. On the other hand, by keeping the content of the (C) organic peroxide at 3 parts by weight or less, good fluidity can be obtained in the (Y) graft copolymer obtained by melt-kneading.
［その他の添加物］
本実施形態に係るＡＢＳ樹脂組成物は、必要に応じ、上記以外の添加物を含有していてもよい。このような添加物としては、例えば、鉱油、炭化水素、脂肪酸、アルコール、脂肪酸エステル、脂肪酸アミド、金属石けん、天然ワックス、シリコーンなどの潤滑剤、水酸化マグネシウム、水酸化アルミニウム等の無機難燃剤、ハロゲン系、リン系等の有機難燃剤、金属粉、タルク、炭酸カルシウム、チタン酸カリウム、ガラス繊維、カーボン繊維、木粉等の有機又は無機の充填剤、酸化防止剤、紫外線防止剤、滑剤、分散剤、カップリング剤、発泡剤、着色剤等の添加剤及び他のポリオレフィン系樹脂、ポリエステル、ポリアセタール、ポリアミド、ポリカーボネート、ポリフェニレンエーテル、等のエンジニアリングプラスチックなどが挙げられる。
[Other additives]
The ABS resin composition according to the present embodiment may contain additives other than the above, if necessary. Examples of such additives include mineral oils, hydrocarbons, fatty acids, alcohols, fatty acid esters, fatty acid amides, metallic soaps, natural waxes, lubricants such as silicones, magnesium hydroxide, inorganic flame retardants such as aluminum hydroxide, Halogen-based, phosphorus-based organic flame retardants, metal powder, talc, calcium carbonate, potassium titanate, glass fibers, carbon fibers, organic or inorganic fillers such as wood powder, antioxidants, UV inhibitors, lubricants, Additives such as a dispersant, a coupling agent, a foaming agent, and a colorant, and other polyolefin-based resins, engineering plastics such as polyester, polyacetal, polyamide, polycarbonate, polyphenylene ether, and the like can be given.
＜樹脂成形品＞
本実施形態に係るＡＢＳ樹脂組成物は、熱可塑性樹脂であるため、射出成形や押出し成形などにより、容易に様々な形状に成形することが可能である。本実施形態に係るＡＢＳ樹脂組成物を成形して得られる樹脂成形品は、機械物性、及び摺動性に優れるため、電気部品、電子部品、機械部品、精密機器部品、自動車部品などの広い分野で利用することができる。
<Resin molding>
Since the ABS resin composition according to this embodiment is a thermoplastic resin, it can be easily molded into various shapes by injection molding or extrusion molding. A resin molded product obtained by molding the ABS resin composition according to the present embodiment has excellent mechanical properties and slidability, and therefore has a wide range of fields such as electric parts, electronic parts, mechanical parts, precision instrument parts, and automobile parts. Can be used at.
以下、実施例及び比較例を挙げて本発明を更に具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
＜エチレン−酢酸ビニル共重合体樹脂組成物＞
［エチレン−酢酸ビニル共重合体樹脂組成物の製造］
製造例１−１〜１−１３及び比較製造例１−１〜１−３について、表１に示す組成でエチレン−酢酸ビニル共重合体樹脂組成物を製造した。この一例として、製造例１−１に係るエチレン−酢酸ビニル共重合体樹脂組成物の製造プロセスを以下に示す。なお、他の製造例及び比較製造例に係るエチレン−酢酸ビニル共重合体樹脂組成物も、製造例１−１と同様のプロセスで製造した。
<Ethylene-vinyl acetate copolymer resin composition>
[Production of ethylene-vinyl acetate copolymer resin composition]
For Production Examples 1-1 to 1-13 and Comparative Production Examples 1-1 to 1-3, ethylene-vinyl acetate copolymer resin compositions having the compositions shown in Table 1 were produced. As an example of this, a production process of the ethylene-vinyl acetate copolymer resin composition according to Production Example 1-1 is shown below. The ethylene-vinyl acetate copolymer resin compositions according to other production examples and comparative production examples were also produced by the same process as in Production Example 1-1.
［製造例１−１に係るエチレン−酢酸ビニル共重合体樹脂組成物の製造］
内容積５Ｌのステンレス製オートクレーブに、純水２５００ｇを入れ、更に懸濁剤としてポリビニルアルコール２．５ｇを溶解させた。この中に、エチレン−酢酸ビニル共重合体（商品名「ウルトラセン５１０」、東ソー株式会社製、ＶＡｃ含有量６％、ＭＦＲ＝２．５（ｇ／１０ｍｉｎ）７００ｇを入れ、攪拌して分散させた。
[Production of ethylene-vinyl acetate copolymer resin composition according to Production Example 1-1]
2500 g of pure water was put into a stainless steel autoclave having an internal volume of 5 L, and 2.5 g of polyvinyl alcohol was further dissolved as a suspending agent. Into this, ethylene-vinyl acetate copolymer (trade name “Ultrasen 510”, manufactured by Tosoh Corporation, VAc content 6%, MFR = 2.5 (g / 10 min) 700 g was put and dispersed by stirring. It was
これとは別に、４．０ｇのラジカル重合開始剤、９．０ｇのラジカル（共）重合性有機過酸化物、及び３．５ｇの架橋剤を、２１０ｇのスチレン（Ｓｔ）及び９０ｇのメタクリル酸グリシジル（ＧＭＡ）に溶解させた溶液を生成し、この溶液をオートクレーブ中に投入し攪拌した。 Separately, 4.0 g of a radical polymerization initiator, 9.0 g of a radical (co) polymerizable organic peroxide, and 3.5 g of a crosslinking agent were added to 210 g of styrene (St) and 90 g of glycidyl methacrylate. A solution dissolved in (GMA) was produced, and this solution was put into an autoclave and stirred.
ラジカル重合開始剤としてはジ（３，５，５−トリメチルヘキサノイル）パーオキサイド（商品名「パーロイル３５５」、１０時間半減期温度＝５９℃、日油株式会社製）を用い、ラジカル（共）重合性有機過酸化物としてはｔ−ブチルペルオキシメタクリロイロキシエチルカーボネート（ＭＥＣ）を用い、架橋剤としては２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン（商品名「パーヘキサ２５Ｂ」、１０時間半減期温度＝１１８℃、日油株式会社製）を用いた。 As the radical polymerization initiator, di (3,5,5-trimethylhexanoyl) peroxide (trade name “Perloyl 355”, 10-hour half-life temperature = 59 ° C., manufactured by NOF CORPORATION) was used, and the radical (co) was used. T-Butylperoxymethacryloyloxyethyl carbonate (MEC) was used as the polymerizable organic peroxide, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name " Perhexa 25B ”, 10-hour half-life temperature = 118 ° C., manufactured by NOF CORPORATION) was used.
そして、オートクレーブを６０〜６５℃に昇温し、３時間攪拌することによって、ラジカル重合開始剤及びラジカル（共）重合性有機過酸化物を含む単量体組成物をエチレン−酢酸ビニル共重合体中に含浸させた。 Then, the autoclave is heated to 60 to 65 ° C. and stirred for 3 hours to give a monomer composition containing a radical polymerization initiator and a radical (co) polymerizable organic peroxide to an ethylene-vinyl acetate copolymer. Impregnated in.
その後、オートクレーブを８０〜８５℃に昇温し、当該温度で７時間保持して重合させ、水洗及び乾燥することにより、（Ｂ）ビニル共重合体であるポリ（Ｓｔ／ＧＭＡ／ＭＥＣ）共重合体と、（Ｃ）有機過酸化物である２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサンと、が（Ａ）エチレン−酢酸ビニル共重合体に含浸されたエチレン−酢酸ビニル共重合体樹脂組成物を得た。 Then, the autoclave was heated to 80 to 85 ° C., held at that temperature for 7 hours to polymerize, washed with water and dried to give a poly (St / GMA / MEC) copolymer (B) vinyl copolymer. Ethylene-in which the combined product and (C) 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, which is an organic peroxide, are impregnated in the (A) ethylene-vinyl acetate copolymer. A vinyl acetate copolymer resin composition was obtained.
得られたエチレン−酢酸ビニル共重合体樹脂組成物からポリ（Ｓｔ／ＧＭＡ／ＭＥＣ）共重合体を酢酸エチルで抽出した。ゲル浸透クロマトグラフィー（ＧＰＣ）による測定の結果、ポリ（Ｓｔ／ＧＭＡ／ＭＥＣ）共重合体の重量平均分子量は４０万であることがわかった。 A poly (St / GMA / MEC) copolymer was extracted with ethyl acetate from the obtained ethylene-vinyl acetate copolymer resin composition. As a result of measurement by gel permeation chromatography (GPC), it was found that the weight average molecular weight of the poly (St / GMA / MEC) copolymer was 400,000.
［比較製造例１−１〜１−３の説明］
比較製造例１−１に係るエチレン−酢酸ビニル共重合体樹脂組成物では、上記実施形態とは異なり、（Ｃ）有機過酸化物を添加せず、主鎖同士の架橋反応が行われていない。
[Description of Comparative Production Examples 1-1 to 1-3]
In the ethylene-vinyl acetate copolymer resin composition according to Comparative Production Example 1-1, unlike the above-described embodiment, (C) the organic peroxide is not added, and the crosslinking reaction between the main chains is not performed. .
比較製造例１−２に係るエチレン−酢酸ビニル共重合体樹脂組成物では、（Ａ）エチレン−酢酸ビニル共重合体における酢酸ビニルの含有量が３２重量％であり、ＭＦＲが３０（ｇ／１０ｍｉｎ）と、製造例１−１〜１−１３に比べて高い。 In the ethylene-vinyl acetate copolymer resin composition according to Comparative Production Example 1-2, the content of vinyl acetate in the ethylene-vinyl acetate copolymer (A) was 32% by weight, and the MFR was 30 (g / 10 min). ) Is higher than those of Production Examples 1-1 to 1-13.
比較製造例１−３に係るエチレン−酢酸ビニル共重合体樹脂組成物では、（Ａ）エチレン−酢酸ビニル共重合体の代わりに低密度ポリエチレンが用いられている。 In the ethylene-vinyl acetate copolymer resin composition according to Comparative Production Example 1-3, low density polyethylene is used instead of the (A) ethylene-vinyl acetate copolymer.
表１中の各略称の意味は以下のとおりである。
ＥＶＡ：エチレン−酢酸ビニル共重合体（各実施例及び各比較例では、適宜、以下の３種類のうちいずれか１つを用いている。）
（Ｉ）「ウルトラセン５１０」、東ソー株式会社製、ＶＡｃ含有量６％、ＭＦＲ＝２．５（ｇ／１０ｍｉｎ）
（ＩＩ）「ウルトラセン５３７」、東ソー株式会社製、ＶＡｃ含有量１５％、ＭＦＲ＝３．０（ｇ／１０ｍｉｎ）
（ＩＩＩ）「ウルトラセン７５０」、東ソー株式会社製、ＶＡｃ含有量３２％、ＭＦＲ＝３０（ｇ／１０ｍｉｎ）
ＬＤＰＥ：低密度ポリエチレン（「スミカセンＧ４０１」住友化学株式会社製、密度＝０．９２６ｇ／ｃｍ３）
Ｓｔ：スチレン
ＧＭＡ：メタクリル酸グリシジル
ＡＮ：アクリロニトリル
ＭＥＣ：ｔ−ブチルペルオキシメタクリロイロキシエチルカーボネート
Ｒ３５５：ジ（３，５，５−トリメチルヘキサノイル）パーオキサイド
ＢＷ：ベンゾイルパーオキサイド（「ナイパーＢＷ」、１０時間半減期温度＝７４℃、日油株式会社製）
２５Ｂ：２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン
ＢｕＥ：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（「パーブチルＥ」、１０時間半減期温度＝９９℃、日油株式会社製）
The meaning of each abbreviation in Table 1 is as follows.
EVA: ethylene-vinyl acetate copolymer (in each of Examples and Comparative Examples, any one of the following three types is appropriately used).
(I) "Ultrasen 510", manufactured by Tosoh Corporation, VAc content 6%, MFR = 2.5 (g / 10min)
(II) "Ultrasen 537", manufactured by Tosoh Corporation, VAc content 15%, MFR = 3.0 (g / 10 min)
(III) "Ultrasen 750", manufactured by Tosoh Corporation, VAc content 32%, MFR = 30 (g / 10min)
LDPE: Low-density polyethylene (“Sumikasen G401” manufactured by Sumitomo Chemical Co., Ltd., density = 0.926 g / cm 3 ).
St: Styrene GMA: Glycidyl Methacrylate AN: Acrylonitrile MEC: t-Butylperoxymethacryloyloxyethyl carbonate R355: Di (3,5,5-trimethylhexanoyl) peroxide BW: Benzoyl peroxide (“Nyper BW”, 10 Time half-life temperature = 74 ° C, manufactured by NOF CORPORATION)
25B: 2,5-dimethyl-2,5-di (t-butylperoxy) hexane BuE: t-butylperoxy-2-ethylhexyl monocarbonate (“perbutyl E”, 10 hour half-life temperature = 99 ° C., day) Oil Co., Ltd.)
＜（Ｙ）グラフト共重合体＞
［（Ｙ）グラフト共重合体の製造］
製造例２−１〜２−１３及び比較製造例２−１〜２−３について、表２に示すように、それぞれ製造例１−１〜１−１３及び比較製造例１−１〜１−３に係るエチレン−酢酸ビニル共重合体樹脂組成物を用いて（Ｙ）グラフト共重合体を製造した。この一例として、製造例２−１に係る（Ｙ）グラフト共重合体の製造プロセスを以下に示す。なお、他の製造例及び比較製造例に係る（Ｙ）グラフト共重合体も、製造例２−１と同様のプロセスで製造した。
<(Y) Graft Copolymer>
[Production of (Y) Graft Copolymer]
Regarding Production Examples 2-1 to 2-13 and Comparative Production Examples 2-1 to 2-3, as shown in Table 2, Production Examples 1-1 to 1-13 and Comparative Production Examples 1-1 to 1-3, respectively. A (Y) graft copolymer was produced using the ethylene-vinyl acetate copolymer resin composition according to the above. As an example of this, the production process of the (Y) graft copolymer according to Production Example 2-1 is shown below. The (Y) graft copolymers according to other production examples and comparative production examples were also produced by the same process as in Production Example 2-1.
［製造例２−１に係る（Ｙ）グラフト共重合体の製造］
まず、製造例１−１で得られたエチレン−酢酸ビニル共重合体樹脂組成物をラボプラストミル一軸押出機（株式会社東洋精機製作所製）で２００℃にて溶融混練し、グラフト化反応させることにより主鎖がエチレン−酢酸ビニル共重合体から成り、側鎖がポリ（Ｓｔ／ＧＭＡ）から成る（Ｙ）グラフト共重合体を得た。
[Production of (Y) Graft Copolymer According to Production Example 2-1]
First, the ethylene-vinyl acetate copolymer resin composition obtained in Production Example 1-1 is melt-kneaded at 200 ° C. with a Labo Plastomill uniaxial extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to cause a grafting reaction. Thus, a (Y) graft copolymer having a main chain of ethylene-vinyl acetate copolymer and a side chain of poly (St / GMA) was obtained.
得られた（Ｙ）グラフト共重合体のＭＦＲ（２２０℃／１０ｋｇｆ）を測定したところ、０．６（ｇ／１０ｍｉｎ）であり、グラフト化反応及びエチレン−酢酸ビニル共重合体の架橋反応が進行していることを確認した。また、得られた（Ｙ）グラフト共重合体を走査型電子顕微鏡（「ＪＥＯＬ ＪＳＭ Ｔ３００」、日本電子株式会社製）で観察したところ、粒径０．１〜０．２μｍの真球状樹脂が均一に分散していることが確認された。 The MFR (220 ° C./10 kgf) of the obtained (Y) graft copolymer was 0.6 (g / 10 min), and the grafting reaction and the crosslinking reaction of the ethylene-vinyl acetate copolymer proceeded. I have confirmed that. Moreover, when the obtained (Y) graft copolymer was observed with a scanning electron microscope (“JEOL JSM T300”, manufactured by JEOL Ltd.), a spherical resin having a particle size of 0.1 to 0.2 μm was uniform. It was confirmed that they were dispersed in.
表２から明らかなように、製造例２−１〜２−１３では、グラフト化反応及び（Ａ）エチレン−酢酸ビニル共重合体の架橋反応が進行することにより、（Ｙ）グラフト共重合体のＭＦＲが０．１以上１．１以下の値となり、適切な流動性が得られた。 As is clear from Table 2, in Production Examples 2-1 to 2-13, the grafting reaction and the crosslinking reaction of the (A) ethylene-vinyl acetate copolymer proceed to give a (Y) graft copolymer. The MFR was a value of 0.1 or more and 1.1 or less, and appropriate fluidity was obtained.
これに対し、比較製造例２−１では、（Ａ）エチレン−酢酸ビニル共重合体の主鎖同士の架橋反応が進行せず、（Ｙ）グラフト共重合体のＭＦＲが４．５（ｇ／１０ｍｉｎ）と製造例２−１と比較して高い値を示した。 On the other hand, in Comparative Production Example 2-1, the crosslinking reaction between the main chains of the (A) ethylene-vinyl acetate copolymer did not proceed, and the MFR of the (Y) graft copolymer was 4.5 (g / g). 10 min), which was higher than that of Production Example 2-1.
比較製造例２−２では、（Ａ）エチレン−酢酸ビニル共重合体のＭＦＲが高いため得られた（Ｙ）グラフト共重合体のＭＦＲが１２．８（ｇ／１０ｍｉｎ）と製造例２−１と比較して高い値を示した。 In Comparative Production Example 2-2, since the MFR of the (A) ethylene-vinyl acetate copolymer was high, the MFR of the (Y) graft copolymer obtained was 12.8 (g / 10 min), and Production Example 2-1. It showed a high value compared with.
比較製造例２−３では、（Ａ）エチレン−酢酸ビニル共重合体の代わりに低密度ポリエチレンが用いられているために、主鎖同士の架橋反応が進行しにくく、（Ｙ）グラフト共重合体のＭＦＲが２．６（ｇ／１０ｍｉｎ）と製造例２−１と比較して高い値を示した。 In Comparative Production Example 2-3, since the low-density polyethylene is used instead of the (A) ethylene-vinyl acetate copolymer, the crosslinking reaction between the main chains hardly proceeds, and the (Y) graft copolymer is obtained. Has an MFR of 2.6 (g / 10 min), which is higher than that of Production Example 2-1.
＜ＡＢＳ樹脂組成物＞
［ＡＢＳ樹脂組成物の製造］
実施例１−１〜１−１５及び比較例１−１〜１−５について、表３に示す配合割合で、（Ｘ）ＡＢＳ樹脂（商品名「トヨラック７００−３１４」、標準グレード、東レ株式会社製、表３中で「ＡＢＳ１」と示す）と、に対して、上記の（Ｙ）グラフト共重合体を適宜所定量ドライブレンドし、２４０℃に設定した二軸押出機にて溶融混練し、ＡＢＳ樹脂組成物を得た。
<ABS resin composition>
[Production of ABS resin composition]
For Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-5, (X) ABS resin (trade name "Toyolac 700-314", standard grade, Toray Industries, Inc.) was used in the mixing ratios shown in Table 3. (Shown as “ABS1” in Table 3), and (Y) the above graft copolymer are appropriately dry blended in a predetermined amount, and melt-kneaded by a twin-screw extruder set to 240 ° C., An ABS resin composition was obtained.
実施例１−１，１−４〜１−１５では、それぞれ製造例２−１〜２−１３で得られた（Ｙ）グラフト共重合体の含有量が１０重量部（（Ｘ）を１００重量部とした場合）であるＡＢＳ樹脂組成物を製造した。 In Examples 1-1, 1-4 to 1-15, the content of the (Y) graft copolymer obtained in Production Examples 2-1 to 2-13 was 10 parts by weight (100 parts by weight of (X)). ABS resin composition).
また、実施例１−２、１−３では、それぞれ製造例２−１で得られた（Ｙ）グラフト共重合体の含有量が１重量部、１５重量部（（Ｘ）を１００重量部とした場合）であるＡＢＳ樹脂組成物を製造した。 In Examples 1-2 and 1-3, the content of the (Y) graft copolymer obtained in Production Example 2-1 was 1 part by weight, and 15 parts by weight ((X) was 100 parts by weight). ABS resin composition which is
比較例１−１に係るＡＢＳ樹脂組成物は、（Ｙ）グラフト共重合体を用いずに、（Ｘ）ＡＢＳ樹脂のみにより製造した。比較例１−２では、製造例２−１で得られた（Ｙ）グラフト共重合体の含有量が３０重量部（（Ｘ）を１００重量部とした場合）であるＡＢＳ樹脂組成物を製造した。比較例１−３〜１−５では、比較製造例２−１〜２−３で得られた（Ｙ）グラフト共重合体の含有量が１０重量部（（Ｘ）を１００重量部とした場合）であるＡＢＳ樹脂組成物を製造した。 The ABS resin composition according to Comparative Example 1-1 was produced only with the (X) ABS resin without using the (Y) graft copolymer. In Comparative Example 1-2, an ABS resin composition in which the content of the (Y) graft copolymer obtained in Production Example 2-1 was 30 parts by weight (when (X) was 100 parts by weight) was produced. did. In Comparative Examples 1-3 to 1-5, when the content of the (Y) graft copolymer obtained in Comparative Production Examples 2-1 to 2-3 was 10 parts by weight ((X) was 100 parts by weight). ) Was produced.
実施例２−１及び比較例２−１について、表３に示す配合割合で、（Ｘ）ＡＢＳ樹脂（商品名「Ａｂｓｏｌａｃ３００」、標準グレード、Ｓｔｙｒｏｌｕｔｉｏｎ製、表３中で「ＡＢＳ２」と示す）に対して、上記の（Ｙ）グラフト共重合体を適宜所定量ドライブレンドし、２４０℃に設定した二軸押出機にて溶融混練し、ＡＢＳ樹脂組成物を得た。 For Example 2-1 and Comparative Example 2-1, the (X) ABS resin (trade name "Absolac300", standard grade, manufactured by Styrolution, shown as "ABS2" in Table 3) at the compounding ratios shown in Table 3. On the other hand, the above-mentioned (Y) graft copolymer was appropriately dry blended in a predetermined amount and melt-kneaded with a twin-screw extruder set at 240 ° C. to obtain an ABS resin composition.
実施例２−１では、製造例２−１で得られた（Ｙ）グラフト共重合体の含有量が１０重量部（（Ｘ）を１００重量部とした場合）であるＡＢＳ樹脂組成物を製造した。
比較例２−１に係るＡＢＳ樹脂組成物は、（Ｙ）グラフト共重合体を用いずに、（Ｘ）ＡＢＳ樹脂のみにより製造した。
In Example 2-1, an ABS resin composition having a content of the (Y) graft copolymer obtained in Production Example 2-1 is 10 parts by weight (when (X) is 100 parts by weight) is produced. did.
The ABS resin composition according to Comparative Example 2-1 was produced only with the (X) ABS resin without using the (Y) graft copolymer.
実施例２−１及び比較例２−１について、評価材の作製及び評価方法は、上記の実施例１−１〜１−１５及び比較例１−１〜１−５と同様である。 Regarding Example 2-1 and Comparative example 2-1, the production and evaluation method of the evaluation material are the same as those of Examples 1-1 to 1-15 and Comparative examples 1-1 to 1-5 described above.
［評価材の作製］
実施例１−１〜１−１５及び比較例１−１〜１−５で得られたＡＢＳ樹脂組成物を射出成形機によって成形することにより、実施例１−１〜１−１５及び比較例１−１〜１−５で得られた評価材を作製した。射出成形の条件としては、バレル温度を２４５℃とし、金型温度を８０℃とした。
[Production of evaluation material]
By molding the ABS resin compositions obtained in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-5 by an injection molding machine, Examples 1-1 to 1-15 and Comparative Example 1 The evaluation materials obtained in -1 to 1-5 were produced. As conditions for injection molding, the barrel temperature was 245 ° C and the mold temperature was 80 ° C.
［評価方法］
・引張り強さ
ＪＩＳ Ｋ−７１１３に準拠し、試験速度５０ｍｍ／ｍｉｎとして行った。引張り強さの目標値は、（Ｘ）ＡＢＳ樹脂の種類に応じて決定され、４０ＭＰａ以上とした。
[Evaluation methods]
Tensile strength Based on JIS K-7113, the test speed was 50 mm / min. The target value of tensile strength was determined according to the type of (X) ABS resin and was set to 40 MPa or more.
・曲げ弾性率
ＪＩＳ Ｋ−７２０３に準拠し、試験速度２ｍｍ／ｍｉｎとして行った。曲げ弾性率の目標値は、（Ｘ）ＡＢＳ樹脂の種類に応じて決定され、２．０ＧＰａ以上とした。
Bending elastic modulus It was performed at a test speed of 2 mm / min based on JIS K-7203. The target value of the flexural modulus was determined according to the type of (X) ABS resin and was set to 2.0 GPa or more.
・摺動性評価（スラスト式摩擦摩耗試験）
試験機：オリエンテック株式会社製 摩擦摩耗試験機 ＥＦＭ−ＩＩＩ−Ｆ
評価材：内径２０ｍｍ、外径２５．６ｍｍの円筒材
評価材材質：表３に示す組成のＡＢＳ樹脂組成物
相手材：内径２０ｍｍ、外径２５．６ｍｍの円筒材
相手材材質：（１）炭素鋼（Ｓ４５Ｃ）、（２）ニートＡＢＳ樹脂
試験条件（相手材材質が（１）の場合）：荷重５０Ｎ、線速度１０ｃｍ／ｓｅｃ
試験条件（相手材材質が（２）の場合）：荷重２０Ｎ、線速度１０ｃｍ／ｓｅｃ
試験時間：１００分間
本試験では、各相手材材質（１）（２）について、それぞれ各評価材の摩耗量（ｍｇ）及び動摩擦係数を求めた。
摩耗量及び動摩擦係数の目標値は、（Ｘ）ＡＢＳ樹脂の種類に応じて決定される。本実施例及び比較例では、相手材が（１）炭素鋼（Ｓ４５Ｃ）の場合において、摩耗量の目標値を５．０ｍｇ以下とし、動摩擦係数の目標値を０．２５以下とした。また、相手材が（２）ニートＡＢＳである場合において、摩耗量の目標値を５．０ｍｇ以下とし、動摩擦係数の目標値を０．２５以下とした。なお、ここでいうニートＡＢＳ樹脂とは、グラフト共重合体を添加していないＡＢＳ樹脂である。
・ Sliding property evaluation (thrust type friction and wear test)
Testing machine: manufactured by Orientec Co., Ltd. Friction and wear testing machine EFM-III-F
Evaluation material: Cylindrical material having an inner diameter of 20 mm and an outer diameter of 25.6 mm Evaluation material: ABS resin composition having the composition shown in Table 3 Counterpart material: Cylindrical material having an inner diameter of 20 mm and outer diameter of 25.6 mm Counterpart material: (1) Carbon Steel (S45C), (2) Neat ABS resin Test conditions (when mating material is (1)): Load 50N, linear velocity 10 cm / sec
Test conditions (when the mating material is (2)): load 20 N, linear velocity 10 cm / sec
Test time: 100 minutes In this test, for each mating material (1) and (2), the wear amount (mg) and the dynamic friction coefficient of each evaluation material were obtained.
The target values of the wear amount and the dynamic friction coefficient are determined according to the type of (X) ABS resin. In this example and the comparative example, when the counterpart material was (1) carbon steel (S45C), the target value of the wear amount was 5.0 mg or less and the target value of the dynamic friction coefficient was 0.25 or less. Further, when the mating material is (2) neat ABS, the target value of the wear amount is 5.0 mg or less and the target value of the dynamic friction coefficient is 0.25 or less. The neat ABS resin here is an ABS resin to which no graft copolymer is added.
・軋み音の評価
得られた評価材を、軋み音評価試験用のプレート（６０ｍｍ×１００ｍｍ×２ｍｍ）と、擦り合わせる相手材用としてニートＡＢＳ樹脂プレート（５０ｍｍ×２５ｍｍ×２ｍｍ）と、に切り出してバリ取りを行った後、温度２５℃、湿度５０％でそれぞれ１２時間状態調整した。また、相手材用のプレート（５０ｍｍ×２５ｍｍ×２ｍｍ）として、ステンレス製のプレートも準備した。
-Evaluation of squeaking sound The obtained evaluation material was cut into a plate (60 mm x 100 mm x 2 mm) for a squeaking sound evaluation test and a neat ABS resin plate (50 mm x 25 mm x 2 mm) to be rubbed against. After deburring, the condition was adjusted for 12 hours at a temperature of 25 ° C. and a humidity of 50%. A stainless steel plate was also prepared as a plate (50 mm × 25 mm × 2 mm) for the mating material.
軋み音評価試験用のプレートと、相手材としての各プレートをＺｉｅｇｌｅｒ社のスティックスリップ測定装置ＳＳＰ−０２に固定し、荷重＝４０Ｎ、速度＝１ｍｍ／ｓの条件でそれぞれ擦り合わせた時の軋み音リスク値の測定を行った。なお、軋み音リスク値は、値が小さいほど軋み音発生のリスクが低いことを示す。軋み音リスク値の判断基準は以下に示す通りである。 A squeaking sound when the plate for squeaking sound evaluation test and each plate as a mating material were fixed to a stick slip measuring device SSP-02 of Ziegler and rubbed under the conditions of load = 40N and speed = 1 mm / s. The risk value was measured. The smaller the squeaking noise risk value, the lower the risk of squeaking noise generation. The criteria for squeaking noise risk value are as follows.
軋み音リスク値１〜３：軋み音発生のリスクが低い
軋み音リスク値４〜５：軋み音発生のリスクがやや高い
軋み音リスク値６〜１０：軋み音発生のリスクが高い
Squeaking noise risk value 1-3: low risk of squeaking noise 4-10: Risk of squeaking noise is slightly high Risk of squeaking noise value 6-10: High risk of squeaking noise
軋み音リスク値の目標値は、（Ｘ）ＡＢＳ樹脂の種類に応じて決定される。本実施例及び比較例では、相手材が（１）炭素鋼（Ｓ４５Ｃ）の場合における軋み音リスク値の目標値を３以下とし、相手材が（２）ニートＡＢＳ樹脂である場合における軋み音リスク値の目標値を３以下とした。 The target value of the squeaking noise risk value is determined according to the type of (X) ABS resin. In this example and the comparative example, the target value of the squeaking noise risk value in the case where the mating material is (1) carbon steel (S45C) is set to 3 or less, and the squeaking noise risk in the case where the mating material is (2) neat ABS resin. The target value was set to 3 or less.
表３は、実施例１−１〜１−１５、実施例２−１及び比較例１−１〜１−５、比較例２−１に係る評価材について、相手材材質に（１）炭素鋼（Ｓ４５Ｃ）及び（２）ニートＡＢＳ樹脂を用いたときのスラスト式摩擦摩耗試験の摺動性評価及び軋み音評価の結果を示す。 Table 3 shows (1) carbon steel as the mating material for the evaluation materials according to Examples 1-1 to 1-15, Example 2-1 and Comparative Examples 1-1 to 1-5 and Comparative Example 2-1. (S45C) and (2) The results of the slidability evaluation and the squeaking noise evaluation in the thrust type friction and wear test when using neat ABS resin are shown.
表３中の各略称の意味は以下のとおりである。
ＡＢＳ１：「トヨラック７００−３１４」、標準グレード、東レ株式会社製
ＡＢＳ２：「Ａｂｓｏｌａｃ３００」、Ｓｔｙｒｏｌｕｔｉｏｎ製
The meaning of each abbreviation in Table 3 is as follows.
ABS1: "Toyolac 700-314", standard grade, manufactured by Toray Industries, Ltd. ABS2: "Absolac300", manufactured by Styrolution
［評価結果］
（実施例について）
・機械物性
実施例１−１〜１−１５及び実施例２−１に係る評価材ではいずれも、引張り強さが４０ＭＰａ以上の大きい値であり、曲げ弾性率が２．０ＧＰａ以上の高い値であった。
[Evaluation results]
(Examples)
Mechanical Properties In the evaluation materials according to Examples 1-1 to 1-15 and Example 2-1, the tensile strength has a large value of 40 MPa or more and the bending elastic modulus has a high value of 2.0 GPa or more. there were.
・摺動性評価
実施例１−１〜１−１５及び実施例２−１に係る評価材ではいずれも、相手材を（１）炭素鋼（Ｓ４５Ｃ）とするスラスト式摩擦摩耗試験において、摩耗量が５．０ｍｇ以下、動摩擦係数が０．２５以下の低い値が得られた。
-Sliding property evaluation In all of the evaluation materials according to Examples 1-1 to 1-15 and Example 2-1, the wear amount in the thrust type friction wear test using the counterpart material (1) carbon steel (S45C) Was 5.0 mg or less and the dynamic friction coefficient was 0.25 or less.
実施例１−１〜１−１５及び実施例２−１に係る評価材ではいずれも、相手材を（２）ニートＡＢＳ樹脂とするスラスト式摩擦摩耗試験においても、摩耗量が５．０ｍｇ以下、動摩擦係数が０．２５以下の低い値であった。 In each of the evaluation materials according to Examples 1-1 to 1-15 and Example 2-1, the wear amount was 5.0 mg or less in the thrust type friction wear test using the mating material (2) neat ABS resin. The dynamic friction coefficient was a low value of 0.25 or less.
・軋み音評価
実施例１−１〜１−１５及び実施例２−１に係る評価材ではいずれも、相手材を（１）炭素鋼（Ｓ４５Ｃ）及び（２）ニートＡＢＳ樹脂とした場合の摺動時の軋み音リスク値が３以下の小さい値であった。
-Squeak noise evaluation In all of the evaluation materials according to Examples 1-1 to 1-15 and Example 2-1, sliding when the mating material is (1) carbon steel (S45C) and (2) neat ABS resin The squeaking noise risk value during movement was a small value of 3 or less.
（比較例について）
（Ｘ）ＡＢＳ樹脂のみを用いる比較例１−１では、相手材を（１）炭素鋼（Ｓ４５Ｃ）とするスラスト式摩擦摩耗試験において、摩耗量が５．０（ｍｇ）、動摩擦係数が０．２５を上回っていた。また、比較例１−１では、相手材を（２）ニートＡＢＳ樹脂とするスラスト式摩擦摩耗試験において、摩耗量が５．０（ｍｇ）、動摩擦係数が０．２５を上回っていた。更に、比較例１−１では、相手材を（１）炭素鋼（Ｓ４５Ｃ）及び（２）ニートＡＢＳ樹脂とした場合の摺動時の軋み音リスク値が３を上回っていた。
(About Comparative Example)
In Comparative Example 1-1 using only (X) ABS resin, the amount of wear was 5.0 (mg) and the coefficient of dynamic friction was 0. 0 in the thrust type friction wear test using the counterpart material (1) carbon steel (S45C). It was over 25. In Comparative Example 1-1, the wear amount was 5.0 (mg) and the dynamic friction coefficient was more than 0.25 in the thrust type friction wear test using the mating material (2) neat ABS resin. Furthermore, in Comparative Example 1-1, the squeaking noise risk value during sliding was greater than 3 when the counterpart materials were (1) carbon steel (S45C) and (2) neat ABS resin.
製造例２−１に係る（Ｙ）グラフト共重合体の含有量が３０重量部（（Ｘ）が１００重量部とした場合）である比較例１−２では、引張り強さが４０ＭＰａ以下及び曲げ弾性率が２．０ＧＰａ以下の低い値であった。 In Comparative Example 1-2 in which the content of the (Y) graft copolymer according to Production Example 2-1 is 30 parts by weight (when (X) is 100 parts by weight), the tensile strength is 40 MPa or less and bending The elastic modulus was a low value of 2.0 GPa or less.
（Ａ）エチレン−酢酸ビニル共重合体の主鎖同士が架橋していない比較例１−３では、相手材を（１）炭素鋼（Ｓ４５Ｃ）とするスラスト式摩擦摩耗試験において、摩耗量が５．０（ｍｇ）を上回っていた。また、比較例１−３では、相手材を（２）ニートＡＢＳ樹脂とするスラスト式摩擦摩耗試験において、摩耗量が５．０（ｍｇ）を上回っていた。 In Comparative Example 1-3 in which the main chains of the ethylene-vinyl acetate copolymer (A) are not cross-linked with each other, the wear amount is 5 in the thrust type friction wear test in which the counterpart material is (1) carbon steel (S45C). It was above 0.0 (mg). Moreover, in Comparative Example 1-3, the wear amount was more than 5.0 (mg) in the thrust type friction wear test using the mating ABS resin (2).
（Ａ）エチレン−酢酸ビニル共重合体における酢酸ビニルの含有量が多く、（Ｙ）グラフト共重合体のＭＦＲが高い値を示した比較例１−４では、相手材を（１）炭素鋼（Ｓ４５Ｃ）とするスラスト式摩擦摩耗試験において、摩耗量が５．０（ｍｇ）、動摩擦係数が０．２５を上回っていた。また、比較例１−４では、相手材を（２）ニートＡＢＳ樹脂とするスラスト式摩擦摩耗試験において、摩耗量が５．０（ｍｇ）、動摩擦係数が０．２５を上回っていた。 In Comparative Example 1-4 in which the content of vinyl acetate in the (A) ethylene-vinyl acetate copolymer was high and the MFR of the (Y) graft copolymer was high, the counterpart material was (1) carbon steel ( In the thrust friction wear test of S45C), the wear amount was 5.0 (mg) and the dynamic friction coefficient was more than 0.25. In Comparative Example 1-4, the amount of wear was 5.0 (mg) and the coefficient of kinetic friction was more than 0.25 in the thrust type friction and wear test using the mating material (2) neat ABS resin.
（Ａ）エチレン−酢酸ビニル共重合体の代わりに低密度ポリエチレンを用いた比較例１−５では、相手材を（２）ニートＡＢＳ樹脂とした場合の軋み音リスク値が３を上回っていた。 In Comparative Example 1-5 in which low density polyethylene was used in place of (A) ethylene-vinyl acetate copolymer, the squeaking noise risk value was more than 3 when the counterpart material was (2) neat ABS resin.
（Ｘ）ＡＢＳ樹脂のみを用いる比較例２−１では、相手材を（１）炭素鋼（Ｓ４５Ｃ）とするスラスト式摩擦摩耗試験において、摩耗量が５．０（ｍｇ）、動摩擦係数が０．２５を上回っていた。また、比較例２−１では、相手材を（２）ニートＡＢＳ樹脂とするスラスト式摩擦摩耗試験において、摩耗量が５．０（ｍｇ）、動摩擦係数が０．２５を上回っていた。更に、比較例２−１では、相手材を（１）炭素鋼（Ｓ４５Ｃ）及び（２）ニートＡＢＳ樹脂とした場合の軋み音リスク値が３を上回っていた。 In Comparative Example 2-1 using only the (X) ABS resin, the amount of wear was 5.0 (mg) and the coefficient of dynamic friction was 0. It was over 25. In Comparative Example 2-1, the wear amount was 5.0 (mg) and the dynamic friction coefficient was more than 0.25 in the thrust type friction wear test using the mating material (2) neat ABS resin. Further, in Comparative Example 2-1, the squeaking noise risk value was more than 3 when the counterpart materials were (1) carbon steel (S45C) and (2) neat ABS resin.
以上、本発明の実施形態について説明したが、本発明は上述の実施形態にのみ限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加え得ることは勿論である。
Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and it goes without saying that various changes can be made without departing from the scope of the present invention.
Claims (3)
前記（Ｙ）グラフト共重合体の主鎖が、（Ａ）エチレン−酢酸ビニル共重合体から成り、
前記（Ｙ）グラフト共重合体の側鎖が、（ｂ−１）スチレンと、（ｂ−２）アクリロニトリル及びメタクリル酸グリシジルの少なくとも１つと、を含有する（Ｂ）ビニル共重合体から成り、
前記（Ｙ）グラフト共重合体の主鎖同士が架橋されており、
前記（Ｘ）ＡＢＳ樹脂の含有量を１００重量部とすると、前記（Ｙ）グラフト共重合体の含有量が１〜２５重量部であり、
前記（Ａ）エチレン−酢酸ビニル共重合体において、酢酸ビニルの含有量が1重量％以上、２０重量％以下であり、
前記（Ｙ）グラフト共重合体の主鎖同士が、前記（Ａ）エチレン−酢酸ビニル共重合体１００重量部に対して０．１〜３重量部の（Ｃ）有機過酸化物によって架橋されている、ＡＢＳ樹脂組成物。 Containing (X) ABS resin and (Y) graft copolymer,
The main chain of the (Y) graft copolymer is composed of (A) ethylene-vinyl acetate copolymer,
The side chain of the (Y) graft copolymer is composed of (b) a vinyl copolymer containing (b-1) styrene and (b-2) at least one of acrylonitrile and glycidyl methacrylate,
The main chains of the (Y) graft copolymer are crosslinked,
When the content of the (X) ABS resin is 100 parts by weight, the content of the (Y) graft copolymer is 1 to 25 parts by weight,
(A) the ethylene - in vinyl acetate copolymer, vinyl acetate content is 1 wt% or more state, and are 20 wt% or less,
The main chains of the (Y) graft copolymer are crosslinked by 0.1 to 3 parts by weight of the (C) organic peroxide with respect to 100 parts by weight of the (A) ethylene-vinyl acetate copolymer. ABS resin composition.
前記（Ａ）エチレン−酢酸ビニル共重合体と、前記（ｂ−１）スチレンと、前記（ｂ−２）アクリロニトリル及びメタクリル酸グリシジルの少なくとも１つと、の含有量の合計を１００重量部とすると、前記（Ａ）エチレン−酢酸ビニル共重合体の含有量が５０〜９０重量部である
ＡＢＳ樹脂組成物。 The ABS resin composition according to claim 1, wherein
When the total content of the (A) ethylene-vinyl acetate copolymer, the (b-1) styrene, and (b-2) at least one of acrylonitrile and glycidyl methacrylate is 100 parts by weight, ABS resin composition in which the content of the (A) ethylene-vinyl acetate copolymer is 50 to 90 parts by weight.
樹脂成形品。
According to claim 1 or 2, wherein ABS resin composition molded article obtained by molding the.
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| PCT/JP2015/081937 WO2016080298A1 (en) | 2014-11-18 | 2015-11-13 | Ethylene-vinyl acetate copolymer resin composition, graft copolymer, thermoplastic resin composition, and molded resin article |
| EP15860127.8A EP3222643B1 (en) | 2014-11-18 | 2015-11-13 | Ethylene-vinyl acetate copolymer resin composition, graft copolymer, thermoplastic resin composition, and molded resin article |
| KR1020177016511A KR102420906B1 (en) | 2014-11-18 | 2015-11-13 | Ethylene-vinyl acetate copolymer resin composition, graft copolymer, thermoplastic resin composition, and molded resin article |
| CN201580059942.XA CN107148432B (en) | 2014-11-18 | 2015-11-13 | Ethylene-vinyl acetate copolymer resin composition, graft copolymer, thermoplastic resin composition and synthetic resin |
| ES15860127T ES2894040T3 (en) | 2014-11-18 | 2015-11-13 | Ethylene-vinyl acetate copolymer resin composition, graft copolymer, thermoplastic resin composition, and resin molded article |
| US15/527,346 US10131778B2 (en) | 2014-11-18 | 2015-11-13 | Ethylene vinyl acetate copolymer resin composition, graft copolymer, thermoplastic resin composition, and molded resin article |
| TW104137796A TWI577724B (en) | 2014-11-18 | 2015-11-17 | Ethylene-vinyl acetate copolymer resin composition, graft copolymer, thermoplastic resin composition and resin molded article |
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