JP6797360B2 - Polyarylene sulfide resin composition, molded article and manufacturing method - Google Patents
Polyarylene sulfide resin composition, molded article and manufacturing method Download PDFInfo
- Publication number
- JP6797360B2 JP6797360B2 JP2016206885A JP2016206885A JP6797360B2 JP 6797360 B2 JP6797360 B2 JP 6797360B2 JP 2016206885 A JP2016206885 A JP 2016206885A JP 2016206885 A JP2016206885 A JP 2016206885A JP 6797360 B2 JP6797360 B2 JP 6797360B2
- Authority
- JP
- Japan
- Prior art keywords
- polyarylene sulfide
- sulfide resin
- resin composition
- range
- polyvinylpyrrolidone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims description 96
- 229920000412 polyarylene Polymers 0.000 title claims description 95
- 239000011342 resin composition Substances 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 229920005989 resin Polymers 0.000 claims description 85
- 239000011347 resin Substances 0.000 claims description 85
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 33
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 33
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 33
- 229920002050 silicone resin Polymers 0.000 claims description 33
- 238000000465 moulding Methods 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 11
- 238000004898 kneading Methods 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000000047 product Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 230000000694 effects Effects 0.000 description 12
- 150000001491 aromatic compounds Chemical class 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- -1 alkali metal salt Chemical class 0.000 description 8
- 230000001771 impaired effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000000816 ethylene group Polymers [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- NNTRMVRTACZZIO-UHFFFAOYSA-N 3-isocyanatopropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCN=C=O NNTRMVRTACZZIO-UHFFFAOYSA-N 0.000 description 1
- NMUBRRLYMADSGF-UHFFFAOYSA-N 3-triethoxysilylpropan-1-ol Chemical compound CCO[Si](OCC)(OCC)CCCO NMUBRRLYMADSGF-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 1
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- OSSMYOQKNHMTIP-UHFFFAOYSA-N 5-[dimethoxy(methyl)silyl]pentane-1,3-diamine Chemical compound CO[Si](C)(OC)CCC(N)CCN OSSMYOQKNHMTIP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 0 CC*(C)[C@@](CCCCC1)C1N Chemical compound CC*(C)[C@@](CCCCC1)C1N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- PJIFJEUHCQYNHO-UHFFFAOYSA-N diethoxy-(3-isocyanatopropyl)-methylsilane Chemical compound CCO[Si](C)(OCC)CCCN=C=O PJIFJEUHCQYNHO-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-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
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- WYZXIJYWXFEAFG-UHFFFAOYSA-N ethyl-(3-isocyanatopropyl)-dimethoxysilane Chemical compound CC[Si](OC)(OC)CCCN=C=O WYZXIJYWXFEAFG-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 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
- 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
- 239000012803 melt mixture Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 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
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 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
- 239000013464 silicone adhesive Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- DDBUVUBWJVIGFH-UHFFFAOYSA-N trichloro(3-isocyanatopropyl)silane Chemical compound Cl[Si](Cl)(Cl)CCCN=C=O DDBUVUBWJVIGFH-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical group C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
本発明は、ポリアリーレンスルフィド樹脂組成物、成形品およびそれらの製造方法に関する。 The present invention relates to polyarylene sulfide resin compositions, molded articles, and methods for producing them.
ポリフェニレンスルフィド（以下ＰＰＳと略すことがある）樹脂に代表されるポリアリーレンスルフィド（以下ＰＡＳと略すことがある）樹脂は、耐熱性に優れつつ、かつ、機械的強度、耐薬品性、成形加工性、寸法安定性にも優れ、これら特性を利用して、電気・電子機器部品、自動車部品材料等として使用されている。 Polyphenylene sulfide (hereinafter sometimes abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin has excellent heat resistance, and has mechanical strength, chemical resistance, and moldability. It is also excellent in dimensional stability and is used as a material for electrical and electronic equipment parts, automobile parts, etc. by utilizing these characteristics.
そして、これら部品はその二次加工としてシリコーン樹脂等からなる部品材料と接着する場合が多々見られる。しかし、ポリアリーレンスルフィド樹脂は他の樹脂との接着性、特に、シリコーン樹脂またはシリコーン樹脂を含む硬化性樹脂組成物からなる接着剤（以下、シリコーン樹脂系接着剤）との接着性が比較的悪い。そのため、例えばシリコーン樹脂系接着剤によるポリアリーレンスルフィド同士の接合、ポリアリーレンスルフィド樹脂と他の材料との接合、あるいはシリコーン系接着剤による電気・電子部品の封止等の際に、ポリアリーレンスルフィド樹脂とシリコーン樹脂やシリコーン樹脂を含む硬化性樹脂組成物との接着性（以下、シリコーン樹脂接着性ということがある）の悪さが問題となっていた。 Then, these parts are often adhered to a part material made of silicone resin or the like as the secondary processing. However, the polyarylene sulfide resin has relatively poor adhesiveness with other resins, particularly with a silicone resin or an adhesive made of a curable resin composition containing a silicone resin (hereinafter referred to as a silicone resin-based adhesive). .. Therefore, for example, when bonding polyarylene sulfides with a silicone resin adhesive, bonding polyarylene sulfide resin with other materials, or sealing electrical and electronic parts with a silicone adhesive, the polyarylene sulfide resin is used. There has been a problem of poor adhesiveness (hereinafter, sometimes referred to as silicone resin adhesiveness) with a silicone resin or a curable resin composition containing a silicone resin.
そこで、ポリアリーレンスルフィド樹脂と酸化マグネシウムを含むポリアリーレンスルフィド樹脂組成物の成形品がシリコーン樹脂接着性を向上させることが知られている（特許文献１参照）。しかしながら、酸化マグネシウムは比較的安定的な化合物であるものの、空気中に放置すると水分の存在で二酸化炭素を吸収しやすく、吸湿により水酸化マグネシウムに変化したり、炭酸ガス及び水分を吸収して炭酸マグネシウムに変化する。このため、製造原料として厳重な管理が必要であることから、空気中であってもより安定して保存できる製造原料が望まれていた。さらに酸化マグネシウムによるシリコーン樹脂接着性の効果はまだ十分とは言えず、実用的なレベルにまで改良されたとは到底言い難いのが現状であった。 Therefore, it is known that a molded product of a polyarylene sulfide resin composition containing a polyarylene sulfide resin and magnesium oxide improves the adhesiveness of a silicone resin (see Patent Document 1). However, although magnesium oxide is a relatively stable compound, it easily absorbs carbon dioxide due to the presence of moisture when left in the air, and changes to magnesium hydroxide due to moisture absorption, or absorbs carbon dioxide gas and moisture to provide carbon dioxide. Changes to magnesium. Therefore, since strict control is required as a manufacturing raw material, a manufacturing raw material that can be stored more stably even in the air has been desired. Furthermore, the effect of magnesium oxide on silicone resin adhesion is not yet sufficient, and it is hard to say that it has been improved to a practical level.
本発明が解決しようとする課題は、シリコーン樹脂接着性に優れた成形品となるポリアリーレンスルフィド樹脂組成物およびそれを成形して得られる、シリコーン樹脂接着性に優れた成形品を提供すること、さらに該成形品と、シリコーン樹脂を含む硬化性樹脂組成物の硬化物とが接着してなる複合成形品を提供すること、およびそれらの製造方法を提供することにある。 An object to be solved by the present invention is to provide a polyarylene sulfide resin composition which is a molded product having excellent silicone resin adhesiveness and a molded product having excellent silicone resin adhesiveness obtained by molding the polyarylene sulfide resin composition. A further object of the present invention is to provide a composite molded product obtained by adhering the molded product and a cured product of a curable resin composition containing a silicone resin, and to provide a method for producing the same.
本発明者は上記課題を解決するために鋭意研究した結果、ポリアリーレンスルフィド樹脂に、高分子量のポリビニルピロリドンを配合して溶融混錬することにより得られた樹脂組成物の成形品が、シリコーン樹脂接着性に優れることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventor has obtained a molded product of a resin composition obtained by blending a high molecular weight polyvinylpyrrolidone with a polyarylene sulfide resin and melt-kneading it. We have found that it has excellent adhesiveness, and have completed the present invention.
すなわち、本発明は、ポリアリーレンスルフィド樹脂（Ａ）と、質量平均分子量が５０，０００〜２，０００，０００の範囲のポリビニルピロリドン（Ｂ）とを必須成分として含有すること、
ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、前記ポリビニルピロリドン（Ｂ）が０．０１〜１００質量部の範囲であること、
前記ポリアリーレンスルフィド樹脂（Ａ）をマトリックスとし、当該マトリックス中に、前記ポリビニルピロリドン（Ｂ）が分散したモルフォロジーを形成していること、を特徴とするポリアリーレンスルフィド樹脂組成物、に関する。
That is, the present invention contains a polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) having a mass average molecular weight in the range of 50,000 to 2,000,000 as essential components.
The polyvinylpyrrolidone (B) is in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A).
The present invention relates to a polyarylene sulfide resin composition, wherein the polyarylene sulfide resin (A) is used as a matrix, and a morphology in which the polyvinylpyrrolidone (B) is dispersed is formed in the matrix.
加えて本発明は、前記ポリアリーレンスルフィド樹脂組成物を成形してなる成形品、に関する。 In addition, the present invention relates to a molded product obtained by molding the polyarylene sulfide resin composition.
さらに本発明は前記ポリアリーレンスルフィド樹脂組成物を成形してなる成形品と、シリコーン樹脂またはシリコーンを含む硬化性樹脂組成物の硬化物とが接着してなる複合成形品、に関する。 Further, the present invention relates to a molded product obtained by molding the polyarylene sulfide resin composition and a composite molded product obtained by adhering a silicone resin or a cured product of a curable resin composition containing silicone.
また、本発明は、ポリアリーレンスルフィド樹脂（Ａ）と、質量平均分子量が５０，０００〜２，０００，０００の範囲のポリビニルピロリドン（Ｂ）とを必須成分として、ポリアリーレンスルフィド樹脂（Ａ）の融点以上で溶融混練することを特徴とするポリアリーレンスルフィド樹脂組成物の製造方法、に関する。 Further, the present invention comprises a polyarylene sulfide resin (A) and a polyvinylpyrrolidone (B) having a mass average molecular weight in the range of 50,000 to 2,000,000 as essential components of the polyarylene sulfide resin (A). The present invention relates to a method for producing a polyarylene sulfide resin composition, which comprises melt-kneading at a temperature equal to or higher than the melting point.
また、本発明は、前記の製造方法で得られたポリアリーレンスルフィド樹脂組成物を成形する、成形品の製造方法、に関する。 The present invention also relates to a method for producing a molded product, which forms the polyarylene sulfide resin composition obtained by the above-mentioned production method.
また、本発明は前記の製造方法により得られた成形品と、シリコーン樹脂を含む硬化性樹脂組成物とを接触させた後、該硬化性樹脂組成物を硬化させることを特徴とする複合成形品の製造方法、に関する。 Further, the present invention is characterized in that the molded product obtained by the above-mentioned production method is brought into contact with a curable resin composition containing a silicone resin, and then the curable resin composition is cured. Regarding the manufacturing method of.
本発明によれば、シリコーン樹脂接着性に優れた成形品となるポリアリーレンスルフィド樹脂組成物およびそれを成形して得られる、シリコーン樹脂接着性に優れた成形品を提供すること、さらに該成形品と、シリコーン樹脂を含む硬化性樹脂組成物の硬化物とが接着してなる複合成形品を提供すること、およびそれらの製造方法を提供することができる。 According to the present invention, it is possible to provide a polyarylene sulfide resin composition which is a molded product having excellent silicone resin adhesiveness and a molded product having excellent silicone resin adhesiveness obtained by molding the polyarylene sulfide resin composition, and further. It is possible to provide a composite molded product obtained by adhering a cured product of a curable resin composition containing a silicone resin, and to provide a method for producing the same.
本発明のポリアリーレンスルフィド樹脂組成物は、ポリアリーレンスルフィド樹脂（Ａ）と、質量平均分子量が５０，０００〜２，０００，０００の範囲のポリビニルピロリドン（Ｂ）とを必須成分として含有すること、
ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、前記ポリビニルピロリドン（Ｂ）が０．０１〜１００質量部の範囲であること、を特徴とする。
The polyarylene sulfide resin composition of the present invention contains the polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) having a mass average molecular weight in the range of 50,000 to 2,000,000 as essential components.
The polyvinylpyrrolidone (B) is in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A).
本発明のポリアリーレンスルフィド樹脂組成物は、ポリアリーレンスルフィド樹脂（Ａ）を必須成分として含有する。本発明で用いるポリアリーレンスルフィド樹脂は、芳香族環と硫黄原子とが結合した構造を繰り返し単位とする樹脂構造を有するものであり、具体的には、下記一般式（２） The polyarylene sulfide resin composition of the present invention contains the polyarylene sulfide resin (A) as an essential component. The polyarylene sulfide resin used in the present invention has a resin structure having a structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit. Specifically, the following general formula (2)
ここで、前記一般式（２）で表される構造部位は、特に該式中のＲ１及びＲ２は、前記ポリアリーレンスルフィド樹脂の機械的強度の点から水素原子であることが好ましく、その場合、下記式（４）で表されるパラ位で結合するもの、及び下記式（５）で表されるメタ位で結合するものが挙げられる。 Here, the structural portion represented by the general formula (2) is preferably a hydrogen atom in particular, R 1 and R 2 in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin. In this case, those that are combined at the para position represented by the following formula (4) and those that are combined at the meta position represented by the following formula (5) can be mentioned.
また、前記ポリアリーレンスルフィド樹脂は、前記一般式（２）や（３）で表される構造部位のみならず、下記の構造式（６）〜（９） Further, the polyarylene sulfide resin has not only the structural parts represented by the general formulas (2) and (3) but also the following structural formulas (6) to (9).
また、前記ポリアリーレンスルフィド樹脂は、その分子構造中に、ナフチルスルフィド結合などを有していてもよいが、他の構造部位との合計モル数に対して、３モル％以下が好ましく、特に１モル％以下であることが好ましい。 Further, the polyarylene sulfide resin may have a naphthyl sulfide bond or the like in its molecular structure, but is preferably 3 mol% or less, particularly 1 in terms of the total number of moles with other structural sites. It is preferably mol% or less.
また、ポリアリーレンスルフィド樹脂の物性は、本発明の効果を損ねない限り特に限定されないが、以下の通りである。 The physical properties of the polyarylene sulfide resin are not particularly limited as long as the effects of the present invention are not impaired, but are as follows.
（溶融粘度）
本発明に用いるポリアリーレンスルフィド樹脂は、３００℃で測定した溶融粘度（Ｖ６）が２〜１０００〔Ｐａ・ｓ〕の範囲であることが好ましく、さらに流動性および機械的強度のバランスが良好となることから１０〜５００〔Ｐａ・ｓ〕の範囲がより好ましく、特に６０〜２００〔Ｐａ・ｓ〕の範囲であることが特に好ましい。但し、本発明において、溶融粘度（Ｖ６）は、ポリアリーレンスルフィド樹脂を島津製作所製フローテスター、ＣＦＴ−５００Ｄを用い、３００℃、荷重：１．９６×１０６Ｐａ、Ｌ／Ｄ＝１０（ｍｍ）／１（ｍｍ）にて、６分間保持した後に溶融粘度を測定した値とする。
(Melting viscosity)
The polyarylene sulfide resin used in the present invention preferably has a melt viscosity (V6) measured at 300 ° C. in the range of 2 to 1000 [Pa · s], and further has a good balance between fluidity and mechanical strength. Therefore, the range of 10 to 500 [Pa · s] is more preferable, and the range of 60 to 200 [Pa · s] is particularly preferable. However, in the present invention, the melt viscosity (V6) is 300 ° C., load: 1.96 × 10 6 Pa, L / D = 10 (mm) using a polyarylene sulfide resin, a flow tester manufactured by Shimadzu Corporation, CFT-500D. ) / 1 (mm), the melt viscosity is measured after holding for 6 minutes.
（非ニュートン指数）
本発明に用いるポリアリーレンスルフィド樹脂（Ａ）の非ニュートン指数は、本発明の効果を損ねない限り特に限定されないが、０．９０〜２．００の範囲であることが好ましい。リニア型ポリアリーレンスルフィド樹脂を用いる場合には、非ニュートン指数が０．９０〜１．５０の範囲であることが好ましく、さらに０．９５〜１．２０の範囲であることがより好ましい。このようなポリアリーレンスルフィド樹脂は機械的物性、流動性、耐磨耗性に優れる。ただし、非ニュートン指数（Ｎ値）は、キャピログラフを用いて３００℃、オリフィス長（Ｌ）とオリフィス径（Ｄ）の比、Ｌ／Ｄ＝４０の条件下で、剪断速度及び剪断応力を測定し、下記式を用いて算出した値である。
(Non-Newtonian index)
The non-Newtonian index of the polyarylene sulfide resin (A) used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.90 to 2.00. When a linear polyarylene sulfide resin is used, the non-Newtonian index is preferably in the range of 0.99 to 1.50, and more preferably in the range of 0.95 to 1.20. Such a polyarylene sulfide resin is excellent in mechanical properties, fluidity, and abrasion resistance. However, for the non-Newtonian index (N value), the shear rate and shear stress are measured under the conditions of 300 ° C., the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40 using a capillograph. , It is a value calculated by using the following formula.
（製造方法）
前記ポリアリーレンスルフィド樹脂（Ａ）の製造方法としては、特に限定されないが、例えば１）硫黄と炭酸ソーダの存在下でジハロゲノ芳香族化合物を、必要ならばポリハロゲノ芳香族化合物ないしその他の共重合成分を加えて、重合させる方法、２）極性溶媒中でスルフィド化剤等の存在下にジハロゲノ芳香族化合物を、必要ならばポリハロゲノ芳香族化合物ないしその他の共重合成分を加えて、重合させる方法、３）ｐ−クロルチオフェノールを、必要ならばその他の共重合成分を加えて、自己縮合させる方法、等が挙げられる。これらの方法のなかでも、２）の方法が汎用的であり好ましい。反応の際に、重合度を調節するためにカルボン酸やスルホン酸のアルカリ金属塩や、水酸化アルカリを添加しても良い。上記２）方法のなかでも、加熱した有機極性溶媒とジハロゲノ芳香族化合物とを含む混合物に含水スルフィド化剤を水が反応混合物から除去され得る速度で導入し、有機極性溶媒中でジハロゲノ芳香族化合物とスルフィド化剤とを、必要に応じてポリハロゲノ芳香族化合物と加え、反応させること、及び反応系内の水分量を該有機極性溶媒１モルに対して０．０２〜０．５モルの範囲にコントロールすることによりポリアリーレンスルフィド樹脂を製造する方法（特開平０７−２２８６９９号公報参照。）や、固形のアルカリ金属硫化物及び非プロトン性極性有機溶媒の存在下でジハロゲノ芳香族化合物と必要ならばポリハロゲノ芳香族化合物ないしその他の共重合成分を加え、アルカリ金属水硫化物及び有機酸アルカリ金属塩を、硫黄源１モルに対して０．０１〜０．９モルの範囲の有機酸アルカリ金属塩および反応系内の水分量を非プロトン性極性有機溶媒１モルに対して０．０２モル以下の範囲にコントロールしながら反応させる方法（ＷＯ２０１０／０５８７１３号パンフレット参照。）で得られるものが特に好ましい。ジハロゲノ芳香族化合物の具体的な例としては、ｐ−ジハロベンゼン、ｍ−ジハロベンゼン、ｏ−ジハロベンゼン、２，５−ジハロトルエン、１，４−ジハロナフタレン、１−メトキシ−２，５−ジハロベンゼン、４，４’−ジハロビフェニル、３，５−ジハロ安息香酸、２，４−ジハロ安息香酸、２，５−ジハロニトロベンゼン、２，４−ジハロニトロベンゼン、２，４−ジハロアニソール、ｐ，ｐ’−ジハロジフェニルエーテル、４，４’−ジハロベンゾフェノン、４，４’−ジハロジフェニルスルホン、４，４’−ジハロジフェニルスルホキシド、４，４’−ジハロジフェニルスルフィド、及び、上記各化合物の芳香環に炭素原子数１〜１８の範囲のアルキル基を有する化合物が挙げられ、ポリハロゲノ芳香族化合物としては１，２，３−トリハロベンゼン、１，２，４−トリハロベンゼン、１，３，５−トリハロベンゼン、１，２，３，５−テトラハロベンゼン、１，２，４，５−テトラハロベンゼン、１，４，６−トリハロナフタレンなどが挙げられる。また、上記各化合物中に含まれるハロゲン原子は、塩素原子、臭素原子であることが望ましい。
(Production method)
The method for producing the polyarylene sulfide resin (A) is not particularly limited, but for example, 1) a dihalogeno aromatic compound in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogeno aromatic compound or other copolymerization component. In addition, a method of polymerizing, 2) a method of adding a dihalogeno aromatic compound in the presence of a sulfidizing agent or the like in a polar solvent, and if necessary, a polyhalogeno aromatic compound or other copolymerizing component to polymerize, 3) Examples thereof include a method of self-condensing p-chlorothiophenol by adding other copolymerization components if necessary. Among these methods, the method 2) is general and preferable. At the time of the reaction, an alkali metal salt of a carboxylic acid or a sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above 2) methods, a hydrous sulfide agent is introduced into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogeno aromatic compound is introduced in the organic polar solvent. And a sulfide agent, if necessary, with a polyhalogeno aromatic compound to react, and the amount of water in the reaction system should be in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent. A method for producing a polyarylene sulfide resin by control (see JP-A-07-2286999), or if necessary with a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotonic polar organic solvent. Polyhalogeno aromatic compounds or other copolymerization components are added to add alkali metal hydrosulfides and organic acid alkali metal salts to organic acid alkali metal salts in the range of 0.01 to 0.9 mol per 1 mol of sulfur source. It is particularly preferable to obtain one obtained by a method of reacting while controlling the amount of water in the reaction system to 0.02 mol or less with respect to 1 mol of the aprotonic polar organic solvent (see WO2010 / 058713 pamphlet). Specific examples of dihalogeno aromatic compounds include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4, 4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p '-Dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenylsulfone, 4,4'-dihalodiphenylsulfoxide, 4,4'-dihalodiphenylsulfide, and the above compounds. Examples of the compound having an alkyl group having an alkyl group in the range of 1 to 18 carbon atoms in the aromatic ring of the above are examples, and examples of the polyhalogeno aromatic compound are 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3. Examples thereof include 5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene and 1,4,6-trihalonaphthalene. Further, it is desirable that the halogen atom contained in each of the above compounds is a chlorine atom or a bromine atom.
重合工程により得られたポリアリーレンスルフィド樹脂を含む反応混合物の後処理方法としては、特に制限されるものではないが、例えば、（１）重合反応終了後、先ず反応混合物をそのまま、あるいは酸または塩基を加えた後、減圧下または常圧下で溶媒を留去し、次いで溶媒留去後の固形物を水、反応溶媒（又は低分子ポリマーに対して同等の溶解度を有する有機溶媒）、アセトン、メチルエチルケトン、アルコール類などの溶媒で１回または２回以上洗浄し、更に中和、水洗、濾過および乾燥する方法、或いは、（２）重合反応終了後、反応混合物に水、アセトン、メチルエチルケトン、アルコール類、エーテル類、ハロゲン化炭化水素、芳香族炭化水素、脂肪族炭化水素などの溶媒（使用した重合溶媒に可溶であり、かつ少なくともポリアリーレンスルフィドに対しては貧溶媒である溶媒）を沈降剤として添加して、ポリアリーレンスルフィドや無機塩等の固体状生成物を沈降させ、これらを濾別、洗浄、乾燥する方法、或いは、（３）重合反応終了後、反応混合物に反応溶媒（又は低分子ポリマーに対して同等の溶解度を有する有機溶媒）を加えて撹拌した後、濾過して低分子量重合体を除いた後、水、アセトン、メチルエチルケトン、アルコール類などの溶媒で１回または２回以上洗浄し、その後中和、水洗、濾過および乾燥をする方法、（４）重合反応終了後、反応混合物に水を加えて水洗浄、濾過、必要に応じて水洗浄の時に酸を加えて酸処理し、乾燥をする方法、（５）重合反応終了後、反応混合物を濾過し、必要に応じ、反応溶媒で１回または２回以上洗浄し、更に水洗浄、濾過および乾燥する方法、等が挙げられる。 The method for post-treating the reaction mixture containing the polyarylene sulfide resin obtained in the polymerization step is not particularly limited. For example, (1) after completion of the polymerization reaction, the reaction mixture is first used as it is, or an acid or a base. After adding the solvent, the solvent was distilled off under reduced pressure or normal pressure, and then the solid substance after the solvent was distilled off was water, a reaction solvent (or an organic solvent having equivalent solubility in a low molecular weight polymer), acetone, and methyl ethyl ketone. , Wash once or twice or more with a solvent such as alcohols, and further neutralize, wash with water, filter and dry, or (2) after completion of the polymerization reaction, add water, acetone, methyl ethyl ketone, alcohols, etc. to the reaction mixture. Solvents such as ethers, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (solvents that are soluble in the polymerization solvent used and at least poor for polyarylene sulfide) are used as precipitants. Addition to precipitate solid products such as polyarylene sulfide and inorganic salts, which are separated by filtration, washed and dried, or (3) after completion of the polymerization reaction, a reaction solvent (or low molecular weight) is added to the reaction mixture. An organic solvent having the same solubility as the polymer) is added and stirred, and then filtered to remove the low molecular weight polymer, and then washed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc. Then, neutralization, washing with water, filtration and drying are performed. (4) After completion of the polymerization reaction, water is added to the reaction mixture for washing with water, filtration, and if necessary, acid treatment with water at the time of washing with water. , (5) After completion of the polymerization reaction, the reaction mixture is filtered, washed once or twice or more with a reaction solvent, and further washed with water, filtered and dried, and the like. ..
尚、上記（１）〜（５）に例示したような後処理方法において、ポリアリーレンスルフィド樹脂の乾燥は真空中で行なってもよいし、空気中あるいは窒素のような不活性ガス雰囲気中で行なってもよい。 In the post-treatment methods as illustrated in (1) to (5) above, the polyarylene sulfide resin may be dried in vacuum, in air, or in an atmosphere of an inert gas such as nitrogen. You may.
本発明のポリアリーレンスルフィド樹脂組成物は、ポリビニルピロリドン（Ｂ）を必須成分として含有する。該ポリビニルピロリドンは、質量平均分子量が、５０，０００〜２，０００，０００の範囲であり、好ましくは５００，０００〜１，５００，０００の範囲であり、さらに好ましくは１，０００，０００〜１，２００，０００の範囲である。重合度ｎは質量平均分子量が上記範囲となる値であれば特に限定されないが、好ましくはｎが４５０〜１８，０００の範囲であることが好ましく、４，５００〜１３，５００の範囲であることが好ましく、さらに９，０００〜１０８，０００の範囲であることが特に好ましい。ポリビニルピロリドンは直鎖型のものでも架橋型のものでも差し支えない。 The polyarylene sulfide resin composition of the present invention contains polyvinylpyrrolidone (B) as an essential component. The polyvinylpyrrolidone has a mass average molecular weight in the range of 50,000 to 2,000,000, preferably in the range of 500,000 to 1,500,000, more preferably 1,000,000 to 1. , 200,000. The degree of polymerization n is not particularly limited as long as the mass average molecular weight is in the above range, but preferably n is in the range of 450 to 18,000 and is in the range of 4,500 to 13,500. Is preferable, and the range is particularly preferably in the range of 9,000 to 108,000. Polyvinylpyrrolidone may be linear or crosslinked.
ポリビニルピロリドン（Ｂ）としては、例えば下記一般式（１） Examples of polyvinylpyrrolidone (B) include the following general formula (1).
上記ポリビニルピロリドンの製造方法は、公知の方法を用いることができ、本発明の効果を損ねない限り特に限定されるものではないが、例えば、２−ピロリドンとアセチレンと原料として反応させる方法（レッペ法）や、Ｎ−ヒドロキシエチルピロリドンの脱水反応による方法の他、好ましくは、Ｎ−ヒドロキシエチルピロリドンを気相脱水反応させて得られた、γ−ブチロラクトン含有量が、例えば５００ｐｐｍ以下に低減させたＮ−ビニルピロリドンを、公知の重合開始剤や塩基性ｐＨ調整剤を適宜加えて、ラジカル重合する方法などが挙げられる。 The method for producing polyvinylpyrrolidone can be a known method and is not particularly limited as long as the effect of the present invention is not impaired. For example, a method of reacting 2-pyrrolidone with acetylene as a raw material (Repe method). ) And the method by dehydration reaction of N-hydroxyethylpyrrolidone, preferably N-hydroxyethylpyrrolidone obtained by vapor phase dehydration reaction and having a γ-butyrolactone content reduced to 500 ppm or less, for example. A method of radically polymerizing vinylpyrrolidone by appropriately adding a known polymerization initiator or basic pH adjuster can be mentioned.
ここで、前記Ｎ−ビニルピロリドンは、下記一般式（１０） Here, the N-vinylpyrrolidone is described by the following general formula (10).
本発明で用いるポリビニルピロリドンは、前記Ｎ−ビニルピロリドンを原料とした単独重合物であることが好ましいが、本発明の効果を損ねない範囲で、前記一般式（１０）で表されるＮ−ビニルピロリドン、その他のモノマーを原料とする共重合物であってもよく、その場合、その他のモノマーの使用量は１０質量％以下であることが好ましく、１質量％以下であることがより好ましく、０．１質量％以下であることがさらに好ましい。 The polyvinylpyrrolidone used in the present invention is preferably a copolymer using the N-vinylpyrrolidone as a raw material, but N-vinyl represented by the general formula (10) is used as long as the effects of the present invention are not impaired. A copolymer using pyrrolidone or another monomer as a raw material may be used. In that case, the amount of the other monomer used is preferably 10% by mass or less, more preferably 1% by mass or less, and 0. It is more preferably 1% by mass or less.
その他のモノマーとしては、例えば、下記一般式（１１） Examples of other monomers include the following general formula (11).
本発明で用いるポリビニルピロリドンは、例えば、株式会社日本触媒製「Ｋ−９０」、同「Ｋ−８５」、同「Ｋ−３０」などとして市販のものを用いることができる。 As the polyvinylpyrrolidone used in the present invention, commercially available products such as "K-90", "K-85", and "K-30" manufactured by Nippon Shokubai Co., Ltd. can be used.
本発明においてポリビニルピロリドン（Ｂ）は、ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、０．０１〜１００質量部の範囲であることが好ましく、０．１〜〜５０質量部の範囲であることがより好ましく、１〜３０質量部の範囲であることがさらに好ましく、２〜２５質量部の範囲であることが最も好ましい。かかる範囲において、本発明のポリアリーレンスルフィド樹脂成形品が良好なシリコーン樹脂接着性を呈するため好ましい。 In the present invention, polyvinylpyrrolidone (B) is preferably in the range of 0.01 to 100 parts by mass, preferably in the range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is more preferably in the range of 1 to 30 parts by mass, and most preferably in the range of 2 to 25 parts by mass. In such a range, the polyarylene sulfide resin molded product of the present invention is preferable because it exhibits good silicone resin adhesiveness.
本発明のポリアリーレンスルフィド樹脂組成物は、必要に応じて、充填剤を任意成分として含有することができる。これら充填剤としては本発明の効果を損なうものでなければ公知慣用の材料を用いることもでき、例えば、繊維状のものや、粒状や板状などの非繊維状のものなど、さまざまな形状の充填剤等が挙げられる。具体的には、ガラス繊維、炭素繊維、シランガラス繊維、セラミック繊維、アラミド繊維、金属繊維、チタン酸カリウム、炭化珪素、珪酸カルシウム、ワラストナイト等の繊維、天然繊維等の繊維状充填剤が使用でき、またガラスビーズ、ガラスフレーク、硫酸バリウム、クレー、パイロフィライト、ベントナイト、セリサイト、マイカ、雲母、タルク、アタパルジャイト、フェライト、珪酸カルシウム、炭酸カルシウム、炭酸マグネシウム、ガラスビーズ、ゼオライト、ミルドファイバー、硫酸カルシウム等の非繊維状充填剤も使用できる。 The polyarylene sulfide resin composition of the present invention may contain a filler as an optional component, if necessary. As these fillers, known and commonly used materials can be used as long as they do not impair the effects of the present invention, and have various shapes such as fibrous ones and non-fibrous ones such as granular and plate-like ones. Examples include fillers. Specifically, glass fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium silicate, warastonite and other fibers, and natural fibers and other fibrous fillers are used. Can also be used, glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, mica, talc, attapulsite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, milled fiber , Non-fibrous fillers such as calcium sulfate can also be used.
本発明において充填剤は必須成分ではなく、添加する場合、その含有量は本発明の効果を損ねなければ特に限定されるものではない。充填剤の含有量としては、例えば、ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、１〜６００質量部の範囲であることが好ましく、さらに１０〜２００質量部の範囲であることがより好ましい。かかる範囲において、樹脂組成物が良好な機械強度と成形性を示すため好ましい。 In the present invention, the filler is not an essential component, and when added, the content thereof is not particularly limited as long as the effect of the present invention is not impaired. The content of the filler is preferably in the range of 1 to 600 parts by mass, and more preferably in the range of 10 to 200 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). preferable. In such a range, the resin composition is preferable because it exhibits good mechanical strength and moldability.
本発明のポリアリーレンスルフィド樹脂組成物は、必要に応じて、シランカップリング剤を任意成分として含有することができる。シランカップリング剤としては、本発明の効果を損ねなければ特に限定されないが、カルボキシ基と反応する官能基、例えば、エポキシ基、イソシアナト基、アミノ基または水酸基を有するシランカップリング剤が好ましいものとして挙げられる。このようなシランカップリング剤としては、例えば、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ基含有アルコキシシラン化合物、γ−イソシアナトプロピルトリメトキシシラン、γ−イソシアナトプロピルトリエトキシシラン、γ−イソシアナトプロピルメチルジメトキシシラン、γ−イソシアナトプロピルメチルジエトキシシラン、γ−イソシアナトプロピルエチルジメトキシシラン、γ−イソシアナトプロピルエチルジエトキシシラン、γ−イソシアナトプロピルトリクロロシラン等のイソシアナト基含有アルコキシシラン化合物、γ−（２−アミノエチル）アミノプロピルメチルジメトキシシラン、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン等のアミノ基含有アルコキシシラン化合物、γ−ヒドロキシプロピルトリメトキシシラン、γ−ヒドロキシプロピルトリエトキシシラン等の水酸基含有アルコキシシラン化合物が挙げられる。本発明においてシランカップリング剤は必須成分ではないが、添加する場合、その配合量は、本発明の効果を損ねなければその添加量は特に限定されないが、ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、０．０１〜１０質量部の範囲であることが好ましく、さらに０．１〜５質量部の範囲であることがより好ましい。かかる範囲において、樹脂組成物が良好な耐コロナ性と成形性、特に離形性を有し、かつ成形品がエポキシ樹脂と優れた接着性を呈しつつ、さらに機械的強度が向上するため好ましい。 The polyarylene sulfide resin composition of the present invention may contain a silane coupling agent as an optional component, if necessary. The silane coupling agent is not particularly limited as long as the effect of the present invention is not impaired, but a silane coupling agent having a functional group that reacts with a carboxy group, for example, an epoxy group, an isocyanato group, an amino group or a hydroxyl group is preferable. Can be mentioned. Examples of such a silane coupling agent include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Containing alkoxysilane compound, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane , Γ-Isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane and other isocyanato group-containing alkoxysilane compounds, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) amino Examples thereof include amino group-containing alkoxysilane compounds such as propyltrimethoxysilane and γ-aminopropyltrimethoxysilane, and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. Although the silane coupling agent is not an essential component in the present invention, when it is added, the blending amount thereof is not particularly limited as long as the effect of the present invention is not impaired, but the addition amount is not particularly limited, but 100 parts by mass of the polyarylene sulfide resin (A). On the other hand, it is preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass. In such a range, the resin composition is preferable because it has good corona resistance and moldability, particularly mold releasability, and the molded product exhibits excellent adhesiveness to the epoxy resin while further improving the mechanical strength.
本発明のポリアリーレンスルフィド樹脂組成物は、必要に応じて、熱可塑性エラストマーを任意成分として含有することができる。熱可塑性エラストマーとしては、ポリオレフィン系エラストマー、弗素系エラストマーまたはシリコーン系エラストマーが挙げられ、このうちポリオレフィン系エラストマーが好ましいものとして挙げられる。これらのエラストマーを添加する場合、その含有量は、本発明の効果を損ねなければ特に限定されないが、ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、０．０１〜１０質量部の範囲であることが好ましく、さらに０．１〜５質量部の範囲であることがより好ましい。かかる範囲において、得られるポリアリーレンスルフィド樹脂組成物の耐衝撃性が向上するため好ましい。 The polyarylene sulfide resin composition of the present invention can contain a thermoplastic elastomer as an optional component, if necessary. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluoroelastomers, and silicone-based elastomers, and among them, polyolefin-based elastomers are preferable. When these elastomers are added, the content thereof is not particularly limited as long as the effects of the present invention are not impaired, but is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is preferably in the range of 0.1 to 5 parts by mass, and more preferably. In such a range, the impact resistance of the obtained polyarylene sulfide resin composition is improved, which is preferable.
前記ポリオレフィン系エラストマーは、例えば、α−オレフィンの単独重合または異なるα−オレフィン同士の共重合により、さらに、官能基を付与する場合には、α−オレフィンと官能基を有するビニル重合性化合物との共重合により得ることができる。α−オレフィンは、例えば、エチレン、プロピレン及びブテン−１等の炭素原子数２〜８の範囲のものが挙げられる。また、官能基としては、カルボキシ基、式−（ＣＯ）Ｏ（ＣＯ）−で表される酸無水物基、それらのエステル、エポキシ基、アミノ基、水酸基、メルカプト基、イソシアネート基、またはオキサゾリン基などが挙げられる。 The polyolefin-based elastomer is, for example, a homopolymerization of α-olefins or a copolymerization of different α-olefins, and when a functional group is further imparted, the α-olefin and a vinyl polymerizable compound having a functional group are used. It can be obtained by copolymerization. Examples of the α-olefin include those in the range of 2 to 8 carbon atoms such as ethylene, propylene and butene-1. The functional group includes a carboxy group, an acid anhydride group represented by the formula − (CO) O (CO) −, an ester thereof, an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, or an oxazoline group. And so on.
このような官能基を有するビニル重合性化合物の具体例としては、例えば、（メタ）アクリル酸及び（メタ）アクリル酸エステル等のα，β−不飽和カルボン酸及びそのアルキルエステル、マレイン酸、フマル酸、イタコン酸及びその他の炭素原子数４〜１０のα，β−不飽和ジカルボン酸及びその誘導体（モノ若しくはジエステル、及びその酸無水物等）、並びにグリシジル（メタ）アクリレート等が挙げられる。これらの中でも、上述したエポキシ基、カルボキシ基、及び、該酸無水物基からなる群から選ばれる少なくとも１種の官能基を有するエチレン−プロピレン共重合体及びエチレン−ブテン共重合体が、機械的強度、特に靭性及び耐衝撃性の向上の点から好ましい。 Specific examples of the vinyl polymerizable compound having such a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid ester and their alkyl esters, maleic acid and fumaric acid. Examples thereof include acids, itaconic acids and other α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono or diesters and their acid anhydrides, etc.), and glycidyl (meth) acrylates. Among these, ethylene-propylene copolymers and ethylene-butene copolymers having at least one functional group selected from the group consisting of the above-mentioned epoxy group, carboxy group, and acid anhydride group are mechanically used. It is preferable from the viewpoint of improving strength, particularly toughness and impact resistance.
更に、本発明のポリアリーレンスルフィド樹脂組成物は、上記成分に加えて、さらに用途に応じて、適宜、前記ポリアリーレンスルフィド樹脂及び前記ポリビニルピロリドンを除く他の合成樹脂、例えばポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、ポリスルフォン樹脂、ポリエーテルスルフォン樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルケトン樹脂、ポリアリーレン樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリ四弗化エチレン樹脂、ポリ二弗化エチレン樹脂、ポリスチレン樹脂、ＡＢＳ樹脂、フェノール樹脂、ウレタン樹脂、液晶ポリマー等（以下、単に合成樹脂という）を任意成分として含有することができる。また、これらの合成樹脂の含有量は、それぞれの目的に応じて異なり、一概に規定することはできないが、本発明のポリアリーレンスルフィド樹脂組成物中における樹脂成分（前記ポリアリーレンスルフィド樹脂、前記ポリビニルピロリドン及び合成樹脂の合計）における割合としてポリアリーレンスルフィド樹脂及び前記ポリビニルピロリドンの合計が７５．０質量％以上の範囲、好ましくは８０〜９９．９９質量％の範囲となるよう、換言すると、上記の合成樹脂が２５．０質量％以下の範囲、好ましくは０．０１〜２０．０質量％の範囲で、本発明の効果を損なわないよう目的や用途に応じて適宜調整して用いればよい。 Further, in addition to the above components, the polyarylene sulfide resin composition of the present invention further comprises, depending on the intended use, the polyarylene sulfide resin and other synthetic resins other than the polyvinylpyrrolidone, such as polyester resin and polyamide resin. Polyethylene resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyether ketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluorinated ethylene A resin, polydifluorinated ethylene resin, polystyrene resin, ABS resin, phenol resin, urethane resin, liquid crystal polymer and the like (hereinafter, simply referred to as synthetic resin) can be contained as an optional component. Further, the contents of these synthetic resins differ depending on their respective purposes and cannot be unconditionally defined, but the resin components in the polyarylene sulfide resin composition of the present invention (the polyarylene sulfide resin, the polyvinyl). In other words, the total of the polyarylene sulfide resin and the polyvinylpyrrolidone is in the range of 75.0% by mass or more, preferably in the range of 80 to 99.99% by mass, as a ratio in the total of pyrrolidone and synthetic resin). The synthetic resin may be used in a range of 25.0% by mass or less, preferably 0.01 to 20.0% by mass, appropriately adjusted according to the purpose and application so as not to impair the effects of the present invention.
また本発明のポリアリーレンスルフィド樹脂組成物は、その他にも着色剤、帯電防止剤、酸化防止剤、耐熱安定剤、紫外線安定剤、紫外線吸収剤、発泡剤、難燃剤、難燃助剤、防錆剤、およびカップリング剤等の公知慣用の添加剤を必要に応じ、任意成分として含有してもよい。これらの添加剤は必須成分ではなく、例えば、ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、好ましくは０．０１〜１０００質量部の範囲で、本発明の効果を損なわないよう目的や用途に応じて適宜調整して用いればよい。 In addition, the polyarylene sulfide resin composition of the present invention also has a colorant, an antistatic agent, an antioxidant, a heat-resistant stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, a flame retardant aid, and an anti-inflammatory agent. If necessary, known and commonly used additives such as a rust agent and a coupling agent may be contained as optional components. These additives are not essential components, and for example, with respect to 100 parts by mass of the polyarylene sulfide resin (A), the purpose and application are preferably in the range of 0.01 to 1000 parts by mass so as not to impair the effects of the present invention. It may be adjusted appropriately according to the above.
本発明のポリアリーレンスルフィド樹脂組成物の製造方法は、ポリアリーレンスルフィド樹脂（Ａ）と、前記ポリビニルピロリドン（Ｂ）とを必須成分として、ポリアリーレンスルフィド樹脂（Ａ）の融点以上で溶融混練する。 In the method for producing a polyarylene sulfide resin composition of the present invention, the polyarylene sulfide resin (A) and the polyvinylpyrrolidone (B) are melt-kneaded at a temperature equal to or higher than the melting point of the polyarylene sulfide resin (A) as essential components.
本発明のポリアリーレンスルフィド樹脂組成物の好ましい製造方法は、上述した含有量となるよう、ポリアリーレンスルフィド樹脂（Ａ）と、前記ポリビニルピロリドン（Ｂ）の各必須成分と、必要に応じて、充填剤などの任意成分を、粉末、ペレット、細片など様々な形態でリボンブレンター、ヘンシェルミキサー、Ｖブレンダーなどに投入してドライブレンドした後、バンバリーミキサー、ミキシングロール、単軸または２軸の押出機およびニーダーなどの公知の溶融混練機に投入し、樹脂温度がポリアリーレンスルフィド樹脂の融点以上となる温度範囲、好ましくは融点＋１０℃以上となる温度範囲、より好ましくは融点＋１０℃〜融点＋１００℃となる温度範囲、さらに好ましくは融点＋２０〜融点＋５０℃となる温度範囲で溶融混練する工程を経て製造することができる。溶融混練機への各成分の添加、混合は同時に行ってもよいし、分割して行っても良い。 A preferable method for producing the polyarylene sulfide resin composition of the present invention is to fill the polyarylene sulfide resin (A) with each of the essential components of the polyvinylpyrrolidone (B) so as to have the above-mentioned content, if necessary. Arbitrary components such as agents are put into a ribbon blender, Henshell mixer, V blender, etc. in various forms such as powder, pellets, and strips for dry blending, and then extruded from a Banbury mixer, mixing roll, single-screw or biaxial. It is put into a known melt-kneader such as a machine and a kneader, and the resin temperature is in a temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably in a temperature range in which the melting point is + 10 ° C. or higher, and more preferably the melting point is + 10 ° C. to + 100 ° C. It can be produced through a step of melt-kneading in a temperature range that is, more preferably, a melting point of +20 to a melting point of +50 ° C. Each component may be added to and mixed with the melt kneader at the same time, or may be divided.
前記溶融混練機としては分散性や生産性の観点から二軸混練押出機が好ましく、例えば、樹脂成分の吐出量５〜５００（ｋｇ／ｈｒ）の範囲と、スクリュー回転数５０〜５００（ｒｐｍ）の範囲とを適宜調整しながら溶融混練することが好ましく、それらの比率（吐出量／スクリュー回転数）が０．０２〜５（ｋｇ／ｈｒ／ｒｐｍ）の範囲となる条件下に溶融混練することがさらに好ましい。また、前記成分のうち、充填剤や添加剤を添加する場合は、前記二軸混練押出機のサイドフィーダーから該押出機内に投入することが分散性の観点から好ましい。かかるサイドフィーダーの位置は、前記二軸混練押出機のスクリュー全長に対する、該押出機樹脂投入部から該サイドフィーダーまでの距離の比率が、０．１〜０．９の範囲であることが好ましい。中でも０．３〜０．７の範囲であることが特に好ましい。 As the melt kneader, a twin-screw kneading extruder is preferable from the viewpoint of dispersibility and productivity. For example, a resin component discharge amount in the range of 5 to 500 (kg / hr) and a screw rotation speed of 50 to 500 (rpm) are preferable. It is preferable to melt-knead while appropriately adjusting the range of, and melt-knead under the condition that the ratio (discharge amount / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). Is even more preferable. Further, when a filler or an additive is added among the components, it is preferable to put the filler into the extruder from the side feeder of the twin-screw kneading extruder from the viewpoint of dispersibility. The position of the side feeder is preferably in the range of 0.1 to 0.9 in the ratio of the distance from the extruder resin input portion to the side feeder with respect to the total length of the screw of the twin-screw kneading extruder. Above all, the range of 0.3 to 0.7 is particularly preferable.
このように溶融混練して得られる本発明のポリアリーレンスルフィド樹脂組成物は、必須成分であるポリアリーレンスルフィド樹脂（Ａ）と、前記ポリビニルピロリドン（Ｂ）と、必要に応じて加える任意成分およびそれらの由来成分を含む溶融混合物であり、該溶融混練後に、公知の方法でペレット、チップ、顆粒、粉末等の形態に加工してから、必要に応じて１００〜１５０℃の温度で予備乾燥を施して、各種成形に供することが好ましい。 The polyarylene sulfide resin composition of the present invention obtained by melt-kneading in this manner comprises a polyarylene sulfide resin (A) which is an essential component, the polyvinylpyrrolidone (B), an optional component added as necessary, and the like. It is a melt mixture containing the components derived from the above, and after the melt kneading, it is processed into pellets, chips, granules, powders and the like by a known method, and then pre-dried at a temperature of 100 to 150 ° C. as necessary. Therefore, it is preferable to use it for various moldings.
上記製造方法により製造される本発明のポリアリーレンスルフィド樹脂組成物は、ポリアリーレンスルフィド樹脂をマトリックスとし、当該マトリックス中に、必須成分である前記ポリビニルピロリドン（Ｂ）と、それに由来する成分、必要に応じて添加する任意成分が分散したモルフォロジーを形成する。その結果、当該ポリアリーレンスルフィド樹脂組成物の成形品がシリコーン樹脂接着性に優れたものとなり好ましい。 The polyarylene sulfide resin composition of the present invention produced by the above production method uses a polyarylene sulfide resin as a matrix, and in the matrix, the polyvinylpyrrolidone (B) which is an essential component and a component derived from the polyvinylpyrrolidone (B), if necessary. It forms a morphology in which arbitrary components added accordingly are dispersed. As a result, the molded product of the polyarylene sulfide resin composition is preferable because it has excellent silicone resin adhesiveness.
本発明のポリアリーレンスルフィド樹脂組成物は、射出成形、圧縮成形、コンポジット、シート、パイプなどの押出成形、引抜成形、ブロー成形、トランスファー成形など各種成形に供することが可能であるが、特に離形性にも優れるため射出成形用途に適している。射出成形にて成形する場合、各種成形条件は特に限定されず、通常一般的な方法にて成形することができる。例えば、射出成形機内で、樹脂温度がポリアリーレンスルフィド樹脂の融点以上の温度範囲、好ましくは該融点＋１０℃以上の温度範囲、より好ましくは融点＋１０℃〜融点＋１００℃の温度範囲、さらに好ましくは融点＋２０〜融点＋５０℃の温度範囲で前記ポリアリーレンスルフィド樹脂組成物を溶融する工程を経た後、樹脂吐出口よりを金型内に注入して成形すればよい。その際、金型温度も公知の温度範囲、例えば、室温（２３℃）〜３００℃、好ましくは１２０〜１８０℃に設定すればよい。 The polyarylene sulfide resin composition of the present invention can be used for various moldings such as injection molding, compression molding, composite, extrusion molding of sheets, pipes, etc., drawing molding, blow molding, transfer molding, etc. It is also suitable for injection molding because of its excellent properties. When molding by injection molding, various molding conditions are not particularly limited, and molding can usually be performed by a general method. For example, in an injection molding machine, the resin temperature is in a temperature range equal to or higher than the melting point of the polyarylene sulfide resin, preferably in a temperature range of the melting point + 10 ° C. or higher, more preferably in a temperature range of + 10 ° C. to + 100 ° C. After undergoing the step of melting the polyarylene sulfide resin composition in a temperature range of +20 to a melting point of +50 ° C., the polyarylene sulfide resin composition may be injected into a mold from a resin discharge port for molding. At that time, the mold temperature may be set to a known temperature range, for example, room temperature (23 ° C.) to 300 ° C., preferably 120 to 180 ° C.
本発明のポリアリーレンスルフィド樹脂組成物を成形してなる成形品は、シリコーン樹脂との接着性に優れつつ、射出成形時のＴＤ方向の機械的強度にも優れる。そのため、ポリアリーレンスルフィド樹脂とシリコーン樹脂からなる硬化物とが接着した複合成形品として好適に用いることができる。複合成形品を製造する際に用いるシリコーン樹脂としては、当業者が接着剤として通常用いるシリコーン樹脂であればよく、縮合型シリコーン樹脂、付加型シリコーン樹脂のいずれであってもよく、また一液型および二液型のいずれを用いてもよいが、均一に硬化することから付加型シリコーン樹脂を用いることが好ましい。前記複合成形品の製造方法としては各種成形方法により成形したポリアリーレンスルフィド樹脂成形品にシリコーン樹脂を接触させた後、該シリコーン樹脂を硬化することにより複合成形品を製造する方法を用いることができる。 The molded product obtained by molding the polyarylene sulfide resin composition of the present invention is excellent in adhesiveness to a silicone resin and also excellent in mechanical strength in the TD direction during injection molding. Therefore, it can be suitably used as a composite molded product in which a cured product made of a polyarylene sulfide resin and a silicone resin is adhered. The silicone resin used in producing the composite molded product may be any silicone resin usually used as an adhesive by those skilled in the art, and may be either a condensation type silicone resin or an addition type silicone resin, or a one-component type. Either the two-component type or the two-component type may be used, but it is preferable to use an addition type silicone resin because it cures uniformly. As a method for producing the composite molded product, a method of producing the composite molded product by bringing the silicone resin into contact with the polyarylene sulfide resin molded product molded by various molding methods and then curing the silicone resin can be used. ..
前記複合成形体の主な用途例としては、各種家電製品、携帯電話、及びＰＣ（Personal Computer）等の電子機器の筐体、箱型の電気・電子部品集積モジュール用保護・支持部材・複数の個別半導体またはモジュール、センサ、ＬＥＤランプ、コネクタ、ソケット、抵抗器、リレーケース、スイッチ、コイルボビン、コンデンサ、バリコンケース、光ピックアップ、発振子、各種端子板、変成器、プラグ、プリント基板、チューナ、スピーカ、マイクロフォン、ヘッドフォン、小型モータ、磁気ヘッドベース、パワーモジュール、端子台、半導体、液晶、ＦＤＤキャリッジ、ＦＤＤシャーシ、モーターブラッシュホルダ、パラボラアンテナ、コンピュータ関連部品等に代表される電気・電子部品；ＶＴＲ部品、テレビ部品、アイロン、ヘアードライヤ、炊飯器部品、電子レンジ部品、音響部品、オーディオ・レーザディスク・コンパクトディスク・ＤＶＤディスク・ブルーレイディスク等の音声・映像機器部品、照明部品、冷蔵庫部品、エアコン部品、タイプライタ部品、ワードプロセッサ部品、あるいは給湯機や風呂の湯量、温度センサなどの水回り機器部品等に代表される家庭、事務電気製品部品；オフィスコンピュータ関連部品、電話器関連部品、ファクシミリ関連部品、複写機関連部品、洗浄用治具、モーター部品、ライタ、タイプライタなどに代表される機械関連部品：顕微鏡、双眼鏡、カメラ、時計等に代表される光学機器、精密機械関連部品；オルタネーターターミナル、オルタネーターコネクタ、ブラシホルダー、スリップリング、ＩＣレギュレータ、ライトディヤ用ポテンシオメーターベース、リレーブロック、インヒビタースイッチ、排気ガスバルブ等の各種バルブ、燃料関係・排気系・吸気系各種パイプ、エアーインテークノズルスノーケル、インテークマニホールド、燃料ポンプ、エンジン冷却水ジョイント、キャブレターメインボディ、キャブレタースペーサ、排気ガスセンサ、冷却水センサ、油温センサ、ブレーキパットウェアーセンサ、スロットルポジションセンサ、クランクシャフトポジションセンサ、エアーフローメータ、ブレーキパッド摩耗センサ、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダ、ウォーターポンプインペラ、タービンベイン、ワイパーモーター関係部品、デュストリビュータ、スタータースイッチ、イグニッションコイルおよびそのボビン、モーターインシュレータ、モーターロータ、モーターコア、スターターリレ、トランスミッション用ワイヤーハーネス、ウィンドウォッシャーノズル、エアコンパネルスイッチ基板、燃料関係電磁気弁用コイル、ヒューズ用コネクタ、ホーンターミナル、電装部品絶縁板、ステップモーターロータ、ランプソケット、ランプリフレクタ、ランプハウジング、ブレーキピストン、ソレノイドボビン、エンジンオイルフィルタ、点火装置ケース等の自動車・車両関連部品、その他各種用途にも適用可能である。 Examples of the main applications of the composite molded body include housings for various home appliances, mobile phones, electronic devices such as PCs (Personal Computers), protection / support members for box-shaped electric / electronic component integration modules, and a plurality of. Individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed boards, tuners, speakers , Microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, and other electrical and electronic parts; VTR parts , TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio / video equipment parts such as audio / laser discs / compact discs / DVD discs / Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, Household and office electrical product parts represented by typewriter parts, word processor parts, water volume of water heaters and baths, water supply equipment parts such as temperature sensors; office computer related parts, telephone equipment related parts, facsimile related parts, copying Machine-related parts, cleaning jigs, motor parts, writers, typewriters, and other machine-related parts: microscopes, binoculars, cameras, watches, and other optical equipment, precision machine-related parts; alternator terminals, alternator connectors , Brush holder, slip ring, IC regulator, potential meter base for light die, relay block, inhibitor switch, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, Fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor, air conditioner Thermostat base, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dustributor , Starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor core, starter reel, wire harness for transmission, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, It can also be applied to automobile / vehicle-related parts such as insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, and ignition device cases, and various other applications.
＜実施例１〜５及び比較例１〜２＞
表１〜２に記載する組成成分および配合量（全て質量部）に従い、各材料をタンブラーで均一に混合した。その後、東芝機械株式会社製ベント付き２軸押出機「ＴＥＭ−３５Ｂ」に前記配合材料を投入し、樹脂成分吐出量２５ｋｇ／ｈｒ、スクリュー回転数２５０ｒｐｍ、樹脂成分の吐出量（ｋｇ／ｈｒ）とスクリュー回転数（ｒｐｍ）との比率（吐出量／スクリュー回転数）＝０．１（ｋｇ／ｈｒ・ｒｐｍ）、設定樹脂温度３３０℃で溶融混練して樹脂組成物のペレットを得た。このペレットを用いて以下の各種評価試験を行った。試験及び評価の結果は、表１〜２に示す。
<Examples 1 to 5 and Comparative Examples 1 to 2>
Each material was uniformly mixed with a tumbler according to the composition components and blending amounts (all by mass) shown in Tables 1 and 2. After that, the compounded material was put into a twin-screw extruder "TEM-35B" with a vent manufactured by Toshiba Machine Co., Ltd., and the resin component discharge amount was 25 kg / hr, the screw rotation speed was 250 rpm, and the resin component discharge amount (kg / hr). Pellets of the resin composition were obtained by melt-kneading at a ratio (discharge amount / screw rotation speed) = 0.1 (kg / hr · rpm) to the screw rotation speed (rpm) and a set resin temperature of 330 ° C. The following various evaluation tests were performed using these pellets. The results of the tests and evaluations are shown in Tables 1 and 2.
［ＰＡＳ樹脂成形品のシリコーン樹脂との接着強度］
得られたペレットをシリンダー温度３２０℃に設定した住友重機械工業製射出成形機（ＳＥ−７５Ｄ）に供給し、金型温度１４０℃に温調したＡＳＴＭ１号ダンベル片成形用金型を用いて射出成形を行い、ＡＳＴＭ１号ダンベル片を得た。得られたＡＳＴＭ１号ダンベル片を中央から２等分し、シリコン接着剤（東レ・ ダウコーニング、ＳＥ−１７１４、一液・加熱・付加硬化型）との接触面積が２５ｍｍ×１２．５ｍｍ＝３１２．５ｍｍ２となるように成形品を重ね合わせ、クリップを用い固定した後、１５０℃に設定した熱風乾燥機中で０．５時間加熱し硬化・接着させた。２３℃下で１日冷却後クリップを外し、得られた試験片を用いて歪み速度１ｍｍ／ｍｉｎ、支点間距離６５ｍｍ、２３℃下でインストロン社製引張試験機を用い引張破断強さを測定し、接着面積で除した値をシリコン接着強度とした。
[Adhesive strength of PAS resin molded products with silicone resin]
The obtained pellets are supplied to an injection molding machine (SE-75D) manufactured by Sumitomo Heavy Industries, Ltd., whose cylinder temperature is set to 320 ° C., and injected using an ASTM No. 1 dumbbell piece molding die whose temperature is adjusted to a mold temperature of 140 ° C. Molding was performed to obtain an ASTM No. 1 dumbbell piece. The obtained ASTM No. 1 dumbbell piece was divided into two equal parts from the center, and the contact area with the silicon adhesive (Toray Dow Corning, SE-1714, one-component / heating / addition curing type) was 25 mm x 12.5 mm = 312. The molded products were overlapped so as to have a size of 5 mm 2 , fixed using a clip, and then heated in a hot air dryer set at 150 ° C. for 0.5 hours to cure and adhere. After cooling at 23 ° C for 1 day, remove the clip, and measure the tensile breaking strength using the obtained test piece at a strain rate of 1 mm / min, a distance between fulcrums of 65 mm, and a tensile tester manufactured by Instron at 23 ° C. The value divided by the bonding area was taken as the silicon bonding strength.
なお、表１〜表２中の配合樹脂、材料は下記のものである。
ＰＰＳ
Ａ１ リニア型ＰＰＳ ＤＩＣ株式会社製「ＭＡ−５２０」（ピーク分子量３５０００、溶融粘度（Ｖ６）１６０Ｐａ・ｓ）
ビニルピロリドン系添加材
Ｂ１ ポリビニルピロリドン樹脂 株式会社日本触媒製「Ｋ−９０」
（重量平均分子量：１，０５０，０００〜１，２００，０００）
Ｂ２ ポリビニルピロリドン樹脂 株式会社日本触媒製「Ｋ−８５」
（重量平均分子量：９００，０００〜１，０５０，０００）
Ｂ３ ポリビニルピロリドン樹脂 株式会社日本触媒製「Ｋ−３０」
（重量平均分子量：８０，０００〜１２０，０００）
ｂ４ ポリビニルピロリドン樹脂 第一工業製薬株式会社「ピッツコールＫ―１７Ｌ」
（重量平均分子量：９，０００）
The compounded resins and materials in Tables 1 and 2 are as follows.
PPS
A1 Linear type PPS DIC Corporation "MA-520" (peak molecular weight 35000, melt viscosity (V6) 160 Pa · s)
Vinylpyrrolidone-based additive B1 Polyvinylpyrrolidone resin "K-90" manufactured by Nippon Shokubai Co., Ltd.
(Weight average molecular weight: 1,050,000 to 1,200,000)
B2 Polyvinylpyrrolidone resin "K-85" manufactured by Nippon Shokubai Co., Ltd.
(Weight average molecular weight: 900,000 to 1,050,000)
B3 Polyvinylpyrrolidone resin "K-30" manufactured by Nippon Shokubai Co., Ltd.
(Weight average molecular weight: 80,000 to 120,000)
b4 Polyvinylpyrrolidone resin Daiichi Kogyo Seiyaku Co., Ltd. "Pittscol K-17L"
(Weight average molecular weight: 9,000)
無機充填剤
Ｃ１ ガラス繊維 日本電気硝子株式会社製「Ｔ−７１７Ｈ」（直径10μmチョップドストランド）
Ｃ２ 酸化マグネシウム （協和化学工業株式会社製「パイロキスマ（登録商標）５００-０４Ｒ」）
Ｃ３ 炭酸カルシウム （丸尾カルシウム株式会社製、「カルテックス５」（粉末状、平均粒径１．２μｍ）
Inorganic filler C1 glass fiber "T-717H" manufactured by Nippon Electric Glass Co., Ltd. (10 μm diameter chopped strand)
C2 Magnesium oxide (Kyowa Chemical Industry Co., Ltd. "Pyroquisma (registered trademark) 500-04R")
C3 Calcium carbonate (Maruo Calcium Co., Ltd., "Caltex 5" (powder, average particle size 1.2 μm)
Claims (9)
ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、前記ポリビニルピロリドン（Ｂ）が０．０１〜１００質量部の範囲であること、
前記ポリアリーレンスルフィド樹脂（Ａ）をマトリックスとし、当該マトリックス中に、前記ポリビニルピロリドン（Ｂ）が分散したモルフォロジーを形成していること、を特徴とするポリアリーレンスルフィド樹脂組成物。 Obtained by blending polyallylene sulfide resin (A) and polyvinylpyrrolidone (B) having a mass average molecular weight in the range of 50,000 to 2,000,000 as essential components and melt-kneading .
The polyvinylpyrrolidone (B) is in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A).
A polyarylene sulfide resin composition, wherein the polyarylene sulfide resin (A) is used as a matrix, and a morphology in which the polyvinylpyrrolidone (B) is dispersed is formed in the matrix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016206885A JP6797360B2 (en) | 2016-10-21 | 2016-10-21 | Polyarylene sulfide resin composition, molded article and manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016206885A JP6797360B2 (en) | 2016-10-21 | 2016-10-21 | Polyarylene sulfide resin composition, molded article and manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018065965A JP2018065965A (en) | 2018-04-26 |
| JP6797360B2 true JP6797360B2 (en) | 2020-12-09 |
Family
ID=62086820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016206885A Active JP6797360B2 (en) | 2016-10-21 | 2016-10-21 | Polyarylene sulfide resin composition, molded article and manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6797360B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6828414B2 (en) * | 2016-12-21 | 2021-02-10 | Dic株式会社 | Polyarylene sulfide resin composition, molded article and manufacturing method |
| KR20220088709A (en) * | 2019-10-29 | 2022-06-28 | 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 | Polyorganosiloxane composition for adhesion of polyphenylene sulfide resin |
| CN113980466B (en) * | 2021-10-29 | 2023-06-13 | 金发科技股份有限公司 | Polyphenylene sulfide composition and preparation method and application thereof |
-
2016
- 2016-10-21 JP JP2016206885A patent/JP6797360B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018065965A (en) | 2018-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6797350B2 (en) | Polyarylene sulfide resin composition, molded article and manufacturing method | |
| JP5510624B2 (en) | Polyarylene sulfide resin composition and molded article | |
| JP6624204B2 (en) | Polyarylene sulfide resin composition, molded article and manufacturing method | |
| JP6797360B2 (en) | Polyarylene sulfide resin composition, molded article and manufacturing method | |
| JPWO2019208377A1 (en) | Polyarylene sulfide resin composition, molded product, composite molded product and method for producing them | |
| JP6809083B2 (en) | Polyarylene sulfide resin compositions, molded articles and methods for producing them | |
| JP6950281B2 (en) | Polyarylene sulfide resin composition, molded article, metal / resin composite structure and manufacturing method | |
| JP7047248B2 (en) | Polyarylene sulfide resin composition, molded product and manufacturing method | |
| JP6638297B2 (en) | Polyarylene sulfide resin composition, molded article and manufacturing method | |
| JP6828414B2 (en) | Polyarylene sulfide resin composition, molded article and manufacturing method | |
| JP7024932B1 (en) | Polyarylene sulfide resin compositions, molded articles and methods for producing them | |
| JP6753470B2 (en) | Polyarylene sulfide resin composition, molded product and manufacturing method | |
| JP6876261B2 (en) | Resin composition and its molded product | |
| JP7139571B2 (en) | Polyarylene sulfide resin composition and molded article | |
| JP2021080363A (en) | Polyarylene sulfide resin composition, molding, composite molding and method for producing them | |
| WO2020080289A1 (en) | Resin composition and molded article thereof | |
| JP7070811B1 (en) | Polyarylene sulfide resin compositions, molded articles and methods for producing them | |
| JP7136372B2 (en) | Polyarylene sulfide resin composition, molded article and method for producing the same | |
| JP7136381B1 (en) | Polyarylene sulfide resin composition, method for producing polyarylene sulfide resin composition, molded article, method for producing molded article | |
| JP7311051B2 (en) | Polyarylene sulfide resin composition, molded article and method for producing the same | |
| JP7180814B2 (en) | Polyarylene sulfide resin composition, molded article and method for producing the same | |
| JP7136394B1 (en) | Polyarylene sulfide resin composition, molded article and method for producing the same | |
| JP6769582B2 (en) | Polyarylene sulfide resin composition, molded product, composite molded product and method for producing them | |
| JP6866609B2 (en) | Polyarylene sulfide resin compositions, molded articles and methods for producing them | |
| JP6919178B2 (en) | Polyarylene sulfide resin composition and molded article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20180220 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20190624 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190821 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200527 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200721 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201013 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20201026 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6797360 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |