WO2023008417A1 - ポリアリーレンサルファイド樹脂組成物及びインサート成形品 - Google Patents
ポリアリーレンサルファイド樹脂組成物及びインサート成形品 Download PDFInfo
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- WO2023008417A1 WO2023008417A1 PCT/JP2022/028754 JP2022028754W WO2023008417A1 WO 2023008417 A1 WO2023008417 A1 WO 2023008417A1 JP 2022028754 W JP2022028754 W JP 2022028754W WO 2023008417 A1 WO2023008417 A1 WO 2023008417A1
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- Prior art keywords
- group
- olefin
- parts
- mass
- resin composition
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 60
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 32
- 229920001577 copolymer Polymers 0.000 claims abstract description 129
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- 239000011347 resin Substances 0.000 claims abstract description 107
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 48
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 47
- 150000001336 alkenes Chemical class 0.000 claims abstract description 44
- 239000002071 nanotube Substances 0.000 claims abstract description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 37
- 239000004711 α-olefin Substances 0.000 claims abstract description 35
- 239000002717 carbon nanostructure Substances 0.000 claims abstract description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- 239000011256 inorganic filler Substances 0.000 claims description 54
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 54
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 21
- -1 alkoxysilane group Chemical group 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 14
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- 239000002184 metal Substances 0.000 claims description 13
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- 239000005977 Ethylene Substances 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 claims description 3
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 4
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- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical group C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-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
- 239000000975 dye Substances 0.000 description 1
- WRAHMWZGOGRESS-UHFFFAOYSA-N ethene;2-(oxiran-2-ylmethoxymethyl)oxirane Chemical group C=C.C1OC1COCC1CO1 WRAHMWZGOGRESS-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
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- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005650 substituted phenylene group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
Definitions
- the present invention relates to polyarylene sulfide resin compositions and insert molded articles.
- PAS resins Polyarylene sulfide resins
- PPS resins polyphenylene sulfide resins
- PAS resins have high heat resistance, mechanical properties, chemical resistance, dimensional stability, Flame retardant. Therefore, it is widely used for electrical and electronic device parts, automotive device parts, chemical device parts, and the like.
- PAS resin has a slow crystallization speed, there are problems in that the cycle time during molding is long and that burrs are often generated during molding.
- Patent Document 3 a resin composition containing two types of PPS resins with different melt viscosities and kaolin, attapulgite, or a mixture thereof having a predetermined average particle size has been proposed (see Patent Document 4).
- the carbon nanotubes used in the resin composition described in Patent Document 3 have an average diameter of 5 to 100 nm and an aspect ratio of 50 to 2000, and are different from the carbon nanotubes targeted by the present invention. Further, in Patent Document 4, kaolin, attapulgite, or a mixture thereof having a predetermined average particle size is believed to have the effect of imparting thixotropy to the material (the effect of increasing the shear rate dependence of melt viscosity).
- the inorganic filler such as kaolin is used for the purpose of increasing the melt viscosity of the material in injection molding at once, so it is thought that a certain amount or more is necessary. On the other hand, it is described that 10 to 150 parts by weight is preferable. Addition of an inorganic filler such as kaolin can suppress the generation of burrs, but there is concern that a large amount of addition may cause other problems such as reduction in moldability and strength.
- PAS resin alone lacks toughness and is brittle. It is If the PAS resin composition can achieve both suppression of burr generation and excellent heat shock resistance, its usefulness will be further increased.
- the present invention has been made in view of the conventional problems described above, and its object is to provide a polyarylene sulfide resin composition capable of achieving both suppression of burr generation and excellent heat shock resistance. to do.
- One aspect of the present invention for achieving the above object is as follows.
- (1) With respect to 100 parts by mass of a polyarylene sulfide resin having a terminal carboxyl group and a melt viscosity of 5 to 500 Pa s measured at a temperature of 310°C and a shear rate of 1200 sec -1 ,
- B (B1) 0.05 to 1.5 parts by mass of carbon nanotubes having a length of more than 10,000 nm and less than or equal to 3,000,000 nm and an aspect ratio of more than 2,000 and less than or equal to 500,000; ) of 0.01 parts by mass or more and less than 10 parts by mass, or (B3) 0.01 to 5 parts by mass of carbon nanostructures,
- C 1.0 to 45.0 parts by mass of an olefin-based copolymer containing a structural unit derived from an ⁇ -olefin having 2 or more carbon atoms
- a polyarylene sulfide resin composition comprising:
- the (C1) olefin-based copolymer is at least one selected from the group consisting of maleic anhydride-modified ethylene-based copolymers, glycidyl methacrylate-modified ethylene-based copolymers, and glycidyl ether-modified ethylene-based copolymers.
- An insert-molded product comprising a resin member containing the polyarylene sulfide resin composition according to any one of (1) to (8) above, and an insert member containing a metal, alloy or inorganic solid.
- the polyarylene sulfide resin composition of the present embodiment comprises: (A) 100 parts by mass of a polyarylene sulfide resin having a terminal carboxyl group and having a melt viscosity of 5 to 500 Pa s measured at a temperature of 310° C. and a shear rate of 1200 sec ⁇ 1
- (B) (B1) carbon nanotubes having a length of more than 10,000 nm and 3,000,000 nm or less and an aspect ratio of more than 2,000 and 500,000 or less are 0.05 to 1.5 parts by mass
- the PAS resin composition of the present embodiment contains (B1) carbon nanotubes (hereinafter also referred to as "CNT”), (B2) inorganic nanotubes, or (B3) carbon nanostructures (hereinafter also referred to as "CNS").
- CNT carbon nanotubes
- B2 inorganic nanotubes inorganic nanotubes
- B3 carbon nanostructures
- B1 CNTs The mechanism by which burrs are suppressed by CNTs having a given length and a given aspect ratio is due to the contribution of increased melt viscosity in the low shear rate region and improved crystallization speed (improved solidification speed due to nucleating agent effect).
- the increase in melt viscosity in the low shear rate region can reduce mold release resistance, and the improvement in crystallization speed can shorten the molding cycle.
- B2 Inorganic nanotubes It is presumed that the mechanism by which burrs are suppressed by the addition of inorganic nanotubes contributes to the improvement of the crystallization speed (improvement of the solidification speed due to the nucleating agent effect). Also, the molding cycle can be shortened by improving the crystallization speed.
- B3 CNS It is presumed that the mechanism by which the addition of CNS contributes to the suppression of burrs by the increase in melt viscosity in the low shear rate region and the improvement in crystallization speed (improvement in solidification speed due to nucleating agent effect).
- the increase in melt viscosity in the low shear rate region can reduce mold release resistance, and the improvement in crystallization speed can shorten the molding cycle.
- the term "nucleating agent” is synonymous with “crystal nucleating agent”, “nucleating agent” and the like.
- the PAS resin composition of the present embodiment contains (C) an olefin-based copolymer containing a structural unit derived from an ⁇ -olefin having 2 or more carbon atoms, it has excellent heat shock resistance.
- the mechanism by which the (C) olefin-based copolymer improves the heat shock resistance is that the inclusion of (C) the olefin-based copolymer easily imparts flexibility to the resin member. It is considered that the softening of the resin member due to the addition of N contributes to the improvement of the heat shock resistance.
- olefin-based copolymers containing structural units derived from ethylene and structural units derived from ⁇ -olefins having 3 or more carbon atoms, and structural units derived from ⁇ -olefins having 2 or more carbon atoms and ⁇ , ⁇ -
- An olefinic copolymer containing a structural unit derived from an unsaturated carboxylic acid alkyl ester easily imparts flexibility to a resin member.
- the (C) olefinic copolymer contains a specific functional group, the functional group reacts with the terminal group of the PAS resin, and this reaction causes mutual interaction between the PAS resin and the olefinic copolymer.
- the functional group is preferably a functional group that reacts with the terminal carboxyl group of the PAS resin.
- the heat shock resistance is also improved by including the above components (B1) to (B3). Although the mechanism is unknown, it is clear from experimental facts (see Examples below). Each component of the PAS resin composition of the present embodiment will be described below.
- PAS resins are characterized by excellent mechanical properties, electrical properties, heat resistance and other physical and chemical properties, and good workability.
- the PAS resin is mainly a polymer compound composed of -(Ar-S)- (where Ar is an arylene group) as a repeating unit.
- Ar is an arylene group
- a PAS resin having a generally known molecular structure is used. can be used.
- arylene group examples include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p,p'-diphenylenesulfone group, p,p'-biphenylene group, p,p'- diphenylene ether group, p,p'-diphenylenecarbonyl group, naphthalene group and the like.
- the PAS resin may be a homopolymer consisting only of the repeating units described above, or a copolymer containing the following heterogeneous repeating units may be preferable from the standpoint of workability and the like.
- a polyphenylene sulfide resin in which p-phenylene groups are used as arylene groups and p-phenylene sulfide groups are used as repeating units is preferably used.
- a combination of two or more different arylene sulfide groups consisting of the above arylene groups can be used. Among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferred. Used.
- PAS resins those containing 70 mol % or more, preferably 80 mol % or more of p-phenylene sulfide groups are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties.
- PAS resins a substantially linear high-molecular-weight polymer obtained by polycondensation from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used.
- the PAS resin used in this embodiment may be a mixture of two or more different molecular weight PAS resins.
- a small amount of a monomer such as a polyhaloaromatic compound having 3 or more halogen substituents is used during condensation polymerization to partially form a branched or crosslinked structure.
- the PAS resin can be produced by a conventionally known polymerization method.
- a PAS resin produced by a general polymerization method is usually washed several times with water or acetone, and then washed with acetic acid, ammonium chloride or the like in order to remove by-product impurities.
- the PAS resin ends contain carboxyl group ends in a predetermined ratio.
- the melt viscosity (310° C., shear rate 1200 sec ⁇ 1 ) of the PAS resin as the base resin used in this embodiment is 5 to 500 Pa from the viewpoint of the balance between mechanical properties and fluidity, including the case of the mixed system. ⁇ Use s.
- the melt viscosity of the PAS resin is preferably 7 to 300 Pa ⁇ s, more preferably 10 to 250 Pa ⁇ s, and particularly preferably 13 to 200 Pa ⁇ s.
- the PAS resin composition of the present embodiment may contain other resin components in addition to the PAS resin as resin components within a range that does not impair its effect.
- Other resin components are not particularly limited, and examples include polyethylene resin, polypropylene resin, polyamide resin, polyacetal resin, modified polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyimide resin, and polyamideimide.
- Resin polyetherimide resin, polysulfone resin, polyethersulfone resin, polyetherketone resin, polyetheretherketone resin, liquid crystal resin, fluorine resin, cyclic olefin resin (cyclic olefin polymer, cyclic olefin copolymer, etc.), thermoplastic Elastomers, silicone-based polymers, various biodegradable resins, and the like are included. Moreover, you may use together 2 or more types of resin components. Among them, polyamide resins, modified polyphenylene ether resins, liquid crystal resins, and the like are preferably used from the viewpoint of mechanical properties, electrical properties, physical/chemical properties, workability, and the like.
- the CNTs used in this embodiment have a length of more than 10,000 nm and no more than 3,000,000 nm and an aspect ratio of more than 2,000 and no more than 500,000. By using the CNTs, it is possible to suppress the generation of burrs even when the amount of addition is relatively small.
- the CNTs used in this embodiment may be either single-walled carbon nanotubes or multi-walled carbon nanotubes.
- the aspect ratio of the CNT is a numerical value obtained by dividing the length of the CNT by the diameter of the CNT, and a manufacturer's value (numerical value published by the manufacturer in a catalog or the like) can be adopted.
- the length of more than 10,000 nm and 3,000,000 nm or less and the aspect ratio of more than 2,000 and 500,000 or less combine to suppress the generation of burrs.
- the length of CNT is preferably 11000-1500000 nm, more preferably 12000-500000 nm.
- the aspect ratio of CNT is preferably 2010 to 250000, more preferably 2030 to 100000.
- the diameter of the CNT is preferably 5 to 100 nm, more preferably 7 to 50 nm.
- 0.05 to 1.5 parts by mass of CNTs are contained with respect to 100 parts by mass of PAS resin. If the CNT is less than 0.05 parts by mass, the occurrence of burrs cannot be suppressed. Moreover, when the CNT exceeds 1.5 parts by mass, conductivity is likely to be imparted.
- the PAS resin composition of the present embodiment is suitable for insert-molded products because it has excellent heat shock resistance. However, when used for an insert-molded product, the PAS resin composition of the present embodiment preferably maintains insulating properties.
- the CNT content is preferably 0.1 to 1.4 parts by mass, more preferably 0.2 to 1.3 parts by mass.
- CNTs Commercially available CNTs according to the present embodiment include CP1002M manufactured by LG Chemical Co., Ltd., NTF series manufactured by Koatsu Gas Kogyo Co., Ltd., and the like.
- the suppression of burr generation by the inorganic nanotubes is considered to be due to the improvement in the solidification speed due to the nucleating agent effect, as described above. Therefore, even if it is added in a relatively small amount, it is possible to suppress the generation of burrs.
- the inorganic nanotube is limited to those containing no carbon atoms. Therefore, in this embodiment, inorganic nanotubes do not include carbon nanotubes.
- Inorganic nanotubes are tube-shaped inorganic substances with diameters on the order of nanometers. Furthermore, many inorganic nanotubes generally have insulating properties, and the use of insulating inorganic nanotubes does not reduce the insulating properties of the PAS resin composition. In that respect, it differs from the one using carbon nanotubes.
- Inorganic nanotubes used in this embodiment include aluminosilicate nanotubes, boron nitride nanotubes, titanium oxide nanotubes, metal sulfide nanotubes, metal halide nanotubes, and the like. Halloysite nanotubes or metahalloysite nanotubes are preferred as the aluminosilicate nanotubes. Among these, halloysite nanotubes are preferred from the viewpoint of low cost and availability. Further, metal sulfide nanotubes include molybdenum sulfide, tungsten sulfide, copper sulfide nanotubes, and the like. Metal halide nanotubes include nickel chloride, cadmium chloride, or cadmium iodide nanotubes.
- the average length of the inorganic nanotubes is preferably 100 nm to 20 ⁇ m, more preferably 500 nm to 15 ⁇ m, even more preferably 1 to 10 ⁇ m, particularly preferably 1 to 5 ⁇ m. .
- the average outer diameter of the inorganic nanotubes is preferably 5 to 100 nm, more preferably 10 to 80 nm, even more preferably 30 to 70 nm.
- the aspect ratio of the inorganic nanotube is preferably 1-4000, more preferably 5-2000.
- the aspect ratio of the inorganic nanotube is a numerical value obtained by dividing the length of the inorganic nanotube by the diameter of the inorganic nanotube, and a manufacturer's value (numerical value published by the manufacturer in a catalog or the like) can be adopted.
- the PAS resin composition of the present embodiment contains 0.01 parts by mass or more and less than 10 parts by mass of inorganic nanotubes with respect to 100 parts by mass of the PAS resin and is less than 0.01 parts by mass, the effect of suppressing the generation of burrs is obtained. If the amount is not sufficient and the amount is 10 parts by mass or more, mechanical properties such as Charpy impact strength tend to deteriorate.
- the content of inorganic nanotubes is preferably 0.5 to 9.9 parts by mass, more preferably 1.0 to 9.5 parts by mass.
- Halloysite G (685445) manufactured by Applied Minerals Co., Ltd., etc. can be mentioned as a commercially available halloysite nanotube among the inorganic nanotubes according to the present embodiment.
- the CNS used in this embodiment is a structure containing a plurality of carbon nanotubes bonded together, and the carbon nanotubes are bonded to other carbon nanotubes in a branched bond or crosslinked structure. Details of such CNS can be found in US Patent Application Publication No. 2013-0071565, US Patent Nos. 9,113,031, 9,447,259, 9,111,658. described in the specification.
- the CNS used in this embodiment may be a commercial product.
- ATHLOS 200, ATHLOS 100, etc. manufactured by CABOT can be used.
- ATHLOS 200 has an average fiber diameter of about 10 nm of carbon nanotubes as the minimum unit constituting the CNS.
- the average fiber diameter of carbon nanotubes as the minimum unit constituting the CNS can be, for example, 0.1 to 50 nm, preferably 0.1 to 30 nm.
- the amount of CNS added is preferably 0.05 to 3 parts by mass, more preferably 0.15 to 2.5 parts by mass, and particularly preferably 0.5 to 1.7 parts by mass.
- the PAS resin composition of the present embodiment is suitable for insert-molded products because it has excellent heat shock resistance. When used for an insert-molded article, the PAS resin composition of the present embodiment preferably maintains insulating properties. From this point of view, the amount of the CNS added is 0.01 to 0.5 parts by mass. It is preferably 0.03 to 0.45 parts by mass, still more preferably 0.05 to 0.4 parts by mass, and particularly preferably 0.1 to 0.35 parts by mass.
- the method for adding the components (B1) to (B3) to the PAS resin is not particularly limited, and conventionally known methods can be used.
- the timing for adding the components (B1) to (B3) includes, for example, the time of polymerizing the PAS resin and the time of melting and kneading the raw materials in the preparation of the PAS resin composition.
- the timing of adding the components (B1) to (B3) during melt kneading of the raw materials is, for example, once the PAS resin and the components (B1) to (B3) are heated and melt kneaded. and may be used as a pelletized masterbatch.
- the masterbatch may be produced using a resin other than the PAS resin as long as the burr suppressing effect of the components (B1) to (B3) is not impaired.
- the PAS resin and components (B1) to (B3) may be added once as a mixture obtained by simply stirring.
- a method of dry blending the PAS resin and components (B1) to (B3) may be used, and a blending method using a tumbler or a Henschel mixer may also be used.
- the PAS resin and the components (B1) to (B3) may be supplied to an extruder, or the PAS resin and Components (B1) to (B3) and other compounding agents may be dry-blended and then supplied to the extruder, or a part of the raw materials may be supplied by a side-feed method.
- the (C) olefin-based copolymer used in the present embodiment contains structural units derived from an ⁇ -olefin having 2 or more carbon atoms.
- the olefinic copolymer is used to improve heat shock resistance. That is, as described above, by including the olefin copolymer, flexibility is easily imparted to the resin member, and the softening of the resin member due to the impartation of flexibility contributes to the improvement of heat shock resistance. considered to contribute.
- (C) As the olefinic copolymer, at least one selected from the group consisting of the following (C1) olefinic copolymer, (C2) olefinic copolymer and (C3) olefinic copolymer Olefinic copolymers are preferred.
- C3
- the olefinic copolymer is an olefinic copolymer containing the above specific functional group. That is, the (C1) olefinic copolymer is an olefinic copolymer containing a structural unit derived from an ⁇ -olefin having 2 or more carbon atoms and the above specific functional group.
- the olefinic copolymer contains the specific functional group, the functional group reacts with the terminal group of the PAS resin, thereby increasing the interaction between the PAS resin and the olefinic copolymer. It is presumed that such enhanced interaction further improves the heat shock resistance.
- the functional group is a functional group that reacts with the carboxyl terminal group of the PAS resin.
- the above functional groups an acid anhydride group, an epoxy group, and a glycidyl group are more preferred, and an epoxy group and a glycidyl group are even more preferred.
- the ⁇ -olefin having 2 or more carbon atoms (hereinafter also simply referred to as “ ⁇ -olefin”) is not particularly limited, and examples include ethylene, propylene, butylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like can be mentioned. Among them, ethylene is preferred.
- the ⁇ -olefins may be used singly or in combination of two or more.
- the content of the structural unit derived from the ⁇ -olefin is not particularly limited, but can be, for example, 0.5 to 20% by mass in the total resin composition.
- the glycidyl group- or epoxy group-containing olefin-based copolymer which is one of the olefin-based copolymers, includes olefin-based copolymers having glycidyl esters, glycidyl ethers, etc. in the side chains, and double bonds. Epoxy-oxidized double bond portion of the olefin-based copolymer having such a compound may be mentioned.
- a more specific embodiment of such a glycidyl group- or epoxy group-containing olefin-based (co)polymer includes an olefin-based copolymer obtained by copolymerizing a monomer having a glycidyl group or an epoxy group.
- Glycidyl group-containing olefinic copolymers obtained by copolymerizing glycidyl esters of ⁇ , ⁇ -unsaturated acids are preferably used.
- the olefin-based copolymer preferably contains a structural unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid in addition to a structural unit derived from an ⁇ -olefin having 2 or more carbon atoms. Structural units derived from glycidyl esters of ⁇ , ⁇ -unsaturated acids are described below.
- the (meth)acrylic acid alkyl ester is also referred to as (meth)alkyl acrylate.
- glycidyl (meth)acrylate is also referred to as glycidyl (meth)acrylate.
- “(meth)acrylic acid” means both acrylic acid and methacrylic acid
- (meth)acrylate” means both acrylate and methacrylate.
- Glycidyl esters of ⁇ , ⁇ -unsaturated acids are not particularly limited, and examples thereof include those having a structure represented by the following general formula (1). can.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- Examples of the compound represented by the general formula (1) include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferred.
- Glycidyl esters of ⁇ , ⁇ -unsaturated acids can be used singly or in combination of two or more.
- the content of structural units derived from glycidyl esters of ⁇ , ⁇ -unsaturated acids is preferably 0.02 to 2.5% by mass, more preferably 0.05 to 1.5% by mass in the total resin composition. %, particularly preferably 0.08 to 1.0% by mass.
- the content of structural units derived from glycidyl esters of ⁇ , ⁇ -unsaturated acids is within this range, it is possible to further suppress the precipitation of mold deposits while maintaining heat shock resistance.
- the (C1) olefin-based copolymer preferably contains a structural unit derived from a (meth)acrylic acid alkyl ester.
- it preferably contains a structural unit derived from an ⁇ , ⁇ -unsaturated acid glycidyl ester and a structural unit derived from a (meth)acrylic acid alkyl ester. Structural units derived from (meth)acrylic acid alkyl esters are described below.
- the (meth)acrylic acid alkyl ester is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, -n-propyl acrylate, isopropyl acrylate, -n-butyl acrylate, isobutyl acrylate, - acrylic acid alkyl esters such as n-hexyl, n-amyl acrylate, and n-octyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, Methacrylic acid alkyl esters such as isobutyl methacrylate, n-hexyl methacrylate, n-amyl methacrylate and n-octyl methacrylate can be mentioned.
- the (meth)acrylic acid alkyl esters may be used singly or in combination of two or more.
- the content of the copolymer component derived from the (meth)acrylic acid alkyl ester is not particularly limited, but can be, for example, 0.2 to 5.5% by mass in the total resin composition.
- (C1) olefin copolymers include, for example, maleic anhydride-modified ethylene copolymers, glycidyl methacrylate-modified ethylene copolymers, glycidyl ether-modified ethylene copolymers, and ethylene alkyl Examples include acrylate copolymers. Among them, at least one olefin copolymer selected from the group consisting of maleic anhydride-modified ethylene copolymers, glycidyl methacrylate-modified ethylene copolymers, and glycidyl ether-modified ethylene copolymers is preferable. , glycidyl methacrylate-modified ethylene copolymers are most preferred.
- Examples of glycidyl methacrylate-modified ethylene copolymers include glycidyl methacrylate graft-modified ethylene copolymers, ethylene-glycidyl methacrylate copolymers, ethylene-glycidyl methacrylate-methyl acrylate copolymers, ethylene-glycidyl methacrylate-ethyl acrylate copolymers, Examples include ethylene-glycidyl methacrylate-propyl acrylate copolymer and ethylene-glycidyl methacrylate-butyl acrylate copolymer.
- an ethylene-glycidyl methacrylate copolymer and an ethylene-glycidyl methacrylate-methyl acrylate copolymer are preferred, and an ethylene-glycidyl methacrylate-methyl acrylate copolymer is particularly preferred, since particularly excellent heat shock resistance can be obtained.
- Specific examples of the ethylene-glycidyl methacrylate copolymer and the ethylene-glycidyl methacrylate-methyl acrylate copolymer include "Bond First" (manufactured by Sumitomo Chemical Co., Ltd.).
- glycidyl ether-modified ethylene copolymers examples include glycidyl ether graft-modified ethylene copolymers and glycidyl ether-ethylene copolymers.
- the olefin copolymer contains ethylene and an ⁇ -olefin having 3 or more carbon atoms as copolymer components.
- the ⁇ -olefin preferably has 3 to 20 carbon atoms, more preferably 5 to 20 carbon atoms, and still more preferably 5 to 15 carbon atoms.
- Examples of ⁇ -olefins having 3 or more carbon atoms include those having 3 or more carbon atoms among the structural units derived from the aforementioned ⁇ -olefins having 2 or more carbon atoms.
- the (C2) olefinic copolymer may be a random copolymer or a block copolymer.
- the olefinic copolymer may be a copolymer comprising 5 to 95% by mass of ethylene and 5 to 95% by mass of ⁇ -olefin.
- (C2) olefin copolymer examples include ethylene-octene copolymer (EO), ethylene-propylene copolymer, ethylene-butylene copolymer, ethylene-pentene copolymer, ethylene-hexene copolymer. Copolymers, ethylene-heptene copolymers and the like can be mentioned, and these copolymers can also be used by mixing them.
- EO ethylene-octene copolymer
- ethylene-propylene copolymer ethylene-butylene copolymer
- ethylene-pentene copolymer ethylene-hexene copolymer.
- Copolymers, ethylene-heptene copolymers and the like can be mentioned, and these copolymers can also be used by mixing them.
- the olefin-based copolymer contains, as copolymerization components, a structural unit derived from an ⁇ -olefin having 2 or more carbon atoms and a structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester.
- it may be a random, block or graft copolymer, or a copolymer modified with at least one selected from the group consisting of unsaturated carboxylic acids, acid anhydrides thereof, and derivatives thereof ( However, those corresponding to (C1) olefinic copolymers are excluded). Since structural units derived from ⁇ -olefins having 2 or more carbon atoms have been described above, structural units derived from ⁇ , ⁇ -unsaturated carboxylic acid alkyl esters will be described below.
- ⁇ Structural Unit Derived from ⁇ , ⁇ -Unsaturated Carboxylic Acid Alkyl Ester examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, methacryl Acid-2-ethylhexyl, hydroxyethyl methacrylate and the like can be used.
- Unsaturated carboxylic acids or acid anhydrides thereof used as modifiers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, citraconic acid, and glutaconic acid. acids, monomethyl maleate, monoethyl maleate, monoethyl fumarate, methyl itaconate, methyl maleic anhydride, maleic anhydride, methyl maleic anhydride, citraconic anhydride, etc., and these may be used singly or in combination of two or more. be.
- olefinic copolymer C3 examples include copolymers of ethylene and (meth)acrylic acid ester, such as ethylene ethyl acrylate copolymer (EEA) and ethylene methyl methacrylate copolymer.
- (C) olefin copolymers (C2) an olefin copolymer containing an ethylene-derived structural unit and an ⁇ -olefin-derived structural unit having 3 or more carbon atoms and (C3) an olefin copolymer containing a structural unit derived from an ⁇ -olefin having 2 or more carbon atoms and a structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid alkyl ester.
- (C1) to (C3) olefin-based copolymers can be produced by performing copolymerization by a conventionally known method.
- the above-mentioned olefin copolymers (C1) to (C3) can be obtained by carrying out copolymerization by a generally well-known radical polymerization reaction.
- the type of olefinic copolymer is not particularly limited, and may be, for example, a random copolymer or a block copolymer.
- the above olefin-based copolymers include, for example, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, poly-2-ethylhexyl (meth)acrylate, polystyrene, polyacrylonitrile .
- the olefin copolymer is contained in an amount of 1.0 to 45.0 parts by mass with respect to 100 parts by mass of the PAS resin. If the amount of the olefin copolymer is less than 1.0 parts by mass, it tends to be difficult to sufficiently improve the heat shock resistance. Molding defects tend to occur due to increased gas generation during molding. On the other hand, when the olefinic copolymer is added, the melt viscosity of the resin composition tends to increase, so the flash tends to be shorter than before the addition of the olefinic copolymer.
- the olefin copolymer is selected from the viewpoints of 2. It preferably contains 0 to 30.0 parts by mass, more preferably 3.5 to 25.0 parts by mass, even more preferably 4.0 to 20.0 parts by mass, 4.0 to 15.0 parts by mass It is particularly preferred to include
- the (C) olefin-based copolymer used in the present embodiment can contain structural units derived from other copolymer components within a range that does not impair its effects.
- the PAS resin composition of the present embodiment preferably contains (D) an inorganic filler (excluding (B1) carbon nanotubes, (B2) inorganic nanotubes, and (B3) carbon nanostructures).
- the inorganic filler preferably contains a fibrous inorganic filler because it can further improve mechanical strength, heat shock resistance, heat resistance, and the like.
- the inorganic filler is preferably a combination of a fibrous inorganic filler and a plate-like inorganic filler and/or a powdery or granular inorganic filler, because it can further improve the mechanical strength and flatness.
- the term “fibrous” refers to a shape having a different diameter ratio of 1 to 4 and an average fiber length (cut length) of 0.01 to 3 mm.
- the term “plate-like” refers to a shape having a diameter ratio of greater than 4 and an aspect ratio of 1 or more and 500 or less.
- the term "powder-like” refers to a shape (including a spherical shape) having a different diameter ratio of 1 or more and 4 or less and an aspect ratio of 1 or more and 2 or less. Both shapes are initial shapes (shapes before melt-kneading).
- the diameter ratio is "major axis of cross section perpendicular to longitudinal direction (longest linear distance of cross section)/minor axis of cross section (longest linear distance perpendicular to major axis)".
- the aspect ratio is "the longest linear distance in the longitudinal direction/the minor axis of the cross section perpendicular to the longitudinal direction (the longest straight distance in the cross section and the longest straight distance in the perpendicular direction)". Both the diameter ratio and the aspect ratio can be calculated using a scanning electron microscope and image processing software. For the average fiber length (cut length), the manufacturer's value (the numerical value published by the manufacturer in a catalog or the like) can be adopted.
- fibrous inorganic fillers examples include glass fiber, carbon fiber, zinc oxide fiber, titanium oxide fiber, wollastonite, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, Mineral fibers such as potassium titanate fibers, metal fibrous materials such as stainless steel fibers, aluminum fibers, titanium fibers, copper fibers, and brass fibers can be used, and one or more of these can be used. Among them, glass fiber is preferable.
- Examples of commercially available glass fiber products include chopped glass fiber (ECS03T-790DE, average fiber diameter: 6 ⁇ m) manufactured by Nippon Electric Glass Co., Ltd., chopped glass fiber (CS03DE 416A, average fiber diameter: 6 ⁇ m) manufactured by Owens Corning Manufacturing Co., Ltd.
- the fibrous inorganic filler may be surface-treated with various surface treatment agents such as generally known epoxy-based compounds, isocyanate-based compounds, silane-based compounds, titanate-based compounds, and fatty acids. Adhesion to the PAS resin can be improved by surface treatment.
- the surface treatment agent may be applied to the fibrous inorganic filler in advance for surface treatment or convergence treatment prior to material preparation, or may be added at the same time as material preparation.
- the fiber diameter of the fibrous inorganic filler is not particularly limited, it can be, for example, 5 ⁇ m or more and 30 ⁇ m or less in the initial shape (shape before melt-kneading).
- the fiber diameter of the fibrous inorganic filler refers to the major diameter of the fiber cross section of the fibrous inorganic filler.
- the cross-sectional shape of the fibrous inorganic filler is not particularly limited, but examples include a round shape and a flat shape.
- fibrous inorganic fillers having different cross-sectional shapes may be used together. The combined use of a fibrous inorganic filler having a round cross-sectional shape and a fibrous inorganic filler having a flat cross-sectional shape is preferable because the heat shock resistance can be further improved.
- plate-like inorganic fillers examples include glass flakes, talc (plate-like), mica, kaolin, clay, alumina (plate-like), various metal foils, and the like, and one or more of these may be used. can be done. Among them, glass flakes and talc are preferable. Examples of commercially available glass flakes include REFG-108 (average particle diameter (50% d): 623 ⁇ m) manufactured by Nippon Sheet Glass Co., Ltd., Fine Flake (average particle diameter (50% d) manufactured by Nippon Sheet Glass Co., Ltd.
- the plate-like inorganic filler may be surface-treated in the same manner as the fibrous inorganic filler.
- Granular inorganic fillers include carbon black, silica, quartz powder, glass beads, glass powder, talc (granular), calcium silicate, aluminum silicate, silicates such as diatomaceous earth, iron oxide, titanium oxide, and zinc oxide. , alumina (granular) and other metal oxides, calcium carbonate, magnesium carbonate and other metal carbonates, calcium sulfate, barium sulfate and other metal sulfates, silicon carbide, silicon nitride, boron nitride, and various metal powders. , these can be used alone or in combination of two or more. Among them, calcium carbonate and glass beads are preferred.
- Examples of commercially available products of calcium carbonate include Whiten P-30 (average particle size (50%d): 5 ⁇ m) manufactured by Toyo Fine Chemical Co., Ltd.).
- Examples of commercially available glass beads include EGB731A (average particle diameter (50% d): 20 ⁇ m) manufactured by Potters Ballotini Co., Ltd., EMB-10 (average particle size diameter (50% d): 5 ⁇ m) and the like.
- the powdery inorganic filler may also be surface-treated in the same manner as the fibrous inorganic filler.
- the inorganic filler is preferably a combination of a fibrous inorganic filler and a plate-like inorganic filler and/or a powdery or particulate inorganic filler, since this can further improve the mechanical strength and flatness.
- fibrous inorganic fillers and plate-like inorganic fillers and/or particulate inorganic fillers include glass fibers and glass flakes, glass fibers and calcium carbonate, glass fibers and glass beads, and glass fibers and glass flakes. and calcium carbonate, and a combination of glass fiber and glass fiber with an irregular cross section (flat shape) and calcium carbonate.
- the (D) inorganic filler is preferably contained in an amount of 5 to 250 parts by mass with respect to 100 parts by mass of the PAS resin.
- the inorganic filler is 5 to 250 parts by mass, sufficient mechanical properties and fluidity can be obtained.
- the inorganic filler is more preferably contained in an amount of 15 to 200 parts by mass, even more preferably 25 to 150 parts by mass, and particularly preferably 30 to 110 parts by mass.
- thermoplastic resins and thermosetting resins in addition to the above components, known additives that are generally added to thermoplastic resins and thermosetting resins in order to impart desired properties according to the purpose, within a range that does not impair the effect release agents, lubricants, plasticizers, flame retardants, coloring agents such as dyes and pigments, crystallization accelerators, crystal nucleating agents, various antioxidants, heat stabilizers, weather stabilizers, corrosion inhibitors An agent or the like may be blended.
- the PAS resin composition of the present embodiment can suppress the generation of burrs.
- a burr inhibitor such as a branched polyphenylene sulfide resin having a very high melt viscosity, such as those described in the above, may be used in combination.
- the PAS resin composition of the present embodiment is particularly excellent in heat shock resistance, it is useful to apply it to molded articles or insert molded articles that require heat shock resistance.
- the method for molding a molded product using the PAS resin composition of the present embodiment is not particularly limited, and various methods known in the technical field can be employed.
- the PAS resin composition of the present embodiment can be put into an extruder, melt-kneaded and pelletized, and the pellets can be put into an injection molding machine equipped with a predetermined mold and injection molded. can.
- the resulting molded article has less burrs due to the use of the PAS resin composition of the present embodiment.
- Examples of molded articles obtained by molding the PAS resin composition of the present embodiment include electric/electronic equipment parts, automotive equipment parts, chemical equipment parts, water-related parts, and the like. Specifically, various automotive cooling system parts, ignition related parts, distributor parts, various sensor parts, various actuator parts, throttle parts, power module parts, ECU parts, various connector parts, piping joints (pipe joints), joints etc.
- LEDs, sensors, sockets, terminal blocks, printed circuit boards, motor parts, electric and electronic parts such as ECU cases, lighting parts, TV parts, rice cooker parts, microwave oven parts, iron parts, It can be used for domestic and office electrical product parts such as copier-related parts, printer-related parts, facsimile-related parts, heaters, and air-conditioner parts.
- an insert-molded product is obtained by insert-molding a resin member containing the PAS resin composition of the present embodiment and an insert member containing a metal, alloy, or inorganic solid. That is, the insert-molded article of this embodiment has a resin member containing the PAS resin composition of this embodiment and an insert member containing a metal, alloy, or inorganic solid. Since the insert-molded product of the present embodiment contains a PAS resin composition that suppresses the generation of burrs and has excellent heat shock resistance, the resin member has few burrs and has excellent heat shock resistance.
- the insert-molded product of this embodiment is a composite molded product obtained by mounting a metal or the like in advance on a molding die and filling the outer side of the mold with the above-described PAS resin composition.
- Molding methods for filling a mold with a resin include injection molding, extrusion compression molding, and the like, but injection molding is generally used.
- the shape and size of the insert-molded product are not particularly limited.
- the material to be inserted into the resin is used for the purpose of taking advantage of its properties and compensating for the defects of the resin, a material that does not change shape or melt when it comes into contact with the resin during molding is used.
- insert-molded article of the present embodiment is applied are the same as those listed in the parts to which the molded article formed by molding the PAS resin composition of the present embodiment are applied. part of which has an insert member.
- Examples 1 to 8 Comparative Examples 1 to 6
- Tables 1 and 2 After dry blending each raw material component shown in Tables 1 and 2, it was put into a twin-screw extruder with a cylinder temperature of 320 ° C. (glass fiber was added separately from the side feed section of the extruder). , melt-kneaded and pelletized.
- Tables 1 and 2 the numerical value of each component indicates parts by mass. Further, the details of each raw material component used are shown below.
- PAS resin/PPS resin 1 Fortron KPS manufactured by Kureha Co., Ltd. (melt viscosity: 130 Pa s (shear rate: 1200 sec ⁇ 1 , 310° C.))
- PPS resin 2 Fortron KPS manufactured by Kureha Co., Ltd. (melt viscosity: 20 Pa s (shear rate: 1200 sec -1 , 310 ° C.))
- melt viscosity of PPS resin was measured as follows. The melt viscosity was measured at a barrel temperature of 310° C. and a shear rate of 1200 sec ⁇ 1 using a capillograph manufactured by Toyo Seiki Seisakusho Co., Ltd. using a flat die of 1 mm ⁇ 20 mmL as a capillary.
- Inorganic filler/glass fiber Chopped strand ECS 03 T-747H manufactured by Nippon Electric Glass Co., Ltd. (fiber diameter: 10.5 ⁇ m, length 3 mm) ⁇ Calcium carbonate: Asahi Komatsu Co., Ltd., MC-35W (average particle size (50% d) 25 ⁇ m)
- FIG. 1 is a diagram showing an insert-molded test piece 1
- FIG. 2 is a diagram showing an insert member 11, and FIG.
- the test piece 1 is molded in a state in which a metal insert member 11 is embedded in a cylindrical resin member 10 made of a resin composition.
- the cylindrical resin member 10 is molded using the pellets obtained as described above.
- the insert member 11 is columnar and has a teardrop-shaped top surface and a bottom surface with an arc on one side and an acute angle on the other side.
- FIG. 1 is a diagram showing an insert-molded test piece 1
- FIG. 2 is a diagram showing an insert member 11, and FIG.
- the test piece 1 is molded in a state in which a metal insert member 11 is embedded in a cylindrical resin member 10 made of a resin composition.
- the cylindrical resin member 10 is molded using the pellets obtained as described above.
- the insert member 11 is columnar and has a teardrop-shaped top surface and a bottom surface with an arc on one side and an acute angle on
- the acute-angled portion has an arcuate tip with a radius of curvature r of 0.2 mm.
- the insert member 11 is higher than the columnar resin member 10, and a part of the insert member 11 protrudes (see FIG. 1(a)). Furthermore, as shown in FIG. 3(a), the center O1 of the circle formed by the arc of the insert member 11 does not coincide with the center O2 of the circle of the resin member 10, and the acute-angled side of the insert member 11 is made of resin. It is arranged so as to be close to the side surface of the member 10 .
- the distance dw between the acute-angled tip of the insert member 11 and the side surface of the resin member 10 is 1 mm. there is In addition, although the dimensions of the test piece are shown in FIG. 3, the unit is mm.
- Comparative Example 1 and Examples 1 and 2 which differ mainly in whether or not they contain CNT
- Comparative Example 3 and Examples 3 and 4 show that an olefinic copolymer and CNT are used in combination. By doing so, the burr length is shortened and the heat shock resistance is excellent.
- Comparative Example 2 which is substantially the same as Example 2 except that it does not contain an olefinic copolymer, was inferior in heat shock resistance.
- Comparative Example 4 which is substantially the same as Example 4 except that it does not contain an olefinic copolymer, was inferior in heat shock resistance.
- Example 5 6.2 parts by mass of the olefinic copolymer (C1-1) in Example 1 was replaced with 3.1 parts by mass of the olefinic copolymer (C1-1) and olefin This is an example of changing to a combination system with 3.1 parts by mass of the system copolymer (C2) or (C3).
- Examples 7 and 8 13.9 parts by mass of the olefinic copolymer (C1-2) in Example 3 was replaced with 7.0 parts by mass of the olefinic copolymer (C1-2), This is an example of changing to a combined system with 7.0 parts by mass of the olefinic copolymer (C2) or (C3).
- Comparative Example 5 is almost the same as Example 1 with CNT and olefinic copolymer removed, and Comparative Example 6 is almost the same as Example 3 with CNT and olefinic copolymer removed. equal. It can be seen that both Comparative Examples 5 and 6 have a long burr length and are inferior in heat shock resistance.
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Abstract
Description
(1)(A)温度310℃及びせん断速度1200sec-1で測定した溶融粘度が5~500Pa・sの、カルボキシル基末端を有するポリアリーレンサルファイド樹脂100質量部に対して、
(B)(B1)長さが10000nm超3000000nm以下であり、アスペクト比が2000超500000以下のカーボンナノチューブを0.05~1.5質量部、(B2)無機ナノチューブ(但し、炭素原子を含まないものに限る。)を0.01質量部以上10質量部未満、又は(B3)カーボンナノストラクチャーを0.01~5質量部と、
(C)炭素原子数2以上のα-オレフィン由来の構成単位を含有するオレフィン系共重合体を1.0~45.0質量部と、
を含む、ポリアリーレンサルファイド樹脂組成物。
(C1)アミノ基、カルボキシル基、水酸基、酸無水物基、エポキシ基、グリシジル基、イソシアネート基、イソチオシアネート基、アセトキシ基、シラノール基、アルコキシシラン基、アルキニル基、オキサゾリン基、チオール基、スルホン酸基、スルホン酸塩残基、及びカルボン酸エステル基からなる群から選択される少なくとも1種の官能基を含有するオレフィン系共重合体、
(C2)エチレン由来の構成単位と炭素原子数3以上のα-オレフィン由来の構成単位とを含有するオレフィン系共重合体、並びに
(C3)炭素原子数2以上のα-オレフィン由来の構成単位とα,β-不飽和カルボン酸アルキルエステル由来の構成単位とを含有するオレフィン系共重合体、
からなる群から選択される少なくとも1種のオレフィン系共重合体である、前記(1)~(4)のいずれかに記載のポリアリーレンサルファイド樹脂組成物。
(B1)CNT
所定の長さで所定のアスペクト比を有するCNTによるバリが抑制されるメカニズムは、低せん断速度領域における溶融粘度の増加や、結晶化速度の向上(核剤効果による固化速度向上)が寄与していると推定される。また、低せん断速度領域における溶融粘度の増加により、離型抵抗の低減を図ることができ、結晶化速度の向上により、成形サイクルの短縮化を図ることができる。
(B2)無機ナノチューブ
無機ナノチューブの添加によりバリが抑制されるメカニズムは、結晶化速度の向上(核剤効果による固化速度向上)が寄与していると推定される。また、結晶化速度の向上により、成形サイクルの短縮化を図ることができる。
(B3)CNS
CNSの添加によりバリが抑制されるメカニズムは、低せん断速度領域における溶融粘度の増加や、結晶化速度の向上(核剤効果による固化速度向上)が寄与していると推定される。また、低せん断速度領域における溶融粘度の増加により、離型抵抗の低減を図ることができ、結晶化速度の向上により、成形サイクルの短縮化を図ることができる。
尚、本実施形態において、「核剤」は、「結晶核剤」、「造核剤」等と同義である。
また、(C)オレフィン系共重合体が特定の官能基を含有していると、当該官能基とPAS樹脂の末端基とが反応し、この反応によりPAS樹脂とオレフィン系共重合体との相互作用が高まることによって、耐ヒートショック性がより一層向上すると推測される。中でも、当該官能基がPAS樹脂のカルボキシル基末端と反応する官能基であることが好ましい。
耐ヒートショック性は、上記(B1)~(B3)の各成分を含むことによっても向上する。そのメカニズムは不明であるが、実験事実から明らかである(後記実施例参照)。
以下に、本実施形態のPAS樹脂組成物の各成分について説明する。
PAS樹脂は、機械的性質、電気的性質、耐熱性その他物理的・化学的特性に優れ、且つ加工性が良好であるという特徴を有する。
PAS樹脂は、主として、繰返し単位として-(Ar-S)-(但しArはアリーレン基)で構成された高分子化合物であり、本実施形態では一般的に知られている分子構造のPAS樹脂を使用することができる。
次いで、(B1)カーボンナノチューブ、(B2)無機ナノチューブ、及び(B3)カーボンナノストラクチャーについて説明する。
本実施形態において用いるCNTは、長さが10000nm超3000000nm以下であり、アスペクト比が2000超500000以下である。当該CNTを用いることで、比較的少量の添加であってもバリの発生を抑えることができる。尚、本実施形態で使用するCNTは、単層カーボンナノチューブ及び多層カーボンナノチューブのいずれでもよい。
ここで、CNTのアスペクト比は、CNTの長さをCNTの直径で除した数値であり、メーカー値(メーカーがカタログ等において公表している数値)を採用することができる。
本実施形態において、無機ナノチューブによるバリ発生の抑制は、上述の通り、核剤効果による固化速度向上に起因すると考えられる。従って、比較的少量の添加であってもバリの発生を抑制することができる。尚、本実施形態において、無機ナノチューブは炭素原子を含まないものに限る。従って、本実施形態において、無機ナノチューブにはカーボンナノチューブは含まない。尚、無機ナノチューブは、直径がナノメートルオーダーサイズのチューブ状の無機物質である。更に、無機ナノチューブは、一般に絶縁性を有するものが多く、絶縁性を有する無機ナノチューブを用いればPAS樹脂組成物の絶縁性が低下することはない。その点においてカーボンナノチューブを用いるものとは異なる。
アルミノシリケートナノチューブとしては、ハロイサイトナノチューブ又はメタハロイサイトナノチューブが好ましい。これらのうち、低コスト及び入手しやすさの観点からハロイサイトナノチューブが好ましい。
また、金属硫化物ナノチューブとしては、モリブデン硫化物、タングステン硫化物、又は銅硫化物ナノチューブ等が挙げられる。金属ハロゲン化物ナノチューブとしては、塩化ニッケル、塩化カドミウム、又はヨウ化カドミウムナノチューブ等が挙げられる。
ここで、無機ナノチューブのアスペクト比は、無機ナノチューブの長さを無機ナノチューブの直径で除した数値であり、メーカー値(メーカーがカタログ等において公表している数値)を採用することができる。
本実施形態で使用するCNSは、複数のカーボンナノチューブが結合した状態で含む構造体であり、カーボンナノチューブは分岐結合や架橋構造で他のカーボンナノチューブと結合している。このようなCNSの詳細は、米国特許出願公開第2013-0071565号明細書、米国特許第9,113,031号明細書、同第9,447,259号明細書、同第9,111,658号明細書に記載されている。
PAS樹脂組成物の調製時において、原料の溶融混練時に(B1)~(B3)成分を添加するタイミングとしては、例えば、一旦、PAS樹脂と(B1)~(B3)成分とを加熱・溶融混練し、ペレット化させたマスターバッチとしてからでもよい。その場合、(B1)~(B3)成分によるバリ抑制効果が損なわれない限り、PAS樹脂以外の樹脂を用いてマスターバッチを作製してもよい。
また、一旦、単にPAS樹脂と(B1)~(B3)成分とを攪拌させて得られる混合物としてから添加してもよい。その場合はPAS樹脂及び(B1)~(B3)成分をドライブレンドする方法等が挙げられ、タンブラー又はヘンシェルミキサー等を用いたブレンド方法としてもよい。
PAS樹脂及び(B1)~(B3)成分を配合して溶融混練する方法としては、例えば、PAS樹脂及び(B1)~(B3)成分をそれぞれ押出機に供給してもよいし、PAS樹脂及び(B1)~(B3)成分、その他の配合剤等をドライブレンドしてから押出機に供給してもよいし、一部の原料をサイドフィード方式で供給してもよい。
本実施形態において用いる(C)オレフィン系共重合体は、炭素原子数2以上のα-オレフィン由来の構成単位を含有する。当該オレフィン系共重合体は、耐ヒートショック性を向上させるために使用される。すなわち、上述のように、当該オレフィン系共重合体を含むことで、樹脂部材に可撓性が付与されやすく、可撓性の付与により樹脂部材が軟らかくなることが、耐ヒートショック性の改善に寄与すると考えられる。
(C1)アミノ基、カルボキシル基、水酸基、酸無水物基、エポキシ基、グリシジル基、イソシアネート基、イソチオシアネート基、アセトキシ基、シラノール基、アルコキシシラン基、アルキニル基、オキサゾリン基、チオール基、スルホン酸基、スルホン酸塩残基、及びカルボン酸エステル基からなる群から選択される少なくとも1種の官能基を含有するオレフィン系共重合体
(C2)エチレン由来の構成単位と炭素原子数3以上のα-オレフィン由来の構成単位とを含有するオレフィン系共重合体
(C3)炭素原子数2以上のα-オレフィン由来の構成単位とα,β-不飽和カルボン酸アルキルエステル由来の構成単位とを含有するオレフィン系共重合体
本実施形態において、(C1)~(C3)オレフィン系共重合体は、1種単独で又は2種以上組み合わせて使用することができる。以下、(C1)~(C3)オレフィン系共重合体のそれぞれについて詳述する。
(C1)オレフィン系共重合体は、上記特定の官能基を含有するオレフィン系共重合体である。すなわち、(C1)オレフィン系共重合体は、炭素原子数2以上のα-オレフィン由来の構成単位とともに上記特定の官能基を含有するオレフィン系共重合体である。オレフィン系共重合体が上記特定の官能基を含有していると、当該官能基とPAS樹脂の末端基とが反応することで、PAS樹脂とオレフィン系共重合体との相互作用が高まる。そのような相互作用の高まりによって、耐ヒートショック性がより一層向上すると推測される。中でも、当該官能基がPAS樹脂のカルボキシル末端基と反応する官能基であることが好ましい。上記官能基の中でも、酸無水物基、エポキシ基、グリシジル基がより好ましく、エポキシ基、グリシジル基が更に好ましい。
以下に先ず、炭素原子数2以上のα-オレフィン由来の構成単位について説明する。
炭素原子数2以上のα-オレフィン(以下、単に「α-オレフィン」とも呼ぶ。)としては、特に限定されず、例えば、エチレン、プロピレン、ブチレン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、4-メチル-1-ペンテン、4-メチル-1-ヘキセン等を挙げることができる。中でも、エチレンが好ましい。当該α-オレフィンは、1種単独で使用することもでき、2種以上を併用することもできる。当該α-オレフィン由来の構成単位の含有量は、特に限定されないが、例えば、全樹脂組成物中0.5~20質量%とすることができる。
α,β-不飽和酸のグリシジルエステル(以下、単に「グリシジルエステル」とも呼ぶ。)としては、特に限定されず、例えば、以下の一般式(1)に示される構造を有するものを挙げることができる。
(メタ)アクリル酸アルキルエステルとしては、特に限定されず、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-n-ヘキシル、アクリル酸-n-アミル、アクリル酸-n-オクチル等のアクリル酸アルキルエステル;メタクリル酸メチル、メタクリル酸エチル、メタクリル酸-n-プロピル、メタクリル酸イソプロピル、メタクリル酸-n-ブチル、メタクリル酸イソブチル、メタクリル酸-n-ヘキシル、メタクリル酸-n-アミル、メタクリル酸-n-オクチル等のメタクリル酸アルキルエステルが挙げられる。中でも、特にアクリル酸メチルが好ましい。(メタ)アクリル酸アルキルエステルは、1種単独で使用することもでき、2種以上を併用することもできる。(メタ)アクリル酸アルキルエステルに由来する共重合成分の含有量は、特に限定されないが、例えば、全樹脂組成物中0.2~5.5質量%とすることができる。
(C2)オレフィン系共重合体は、共重合成分としてエチレンと炭素原子数3以上のα-オレフィンとを含有する。(C2)オレフィン系共重合体において、α-オレフィンの炭素数は3~20が好ましく、5~20がより好ましく、5~15が更に好ましい。尚、炭素原子数3以上のα-オレフィンの例示としては、上述の炭素原子数2以上のα-オレフィン由来の構成単位のうち、炭素原子数が3以上のものが挙げられる。また、(C2)オレフィン系共重合体はランダム共重合体であっても、ブロック共重合体であってもよい。(C2)オレフィン系共重合体は、エチレン5~95質量%とα-オレフィン5~95質量%からなる共重合体であってもよい。(C2)オレフィン系共重合体の具体例としては、エチレン-オクテン共重合体(EO)、エチレン-プロピレン共重合体、エチレン-ブチレン共重合体、エチレン-ペンテン共重合体、エチレン-ヘキセン共重合体、エチレン-ヘプテン共重合体等が挙げられ、更にこれらの共重合体を混合しても使用できる。
(C3)オレフィン系共重合体は、共重合成分として炭素原子数2以上のα-オレフィン由来の構成単位とα,β-不飽和カルボン酸アルキルエステル由来の構成単位とを含有する。また、ランダム、ブロック又はグラフト共重合体や、その共重合体を不飽和カルボン酸及びその酸無水物及びそれらの誘導体からなる群より選択される少なくとも1種で変性したものであってもよい(但し、(C1)オレフィン系共重合体に該当するものを除く。)。
炭素原子数2以上のα-オレフィン由来の構成単位については上述したので、以下においてはα,β-不飽和カルボン酸アルキルエステル由来の構成単位について説明する。
α,β-不飽和カルボン酸アルキルエステルとしては、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-t-ブチル、アクリル酸イソブチル、アクリル酸-2-エチルヘキシル、アクリル酸ヒドロキシエチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸-n-プロピル、メタクリル酸イソプロピル、メタクリル酸-n-ブチル、メタクリル酸-t-ブチル、メタクリル酸イソブチル、メタクリル酸-2-エチルヘキシル、メタクリル酸ヒドロキシエチル等を用いることができる。
オレフィン系共重合体C3の具体例としては、エチレンアクリル酸エチル共重合体(EEA)、エチレンメタクリル酸メチル共重合体等のエチレンと(メタ)アクリル酸エステルとの共重合体等が挙げられる。
本実施形態のPAS樹脂組成物は、(D)無機充填剤(但し、(B1)カーボンナノチューブ、(B2)無機ナノチューブ、及び(B3)カーボンナノストラクチャーを除く。)を含むことが好ましい。中でも、無機充填剤は、機械的強度、耐ヒートショック性、耐熱性等をより向上させることができるため、繊維状無機充填剤を含んでいることが好ましい。特に、断面形状が丸型形状の繊維状無機充填剤と断面形状が扁平形状の繊維状無機充填剤とを併用すると、耐ヒートショック性をより向上させることができるため好ましい。
また、(D)無機充填剤は、繊維状無機充填剤と板状無機充填剤及び/又は粉粒状無機充填剤との組合せからなると、機械的強度や平面度をより向上させることができるため好ましい。
本実施形態において、「繊維状」とは、異径比が1以上4以下、かつ、平均繊維長(カット長)が0.01~3mmの形状をいう。また、「板状」とは、異径比が4より大きく、かつ、アスペクト比が1以上500以下の形状をいう。更に、「粉粒状」とは、異径比が1以上4以下、かつ、アスペクト比が1以上2以下の形状(球状を含む。)をいう。いずれの形状も初期形状(溶融混練前の形状)である。異径比とは、「長手方向に直角の断面の長径(断面の最長の直線距離)/当該断面の短径(長径と直角方向の最長の直線距離)」である。アスペクト比とは、「長手方向の最長の直線距離/長手方向に直角の断面の短径(当該断面における最長距離の直線と直角方向の最長の直線距離)」である。異径比及びアスペクト比は、いずれも、走査型電子顕微鏡及び画像処理ソフトを用いて算出することができる。また、平均繊維長(カット長)はメーカー値(メーカーがカタログなどにおいて公表している数値)を採用することができる。
繊維状無機充填剤の繊維径は、特に限定されないが、初期形状(溶融混練前の形状)において、例えば5μm以上30μm以下とすることができる。ここで、繊維状無機充填剤の繊維径とは、繊維状無機充填剤の繊維断面の長径をいう。
繊維状無機充填剤の断面形状は、特に限定されないが丸型形状や扁平形状等を挙げることができる。また、断面形状の異なる繊維状無機充填剤を併用してもよい。断面形状が丸型形状の繊維状無機充填剤と断面形状が扁平形状の繊維状無機充填剤とを併用すると、耐ヒートショック性をより向上させることができるため好ましい。
ガラスフレークの上市品の例としては、日本板硝子(株)製、REFG-108(平均粒子径(50%d):623μm)、(日本板硝子(株)製、ファインフレーク(平均粒子径(50%d):169μm)、日本板硝子(株)製、REFG-301(平均粒子径(50%d):155μm)、日本板硝子(株)製、REFG-401(平均粒子径(50%d):310μm)等が挙げられる。
タルクの上市品の例としては、松村産業(株)製 、クラウンタルクPP、林化成(株)製、 タルカンパウダーPKNN等が挙げられる。
板状無機充填剤は、繊維状無機充填剤と同様に表面処理されていてもよい。
炭酸カルシウムの上市品の例としては、東洋ファインケミカル(株)製、ホワイトンP-30(平均粒子径(50%d):5μm)等が挙げられる。また、ガラスビーズの上市品の例としては、ポッターズ・バロティーニ(株)製、EGB731A(平均粒子径(50%d):20μm)、ポッターズ・バロティーニ(株)製、EMB-10(平均粒子径(50%d):5μm)等が挙げられる。
粉粒状無機充填剤も、繊維状無機充填剤と同様に表面処理されていてもよい。
繊維状無機充填剤と板状無機充填剤及び/又は粉粒状無機充填剤との組合せの例としては、ガラス繊維とガラスフレーク、ガラス繊維と炭酸カルシウム、ガラス繊維とガラスビーズ、ガラス繊維とガラスフレークと炭酸カルシウム、ガラス繊維と異形断面(扁平形状)のガラス繊維と炭酸カルシウム、等の組合せが挙げられる。
本実施形態においては、その効果を害さない範囲で、上記各成分の他、その目的に応じた所望の特性を付与するために、一般に熱可塑性樹脂及び熱硬化性樹脂に添加される公知の添加剤、すなわち、離型剤、潤滑剤、可塑剤、難燃剤、染料や顔料等の着色剤、結晶化促進剤、結晶核剤、各種酸化防止剤、熱安定剤、耐候性安定剤、腐食防止剤等を配合してもよい。尚、本実施形態のPAS樹脂組成物によりバリの発生を抑えることができるが、必要に応じてアルコキシシラン化合物や、例えば、国際公開第2006/068161号や国際公開第2006/068159号等に記載されているような、溶融粘度が非常に高い分岐型ポリフェニレンサルファイド系樹脂等のバリ抑制剤を併用してもよい。
本実施形態のPAS樹脂組成物は、特に耐ヒートショック性に優れることから、耐ヒートショック性が要求される成形品又はインサート成形品に適用することが有用である。
本実施形態のPAS樹脂組成物を用いて成形品を成形する方法としては特に限定はなく、当該技術分野で知られている各種方法を採用することができる。例えば、本実施形態のPAS樹脂組成物を押出機に投入して溶融混練してペレット化し、このペレットを所定の金型を装備した射出成形機に投入し、射出成形することで作製することができる。そして、得られる成形品は、本実施形態のPAS樹脂組成物を用いるためバリの発生が少ない。
また、その他の用途として、例えば、LED、センサー、ソケット、端子台、プリント基板、モーター部品、ECUケース等の電気・電子部品、照明部品、テレビ部品、炊飯器部品、電子レンジ部品、アイロン部品、複写機関連部品、プリンター関連部品、ファクシミリ関連部品、ヒーター、エアコン用部品等の家庭・事務電気製品部品に用いることができる。
本実施形態のインサート成形品が適用される部品としては、上記の本実施形態のPAS樹脂組成物を成形してなる成形品が適用される部品で挙げたものと同様であり、そのような部品の一部にインサート部材を有するものが挙げられる。
各実施例・比較例において、表1~2に示す各原料成分をドライブレンドした後、シリンダー温度320℃の二軸押出機に投入して(ガラス繊維は押出機のサイドフィード部より別添加)、溶融混練し、ペレット化した。尚、表1~2において、各成分の数値は質量部を示す。
また、使用した各原料成分の詳細を以下に示す。
・PPS樹脂1:(株)クレハ製、フォートロンKPS(溶融粘度:130Pa・s(せん断速度:1200sec-1、310℃))
・PPS樹脂2:(株)クレハ製、フォートロンKPS(溶融粘度:20Pa・s(せん断速度:1200sec-1、310℃))
上記PPS樹脂の溶融粘度は以下のようにして測定した。
(株)東洋精機製作所製、キャピログラフを用い、キャピラリーとして1mmφ×20mmLのフラットダイを使用し、バレル温度310℃、せん断速度1200sec-1での溶融粘度を測定した。
・CNT:LG化学社製、CP1002M(平均径:9nm、平均長さ:19000nm、アスペクト比:2111)
(3)オレフィン系共重合体
・オレフィン系共重合体C1-1(グリシジル基含有オレフィン系共重合体):住友化学(株)製、ボンドファースト(登録商標)BF-7L(エチレン-グリシジルジメタクリレート-メチルアクリレート共重合体、グリシジルメタクリレート含有量:3質量%)
・オレフィン系共重合体C1-2(グリシジル基含有オレフィン系共重合体):住友化学(株)製、ボンドファースト(登録商標)7M(エチレン-グリシジルジメタクリレート-メチルアクリレート共重合体、グリシジルメタクリレート含有量:6質量%)
・オレフィン系共重合体C2:エチレン-オクテン共重合体、ダウ・ケミカル日本(株)製、Engage 8440
・オレフィン系共重合体C3:エチレンエチルアクリレート共重合体、(株)NUC製、NUC-6570
・ガラス繊維:日本電気硝子(株)製、チョップドストランドECS 03 T-747H(繊維径:10.5μm、長さ3mm)
・炭酸カルシウム:旭鉱末(株)製、MC-35W(平均粒子径(50%d)25μm)
得られた各実施例・比較例のペレットを用いて以下の評価を行った。
(1)バリ長
一部に20μmの金型間隙を有するバリ測定部が外周に設けられている円盤状キャビティーの金型を用いて、シリンダー温度320℃、金型温度150℃で、キャビティーが完全に充填するのに必要な最小圧力で射出成形した。そして、その部分に発生するバリ長さを写像投影機((株)ミツトヨ製、CNC画像測定機(型式:QVBHU404-PRO1F))にて拡大して測定した。測定結果を表1~2に示す。
(株)東洋精機製作所製、キャピログラフを用い、キャピラリーとして1mmφ×20mmLのフラットダイを使用し、バレル温度310℃、せん断速度1000sec-1での溶融粘度(MV)を測定した。測定結果を表1~2に示す。
(耐ヒートショック性試験)
まず、各実施例・比較例で得たペレットと金属製のインサート部材を用い、図1~図3に示す試験片をインサート成形した。図1は、インサート成形した試験片1を示す図であり、図2は、インサート部材11を示す図であり、図3は試験片1の寸法を示す図である。試験片1は、図1に示すように、樹脂組成物からなる円柱形の樹脂部材10に金属製のインサート部材11が埋入した状態で成形されている。円柱形の樹脂部材10は、上記のようにして得られたペレットを用いて成形されたものである。インサート部材11は、図2に示すように、柱状であって、その上面及び底面の形状が一側が円弧状、他側が鋭角形状の涙型の形状をなす。鋭角形状部分は部分拡大図である図1(b)に示すように、先端が円弧状になっており、その曲率半径rは0.2mmである。また、インサート部材11は、円柱形の樹脂部材10の高さより高く、その一部が突出している(図1(a)参照)。更に、図3(a)に示すように、インサート部材11の円弧を一部とする円の中心O1と、樹脂部材10の円の中心O2とは一致せず、インサート部材11の鋭角形状側が樹脂部材10の側面に近接するように配置されている。そして、インサート部材11の鋭角形状の先端と、樹脂部材10の側面との距離dwは1mmであり、樹脂部材10において、インサート部材11の鋭角形状の先端近傍が肉厚の薄いウェルド部となっている。尚、図3に試験片の寸法を示しているが、その単位はmmである。
また、別の視点からは、オレフィン系共重合体もCNTも含まない比較例5及びCNTは含まないがオレフィン系共重合体は含む比較例1と、実施例1~2との比較(いずれもPAS樹脂はPPS樹脂1であり、他の成分の含有量は同等)から、オレフィン系共重合体を含むと耐ヒートショック性が向上し、バリ長が短くなるものの、バリの抑制効果としては不十分である。オレフィン系共重合体に加えて更にCNTを添加することでバリが抑制されるだけでなく、耐ヒートショック性の向上も認められる。同様のことが、オレフィン系共重合体もCNTも含まない比較例6及びCNTは含まないがオレフィン系共重合体は含む比較例3と、実施例3~4との比較(いずれもPAS樹脂はPPS樹脂2であり、他の成分の含有量は同等)においても言える。
更に、CNTの含有量が異なる比較例1及び実施例1~2の比較、並びに比較例3及び実施例3~4の比較から、CNTの含有量が増えるほど、耐ヒートショック性が顕著に向上していることが分かる。すなわち、耐ヒートショック性は、CNTを含むことによっても向上することが示された。
一方、実施例5及び6は、実施例1におけるオレフィン系共重合体(C1-1)6.2質量部を、それぞれ、オレフィン系共重合体(C1-1)3.1質量部と、オレフィン系共重合体(C2)又は(C3)3.1質量部との併用系に変更した例である。同様に、実施例7及び8は、実施例3におけるオレフィン系共重合体(C1-2)13.9質量部を、それぞれ、オレフィン系共重合体(C1-2)7.0質量部と、オレフィン系共重合体(C2)又は(C3)7.0質量部との併用系に変更した例である。実施例5~8のいずれの例も、バリ長が短くなり、かつ、耐ヒートショック性に優れることが分かる。
更に、比較例5は、実施例1からCNT及びオレフィン系共重合体を除いた例にほぼ等しく、また、比較例6は、実施例3からCNT及びオレフィン系共重合体を除いた例にほぼ等しい。比較例5及び6のいずれも、バリ長が長くなり、かつ、耐ヒートショック性に劣ることが分かる。
10 樹脂部材
11 インサート部材
Claims (9)
- (A)温度310℃及びせん断速度1200sec-1で測定した溶融粘度が5~500Pa・sの、カルボキシル基末端を有するポリアリーレンサルファイド樹脂100質量部に対して、
(B)(B1)長さが10000nm超3000000nm以下であり、アスペクト比が2000超500000以下のカーボンナノチューブを0.05~1.5質量部、(B2)無機ナノチューブ(但し、炭素原子を含まないものに限る。)を0.01質量部以上10質量部未満、又は(B3)カーボンナノストラクチャーを0.01~5質量部と、
(C)炭素原子数2以上のα-オレフィン由来の構成単位を含有するオレフィン系共重合体を1.0~45.0質量部と、
を含む、ポリアリーレンサルファイド樹脂組成物。 - 前記(A)ポリアリーレンサルファイド樹脂100質量部に対して、更に(D)無機充填剤(但し、前記(B1)カーボンナノチューブ、前記(B2)無機ナノチューブ、及び(B3)前記カーボンナノストラクチャーを除く。)5~250質量部を含む、請求項1に記載のポリアリーレンサルファイド樹脂組成物。
- 前記(D)無機充填剤が、繊維状無機充填剤である、請求項2に記載のポリアリーレンサルファイド樹脂組成物。
- 前記(D)無機充填剤が、繊維状無機充填剤と、板状無機充填剤及び/又は粉粒状無機充填剤との組合せからなる、請求項2に記載のポリアリーレンサルファイド樹脂組成物。
- 前記(C)炭素原子数2以上のα-オレフィン由来の構成単位を含有するオレフィン系共重合体が、
(C1)アミノ基、カルボキシル基、水酸基、酸無水物基、エポキシ基、グリシジル基、イソシアネート基、イソチオシアネート基、アセトキシ基、シラノール基、アルコキシシラン基、アルキニル基、オキサゾリン基、チオール基、スルホン酸基、スルホン酸塩残基、及びカルボン酸エステル基からなる群から選択される少なくとも1種の官能基を含有するオレフィン系共重合体、
(C2)エチレン由来の構成単位と炭素原子数3以上のα-オレフィン由来の構成単位とを含有するオレフィン系共重合体、並びに
(C3)炭素原子数2以上のα-オレフィン由来の構成単位とα,β-不飽和カルボン酸アルキルエステル由来の構成単位とを含有するオレフィン系共重合体、
からなる群から選択される少なくとも1種のオレフィン系共重合体である、請求項1~4のいずれか1項に記載のポリアリーレンサルファイド樹脂組成物。 - 前記(C1)オレフィン系共重合体が、α,β-不飽和酸のグリシジルエステル由来の構成単位を含有する、請求項5に記載のポリアリーレンサルファイド樹脂組成物。
- 前記(C1)オレフィン系共重合体が、無水マレイン酸変性エチレン系共重合体、グリシジルメタクリレート変性エチレン系共重合体、グリシジルエーテル変性エチレン系共重合体からなる群から選択される少なくとも1種のオレフィン系共重合体である、請求項5又は6に記載のポリアリーレンサルファイド樹脂組成物。
- 前記(C1)オレフィン系共重合体が、更に(メタ)アクリル酸アルキルエステル由来の構成単位を含有する、請求項5~7のいずれか1項に記載のポリアリーレンサルファイド樹脂組成物。
- 請求項1~8のいずれか1項に記載のポリアリーレンサルファイド樹脂組成物を含む樹脂部材と、金属、合金又は無機固体物を含むインサート部材とを有する、インサート成形品。
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