JPH03153757A - Polyphenylene sulfide resin composition - Google Patents
Polyphenylene sulfide resin compositionInfo
- Publication number
- JPH03153757A JPH03153757A JP29435089A JP29435089A JPH03153757A JP H03153757 A JPH03153757 A JP H03153757A JP 29435089 A JP29435089 A JP 29435089A JP 29435089 A JP29435089 A JP 29435089A JP H03153757 A JPH03153757 A JP H03153757A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- resin
- polyphenylene sulfide
- pps
- 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.)
- Pending
Links
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 65
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 63
- 239000011342 resin composition Substances 0.000 title claims description 31
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 24
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 14
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 53
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 10
- 238000005452 bending Methods 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 32
- 239000004721 Polyphenylene oxide Substances 0.000 description 25
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 25
- -1 polysulfan Polymers 0.000 description 17
- 125000003700 epoxy group Chemical group 0.000 description 14
- 239000000835 fiber Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 239000004793 Polystyrene Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000012779 reinforcing material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920000265 Polyparaphenylene Polymers 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 239000012763 reinforcing filler Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- 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 group 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
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 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
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- NMSZFQAFWHFSPE-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCC1CO1 NMSZFQAFWHFSPE-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 101100172118 Caenorhabditis elegans eif-2Bgamma gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920004939 Cariflex™ Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920013633 Fortron Polymers 0.000 description 1
- 239000004738 Fortron® Substances 0.000 description 1
- 239000004724 Iupiace Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000004305 biphenyl Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000002224 dissection Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 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
- 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〕
本発明は、ポリフェニレンサルファイド系樹脂組成物に
関する。更に詳しくは、ポリスチレン系樹脂付加のポリ
フェニレンサルファイドに特定組成比のスチレン系ポリ
マーとポリフェニレンエーテルとの混合組成物または／
及びスチレン系ポリマーとポリフェニレンエーテルとの
グラフト共重合体を含有するポリフェニレンサルファイ
ド系熱可塑性樹脂組成物に関するもので、機械的強度、
耐熱性等ポリフェニレンサルファイド樹脂本来の特性を
実質的に損なうことなく、伸び、衝撃強度等が改良され
機械的特性バランスの良好なポリフェニレンサルファイ
ド系熱可塑性樹脂組成物に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a polyphenylene sulfide resin composition.More specifically, the present invention relates to a polyphenylene sulfide resin composition. Mixed composition or/
and a polyphenylene sulfide thermoplastic resin composition containing a graft copolymer of a styrene polymer and polyphenylene ether, which has excellent mechanical strength,
The present invention relates to a polyphenylene sulfide-based thermoplastic resin composition that has improved elongation, impact strength, etc., and has a good balance of mechanical properties without substantially impairing the inherent properties of polyphenylene sulfide resin such as heat resistance.
ポリフェニレンサルファイド（以下、単にＰＰＳとする
。）樹脂は、機械的強度、耐熱性、耐薬品性等が優れ、
且つ難燃性であるため、電気、電子部品や自動車部品等
の剛性や耐熱性が要求される分野での用途開発が盛んに
なされている。Polyphenylene sulfide (hereinafter simply referred to as PPS) resin has excellent mechanical strength, heat resistance, chemical resistance, etc.
In addition, because it is flame retardant, it is being actively developed for use in fields where rigidity and heat resistance are required, such as electrical and electronic parts and automobile parts.
しかし、これらの用途開発の際、ＰＰＳが伸びや衝撃強
度が極端に低く極めて脆いため、ＰＰＳ単独では成形材
料として使用することができず、これら欠点を補った樹
脂組成物が提案されている。However, when developing these uses, PPS cannot be used alone as a molding material because it has extremely low elongation and impact strength and is extremely brittle, and resin compositions that compensate for these drawbacks have been proposed.
例えば、特開昭５３−９８３５６号公報では、ＰＰＳに
ガラス繊維等の強化材を添加混合した強化樹脂組成物が
提示されている。For example, JP-A-53-98356 proposes a reinforced resin composition in which a reinforcing material such as glass fiber is added and mixed with PPS.
また、ＰＰＳの脆化性を改良するために、ポリフェニレ
ンエーテル（以下、単にＰＰＥとする。Furthermore, in order to improve the embrittlement of PPS, polyphenylene ether (hereinafter simply referred to as PPE) was used.
）等の各種エンジニアリングプラスチックと溶融ブレン
ドした樹脂組成物が数多く提案されている。) and other various engineering plastics have been proposed.
例えば、特開昭５０−１５６５６１号公報ではＰＰＳと
ＰＰＥとの混合組成の樹脂組成物が、同５５−１３５１
６０号公報ではＰＰＳとＰＰＥまたはナイロン樹脂ある
いは飽和ポリエステル樹脂を特定割合で配合した樹脂組
成物が、同５Ｂ−１５７８５９号公報ではＰＰＳとスチ
レン系樹脂をグラフトさせたＰＰＥとからなる樹脂組成
物が、また同５９−１６４３６０号公報ではＰＰＳ、ボ
リアリレート、ポリサルファン、ＰＰＥ等から選ばれた
樹脂及びエポキシ樹脂からなる樹脂組成物がそれぞれ提
案されている。For example, in JP-A-50-156561, a resin composition having a mixed composition of PPS and PPE is disclosed in JP-A-55-1351.
No. 60 discloses a resin composition in which PPS and PPE or nylon resin or saturated polyester resin are blended in a specific ratio, and Publication No. 5B-157859 discloses a resin composition consisting of PPS and PPE grafted with a styrene resin. Moreover, in the same publication No. 59-164360, resin compositions each consisting of a resin selected from PPS, polyarylate, polysulfan, PPE, etc. and an epoxy resin are proposed.
しかし、上記した種々のＰＰＳの改良に関する提案にお
いて、ガラス繊維等強化材を混合した強化樹脂組成物は
、衝撃強度は改善されるものの、低い伸びは改善されず
、逆に溶融粘度が大幅に上昇し成形加工性が悪くなった
り、添加のガラス繊維のため得られる成形品の表面平滑
性が悪く、成形品外観が劣る等の欠点が生じる。However, in the various proposals for improving PPS mentioned above, reinforced resin compositions mixed with reinforcing materials such as glass fibers improved impact strength but did not improve low elongation, and conversely, melt viscosity significantly increased. However, there are disadvantages such as poor molding processability, poor surface smoothness of the molded product obtained due to the added glass fiber, and poor appearance of the molded product.
また、ＰＰＳと各種エンジニアリングプラスチックとか
らなる樹脂組成物においては、添加混合される樹脂のＰ
ＰＳとの相溶性が低いため、分散状態において分散粒子
の平均分散粒子径が大きく、伸びや衝撃強度の改善が十
分でないだけでなく引張強度や曲げ弾性率の低下が著し
く、提案された樹脂組成物単独を成形材料として使用す
ることは困難とされている。In addition, in resin compositions made of PPS and various engineering plastics, P of the resin to be added and mixed is
Due to the low compatibility with PS, the average dispersed particle size of the dispersed particles is large in the dispersed state, and not only is the improvement in elongation and impact strength insufficient, but also the tensile strength and flexural modulus are significantly reduced. It is difficult to use the material alone as a molding material.
本発明は、従来のＰＰＳ樹脂組成物では達成できなかっ
たＰＰＳの有する機械的強度、耐熱性等の優れた特性を
損なうことなく、高弾性率を保持しつつ、ガラス繊維等
の強化材を添加することなく欠点である衝撃強度を改善
し、且つ低い伸びが改良されたポリフェニレンサルファ
イド系熱可塑性樹脂組成物を提供することを目的とする
。The present invention adds reinforcing materials such as glass fiber while maintaining high elastic modulus without impairing the excellent properties of PPS such as mechanical strength and heat resistance, which could not be achieved with conventional PPS resin compositions. It is an object of the present invention to provide a polyphenylene sulfide-based thermoplastic resin composition that has improved impact strength, which is a drawback, without causing any damage, and also has improved low elongation.
本発明によれば、（ａ）ポリスチレン系樹脂付加のポリ
フェニレンサルファイドを４０〜９８重量部、（ｂ）ス
チレン系ポリマー５〜７０重量部とポリフェニレンエー
テル９５〜３０重量部との混合組成物または／及びスチ
レン系ポリマーとポリフェニレンエーテルとのグラフト
共重合体を６０〜２重量部含むことを特徴とする。ポリ
フェニレンサルファイド系樹脂組成物が提供される。According to the present invention, (a) 40 to 98 parts by weight of polyphenylene sulfide added with polystyrene resin, (b) a mixed composition of 5 to 70 parts by weight of styrene polymer and 95 to 30 parts by weight of polyphenylene ether; and/or It is characterized by containing 60 to 2 parts by weight of a graft copolymer of a styrene polymer and polyphenylene ether. A polyphenylene sulfide resin composition is provided.
また、上記のポリフェニレンサルファイド系樹脂組成物
１００重量部に対し、更に（ｃ）熱可塑性エラストマー
を１〜６０重量部を含むことを特徴とするポリフェニレ
ンサルファイド系樹脂組成物が提供される。Further, there is provided a polyphenylene sulfide resin composition characterized in that it further contains 1 to 60 parts by weight of (c) a thermoplastic elastomer based on 100 parts by weight of the above polyphenylene sulfide resin composition.
本発明は、上記のように（ａ）成分としてポリスチレン
系樹脂付加のＰＰＳと、（ロ）成分として特定組成比の
スチレン系ポリマーとＰＰＥとの混合物、スチレン系ポ
リマーをグラフトしたＰＰＥ共重合体またはこれらの混
合物とを組合わせて配合することにより、また更に要す
れば（ｃ）成分として熱可塑性エラストマーを配合する
ことにより、伸び及び衝撃強度が改良されると共に、分
散粒子の平均分散粒子径が微細であり、引張強度及び曲
げ強度の低下がなく、且つＰＰＳの高弾性率等の機械的
強度を損なうこともない。As described above, the present invention includes PPS added with a polystyrene resin as the component (a), a mixture of a styrene polymer and PPE in a specific composition ratio as the component (b), a PPE copolymer grafted with a styrene polymer, or By blending these mixtures in combination, and if necessary by blending a thermoplastic elastomer as component (c), elongation and impact strength are improved, and the average dispersed particle diameter of the dispersed particles is improved. It is fine and does not reduce the tensile strength and bending strength, and does not impair the mechanical strength such as the high elastic modulus of PPS.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
本発明の（ａ）成分であるポリスチレン系樹脂付加のＰ
ＰＳは、ＰＰＳに対し親和性のエポキシ基、アリール基
等の官能基を有するポリスチレンとＰＰＳとを所定の反
応条件で反応させることにより得ることができる。P of polystyrene resin addition which is component (a) of the present invention
PS can be obtained by reacting polystyrene having a functional group such as an epoxy group or an aryl group with affinity for PPS with PPS under predetermined reaction conditions.
一般にＰＰＳは、他の樹脂を付加することの困難が知ら
れているが、本発明においては、ＰＰＳに対して親和性
を有する基例えば、エポキシ基やアリール基を、好まし
くはエポキシ基を予めポリスチレンに保持させることに
より、ＰＰＳにポリスチレン系樹脂を付加させて、（ａ
）成分であるボリスチレン系樹脂付加のＰＰＳを得るこ
とができる。Generally, it is known that it is difficult to add other resins to PPS, but in the present invention, a group having an affinity for PPS, such as an epoxy group or an aryl group, preferably an epoxy group, is added to the polystyrene in advance. By holding the polystyrene resin in PPS, (a
) PPS added with a polystyrene resin can be obtained.
例えば、ＰＰＳとエポキシ基を有するポリスチレン系樹
脂を直接または過酸化物または酸触媒の存在下または不
存在下においてα−クロルナフタレン、Ｎ−メチル−２
−ピロリドン等の溶液中で均一に攪拌しながら、２００
°Ｃ以上、好ましくは２５０〜３８０℃の温度で反応さ
せ、反応混合物をアセトン、クロロホルム等の溶剤で洗
浄し未反応のエポキシ基を有するポリスチレン系樹脂を
除去して（ａ）成分のポリスチレン系樹脂付加のＰＰＳ
を得ることができる。For example, α-chloronaphthalene, N-methyl-2
- While stirring uniformly in a solution such as pyrrolidone,
The polystyrene resin of component (a) is reacted at a temperature of ℃ or above, preferably 250 to 380℃, and the reaction mixture is washed with a solvent such as acetone or chloroform to remove unreacted epoxy group-containing polystyrene resin. Additional PPS
can be obtained.
この場合、反応時間は１０分以上とし、二軸混練機を用
いて直接反応させる場合には、混練即ち反応時間をより
長くする必要がある。また、未反応のポリスチレン系樹
脂が残存すると（ｂ）成分のスチレン系ポリマーとＰＰ
Ｅとの混合物、スチレン系ポリマーをグラフトしたＰＰ
Ｅ共重合体またはこれらの混合物との混合性が悪く、伸
び等が改善されない。更に、ＰＰＳと官能基を有するポ
リスチレン系樹脂との混合比は、ＰＰＳを３０〜９８重
量部、官能基を有するポリスチレン系樹脂を２〜７０重
量部、好ましくはＰＰＳを５０〜９５重量部、官能基を
有するポリスチレン系樹脂を５〜５０重量部とする。Ｐ
ＰＳが９８重量部を超えると本発明の（ｂ）成分との混
合性が悪くなり、一方、３０重量部より少ないと得られ
るポリフェニレンサルファイド系樹脂組成物の機械的強
度が低下し、好ましくない。In this case, the reaction time is 10 minutes or more, and when the reaction is carried out directly using a twin-screw kneader, the kneading or reaction time needs to be longer. In addition, if unreacted polystyrene resin remains, the styrene polymer of component (b) and PP
Mixture with E, PP grafted with styrenic polymer
Mixability with E copolymer or a mixture thereof is poor, and elongation etc. are not improved. Furthermore, the mixing ratio of PPS and polystyrene resin having a functional group is 30 to 98 parts by weight of PPS, 2 to 70 parts by weight of polystyrene resin having a functional group, preferably 50 to 95 parts by weight of PPS, The amount of polystyrene resin having groups is 5 to 50 parts by weight. P
If PS exceeds 98 parts by weight, the miscibility with component (b) of the present invention will deteriorate, while if it is less than 30 parts by weight, the mechanical strength of the resulting polyphenylene sulfide resin composition will decrease, which is not preferable.
本発明に使用するＰＰＳは、耐熱性、耐薬品性及び機械
的特性から、下記構造式（１）で示されるフェニレンサ
ルファイド単位構造が７０モル％以上であるものが好ま
しい。The PPS used in the present invention preferably has a phenylene sulfide unit structure represented by the following structural formula (1) in an amount of 70 mol % or more in view of heat resistance, chemical resistance, and mechanical properties.
フェニレンサルファイド単位が７０モル％より少ないと
耐熱性が低下する。残余の３０モル％は、上記構造式（
２）のメタ結合、構造式（３）のエーテル結合、構造式
（４）のスルフォン結合、構造式（５）でＲが炭素数１
２個以下のアルキル基またはアルコキシ基、フェニル基
及びニトロ基のいずれかの置換フェニレンサルファイド
結合、構造式（６）のビフェニル結合、構造式（７）の
ナフチル結合及び三官能フェニルサルファイド結合等か
らなる。If the phenylene sulfide unit content is less than 70 mol%, heat resistance will decrease. The remaining 30 mol% is represented by the above structural formula (
2) meta bond, Structural formula (3) ether bond, Structural formula (4) sulfone bond, Structural formula (5) where R has 1 carbon number.
Consisting of substituted phenylene sulfide bonds of any of two or less alkyl groups or alkoxy groups, phenyl groups and nitro groups, biphenyl bonds of structural formula (6), naphthyl bonds of structural formula (7), trifunctional phenyl sulfide bonds, etc. .
また、ＰＰＳのメルトフローレイトが、ＡＳＴＭ Ｄ
１２３８−７４Ｔで定めるメルトインデサーで３１５°
Ｃ１荷重５ｋｇで測定して、５〜１００００ ｇ／１０
分、好ましくは５〜５００ ｇ／１０分のものを使用す
る。In addition, the melt flow rate of PPS is ASTM D
315° with melt indexer specified by 1238-74T
Measured with C1 load 5kg, 5-10000 g/10
minutes, preferably 5 to 500 g/10 minutes.
これらＰＰＳは、市販されているものを用いることがで
きる。例えば、フィリップ社製の商品名「ライドンＰＰ
Ｓ、、トープレン社製の商品名「トーブレン」、東ソー
・サスティール社製の商品名「サスティール」、呉羽化
学工業■製の商品名「フォートロン」等である。Commercially available PPSs can be used as these PPSs. For example, the product name “Rydon PP” manufactured by Philips
S., the product name "Tovren" manufactured by Topren Co., Ltd., the product name "Sasteel" manufactured by Tosoh Sasteel Co., Ltd., and the product name "Fortron" manufactured by Kureha Chemical Industry ■.
本発明で用いるＰＰＳに対して親和性のある官能基を有
するポリスチレン系樹脂は、例えば官能基がエポキシ基
の場合、
シジルエステルまたはα、β−不飽和グリシジルエーテ
ル等のα、β−不飽和グリシジル化合物とスチレン系モ
ノマーとの共重合反応によって得ることができる。For example, when the functional group is an epoxy group, the polystyrene resin used in the present invention has an epoxy group, an α,β-unsaturated glycidyl ester or an α,β-unsaturated glycidyl ether, etc. It can be obtained by a copolymerization reaction between a compound and a styrene monomer.
具体的には、スチレン系モノマーとしては、スチレン、
メチルスチレン、ビニルキシレン、ジクロルスチレン、
ブロムスチレン、ジブロムスチレン、ｐ−ｔ−７’チル
スチレン、エチルスチレン、ビニルナフタレン等が挙げ
られ、また、α、β−不飽和酸のグリシジルエステルと
してはアクリル酸グリシジル、メタクリル酸グリシジル
、エタクリル酸グリシジル、イタコン酸グリシジルが、
α、β−不飽和グリシジルエーテルとしてはアリルグリ
シジルエーテル、ビニールグリシジルエーテルが挙げら
れる。通常は、スチレンとタタクリル酸グリシジルを用
いる。Specifically, the styrenic monomers include styrene,
Methylstyrene, vinylxylene, dichlorostyrene,
Examples of glycidyl esters of α, β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. , glycidyl itaconate,
Examples of the α,β-unsaturated glycidyl ether include allyl glycidyl ether and vinyl glycidyl ether. Typically, styrene and glycidyl tataacrylate are used.
スチレン系モノマーとα、β−不飽和グリシジル化合物
の共重合反応は、公知のラジカル重合反応を利用して、
塊状重合、溶液重合、懸濁重合または乳化重合によって
行うことができる。また、この反応は、α、β−不飽和
グリシジル化合物とスチレンモノマーとを直接反応させ
てもよいし、スチレン系モノマーを予め重合させたスチ
レン系樹脂とα、β−不飽和グリシジル化合物とを反応
させてもよい。The copolymerization reaction of the styrenic monomer and the α,β-unsaturated glycidyl compound is carried out using a known radical polymerization reaction.
It can be carried out by bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization. In addition, this reaction may be carried out by directly reacting an α,β-unsaturated glycidyl compound with a styrene monomer, or by reacting a styrene resin prepared by polymerizing a styrene monomer with an α,β-unsaturated glycidyl compound. You may let them.
スチレン系樹脂とα、β−不飽和グリシジル化合物を溶
融状態で反応させる場合は、押出機、コニーダー、バン
バリーミキサ−等の溶融混合機を用いて行ってもよい。When the styrene resin and the α,β-unsaturated glycidyl compound are reacted in a molten state, a melt mixer such as an extruder, a co-kneader, or a Banbury mixer may be used.
スチレン系モノマーとα、β−不飽和グリシジル化合物
との反応比率は、重量比でα、β−不飽和クリシりル化
合物：スチレン系モノマー＝０．５〜５０：９５．５〜
５０、好ましくは２〜２０＝９８〜８０とするのがよい
。α、β−不飽和グリシジル化合物が０．５重量部より
少ないとＰＰＳとの反応速度が遅く実用的でなく、また
、５０重量部より多くなるとゲル化反応が起こり、ＰＰ
Ｓにポリスチレン系樹脂を付加することが困難となるた
め好ましくない。The reaction ratio of the styrene monomer and the α,β-unsaturated glycidyl compound is α,β-unsaturated glycidyl compound:styrene monomer=0.5-50:95.5-
50, preferably 2-20=98-80. If the amount of the α,β-unsaturated glycidyl compound is less than 0.5 parts by weight, the reaction rate with PPS is too slow to be practical, and if it is more than 50 parts by weight, a gelation reaction occurs and the PP
This is not preferred because it becomes difficult to add polystyrene resin to S.
本発明のＰＰＳに対して親和性のある官能基を有するポ
リスチレン系樹脂は、上記のようなα。The polystyrene resin having a functional group having an affinity for PPS of the present invention is α as described above.
β−不飽和グリシジル化合物との共重合体を用いること
ができ、共重合体は、ランダム共重合体、ブロック共重
合体、グラフト共重合体またはこれらの混合物であって
もよい。通常は、ランダム共重合体を用いるのが好まし
い。また、このポリスチレン系樹脂の数平均分子量は通
常、３０００〜１２００００、好ましくは１００００〜
５００００であるが、数平均分子量は共重合反応に用い
るラジカル開始剤の量、反応温度等によって調節するこ
とができる。Copolymers with β-unsaturated glycidyl compounds can be used, and the copolymers may be random copolymers, block copolymers, graft copolymers or mixtures thereof. Usually, it is preferable to use a random copolymer. Further, the number average molecular weight of this polystyrene resin is usually 3,000 to 120,000, preferably 10,000 to 120,000.
50,000, but the number average molecular weight can be adjusted by adjusting the amount of radical initiator used in the copolymerization reaction, reaction temperature, etc.
また、本発明において、上記したようなＰＰＳに対して
親和性のある官能基を有するポリスチレン系樹脂１００
重量部に対し、２０重量部以下好ましくは１０重量部以
下のエチレン、プロピレン、ブチレン、ブタジェン、イ
ソプレン、アクリロニトリル、メチルアクリレート、メ
チルメタクリレート等のモノマーの１種または２種以上
を共重合させて用いることもできる。In addition, in the present invention, polystyrene resin 100 having a functional group having an affinity for PPS as described above is used.
20 parts by weight or less, preferably 10 parts by weight or less of one or more monomers such as ethylene, propylene, butylene, butadiene, isoprene, acrylonitrile, methyl acrylate, and methyl methacrylate are copolymerized and used based on the weight part. You can also do it.
本発明の［有］）成分である特定組成比のスチレン系ポ
リマーとＰＰＥとの混合物、スチレン系ポリマーをグラ
フトしたＰＰＥ共重合体またはこれらの混合物において
、スチレン系ポリマーとＰＰＥとの混合物は押出機、バ
ンバリーミキサ−、ニーダ−等の通常の溶融混練加工機
で配合混合することによって得ることができ、スチレン
系ポリマーとＰＰＥとのグラフト共重合体は、例えば特
開昭５０−５１１９７号公報等に記載される公知の方法
によって製造することができ、これらの混合物は上記の
溶融混練加工機により同様に得ることができる。In a mixture of a styrenic polymer and PPE having a specific composition ratio, a PPE copolymer grafted with a styrenic polymer, or a mixture thereof, which is a component of the present invention, the mixture of the styrenic polymer and PPE is prepared using an extruder. A graft copolymer of a styrene polymer and PPE is disclosed in, for example, JP-A No. 50-51197, etc. They can be produced by the known methods described, and these mixtures can likewise be obtained by the melt-kneading processing machines described above.
上記（ｂ）成分において、スチレン系ポリマーとＰＰＥ
の構成比率は、スチレン系ポリマーが５〜７０重量部、
ＰＰＰが９５〜３０重量部の範囲で、好ましくはスチレ
ン系ポリマーが１０〜６０重１部、ＰＰＰが９０〜４０
重量部の範囲で用いるのが好ましい。ＰＰＥが９５重量
部より多くなると本発明のポリフェニレンサルファイド
系樹脂組成物の溶融粘度が高くなり、成形加工性が悪く
なると共に耐溶剖性が悪くなり実用的でなくなる。−方
、ＰＰＥが３０重量部より少ないとポリフェニレンサル
ファイド系樹脂組成物の伸びや衝撃強度の改善が劣る。In the above component (b), styrenic polymer and PPE
The composition ratio of styrenic polymer is 5 to 70 parts by weight,
PPP is in the range of 95 to 30 parts by weight, preferably 10 to 60 parts by weight of styrenic polymer, and 90 to 40 parts by weight of PPP.
It is preferable to use within the range of parts by weight. When the PPE content exceeds 95 parts by weight, the melt viscosity of the polyphenylene sulfide resin composition of the present invention increases, resulting in poor moldability and poor dissection resistance, making it impractical. - On the other hand, if the PPE content is less than 30 parts by weight, the improvement in elongation and impact strength of the polyphenylene sulfide resin composition will be poor.
本発明の（ｂ）成分に用いられるＰＰＥは、下記の一般
式（８）で示されるもので、具体例としては、ｚ
（但し、Ｒ３、ｈは炭素数１〜４のアルキル基またはハ
ロゲン原子を、ｎは重合度を表す、）ポリ（２，６−シ
メチルフエニレンー１．４−エーテル）、ポリ（２，６
−ジメチルフェニレンー１．４−エーテル）、ポリ（２
−メチル−６−エチルフェニレン−１，４−エーテル）
、ポリ（２゜６−シクロルフエニレンー１．４−エーテ
ル）、ポリ（２，６−ジーｎ−プロビルセニレン−１゜
４−エーテル）、ポリ（２−メチル−６−ｎ−プチルセ
ニレンー１．４−エーテル）、ポリ（２−メチル−６−
プロムセニレンー１．４−エーテル）、ポリ（２，６−
ジ〜ｎ−ブチルフェニレン１．４−エーテル）、ポリ（
２−メチル−６−プロムフエニレンー１． ４−エーテ
ル）、ポリ（２，６−ジフェニルフェニレン−１，４−
エーテル）等が挙げられる。The PPE used as component (b) of the present invention is represented by the following general formula (8), and specific examples include z (where R3 and h are an alkyl group having 1 to 4 carbon atoms or a halogen atom). , n represents the degree of polymerization, ) poly(2,6-dimethylphenylene-1,4-ether), poly(2,6
-dimethylphenylene-1,4-ether), poly(2
-methyl-6-ethylphenylene-1,4-ether)
, poly(2゜6-cyclolphenylene-1,4-ether), poly(2,6-di-n-probylsenylene-1゜4-ether), poly(2-methyl-6-n-butylsenylene-1. 4-ether), poly(2-methyl-6-
Promsenylene-1,4-ether), poly(2,6-
di~n-butylphenylene 1,4-ether), poly(
2-Methyl-6-promphenylene-1. 4-ether), poly(2,6-diphenylphenylene-1,4-
ether), etc.
また、ＰＰＥの還元粘度（０，５ｇ／ｄＡのクロロホル
ム溶液、３０℃で測定）が０．２〜０．８、好ましくは
０．３〜０．７の範囲のものが通常用いられる。Further, PPE having a reduced viscosity (measured in a 0.5 g/dA chloroform solution at 30° C.) of 0.2 to 0.8, preferably 0.3 to 0.7 is usually used.
また、本発明の伽）成分で用いるスチレン系ポリマーは
、スチレン、α−メチルスチレン、２，４−ジメチルス
チレン、モノクロルスチレン、ジクロルスチレン、Ｐ−
メチルスチレン、エチルスチレン等の七ツマ−の１種ま
たは２種以上を重合して得ることができる。また、重合
の際、共重合可能なビニル化合物、例えば、メチルメタ
クリレート、アクリロニトリル、メタクリニトリル、ブ
チルアルリレート、ブタジェン等を２０％以下で添加し
て重合させてもよい。In addition, the styrenic polymer used in component (a) of the present invention includes styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, dichlorostyrene, P-
It can be obtained by polymerizing one or more types of heptamines such as methylstyrene and ethylstyrene. Further, during polymerization, a copolymerizable vinyl compound such as methyl methacrylate, acrylonitrile, methacrinitrile, butyl allylate, butadiene, etc. may be added in an amount of 20% or less.
本発明の（ロ）成分としては、例えば市販の商品名ノリ
ル（ＧＥ社製）、商品名ザイロン（旭化成■製）、商品
名ユピエース（三菱瓦斯化学■製）等のスチレン系ポリ
マーとＰＰＥの混合物やグラフ）ＰＰＥ共重合体を用い
ることができる。Component (b) of the present invention includes a mixture of PPE and a styrenic polymer such as commercially available Noryl (manufactured by GE), Zylon (manufactured by Asahi Kasei), and Iupiace (manufactured by Mitsubishi Gas Chemical). or graph) PPE copolymers can be used.
本発明のポリフェニレンサルファイド系樹脂組成物は、
上記の成分（ａ）を４０〜９８重量部、好ましくは５０
〜９５重量部及び成分（ｂ）を２〜６０重量部、好まし
くは５〜５０重量部混蓋部て得ることができる。The polyphenylene sulfide resin composition of the present invention is
40 to 98 parts by weight, preferably 50 parts by weight of the above component (a)
~95 parts by weight and 2 to 60 parts by weight, preferably 5 to 50 parts by weight of component (b).
更に、本発明においては、上記の（ａ）成分と（ｂ）成
分とから構成されるの混合物に（ｃ）成分として熱可塑
性エラストマーを添加混合して樹脂組成物としてもよい
。Furthermore, in the present invention, a resin composition may be prepared by adding and mixing a thermoplastic elastomer as the component (c) to the mixture composed of the components (a) and (b).
本発明の（ｃ）成分の熱可塑性エラストマーは、例えば
、スチレン系、オレフィン系、ウレタン系、ポリエステ
ル系、ポリアミド系、塩素化ポリエチレン、１．２−ポ
リブタジェン、フッ素系、アイオノマー等、またこれら
上記エラトマーに酸無水物基あるいはエポキシ基等を有
するもの等公知の各種のエラストマーを使用することが
できる。The thermoplastic elastomer of component (c) of the present invention includes, for example, styrene type, olefin type, urethane type, polyester type, polyamide type, chlorinated polyethylene, 1,2-polybutadiene, fluorine type, ionomer, etc., and the above-mentioned elastomers. Various known elastomers, such as those having acid anhydride groups or epoxy groups, can be used.
スチレン系として、具体的には、スチレン・ブタジェン
・スチレンブロックコポリマー、スチレン・イソプレン
・スチレンブロックコポリマースチレン・エチレン・ブ
チレン・スチレンブロックコポリマーや、これらの無水
マレイン酸変成物、グリシジル変成物等が挙げられる。Specific examples of styrene-based polymers include styrene/butadiene/styrene block copolymers, styrene/isoprene/styrene block copolymers, styrene/ethylene/butylene/styrene block copolymers, maleic anhydride modified products, glycidyl modified products, etc. .
これらスチレン系熱可塑性エラストマーの市販品として
は、例えば、商品名カリフレックスＴＲ（シェル化学■
製）、商品名タフプレン（旭化成■製）、タフチック（
旭化成■製）、商品名ＪＳＲＴＲ（日本合成−ｒム■製
）、商品名クレイトンＧ（シェル化学側製）、商品名住
友ＴＰＥ−３Ｂシリーズ（住人化学■製）等がある。Commercially available products of these styrenic thermoplastic elastomers include, for example, the product name CARIFLEX TR (Shell Chemical Co., Ltd.
(manufactured by Asahi Kasei), product name: Toughprene (manufactured by Asahi Kasei), Tufftic (manufactured by Asahi Kasei),
Asahi Kasei ■), trade name JSRTR (manufactured by Nippon Gosei-rm ■), trade name Clayton G (made by Shell Kagaku), and trade name Sumitomo TPE-3B series (made by Sumitomo Chemical ■).
また、オレフィン系として、具体的には、エチレン−（
メタ）アクリル酸共重合体、エチレン−プロピレン共重
合体、エチレン−ブテン−１共重合体や、またこれら上
記エラトマーに酸無水物基あるいはエポキシ基等を有す
るもの等公知の各種のエラストマーを使用することがで
きる。In addition, as an olefin, specifically, ethylene-(
Various known elastomers are used, such as meth)acrylic acid copolymers, ethylene-propylene copolymers, ethylene-butene-1 copolymers, and those having acid anhydride groups or epoxy groups in the above-mentioned elastomers. be able to.
これらオレフィン系熱可塑性エラストマーの市販品とし
ては、例えば、商品名ミラストマー（三井石油化学工業
■製）、商品名住人ＴＰＥ （住人化学■製）、商品名
サーモラン（日本合成ゴム■製）、商品名５ＡＮＴＯＰ
ＲＥＮＥ （モンサンド社製）、商品名ＬＥＶＡＦＬＥ
Ｘ−ＥＰ （パイ！ル社製）等がある。Commercially available products of these olefinic thermoplastic elastomers include, for example, the product name Milastomer (manufactured by Mitsui Petrochemical Industries, Ltd.), the product name Jusumu TPE (manufactured by Sumima Chemical Co., Ltd.), the product name Thermolan (manufactured by Japan Synthetic Rubber Co., Ltd.), and the product name 5ANTOP
RENE (manufactured by Monsando), product name LEVAFLE
There are X-EP (manufactured by Pa! Le Co., Ltd.), etc.
ウレタン系熱可塑性エラストマーの市販品としては、例
えば、商品名エラストラン（日本エラストラン社製）、
商品名ＥＳＴＥＮＥ （Ｂ、Ｆ、グツドリッチ社製）等
がある。Commercially available urethane thermoplastic elastomers include, for example, the trade name Elastran (manufactured by Nihon Elastran Co., Ltd.);
There are product names such as ESTENE (B, F, manufactured by Gutdrich).
ポリエステル系熱可塑性エラストマーの市販品としては
、例えば、商品名ハイトレル（東し・デエポン■製）、
商品名ペルプレン（東洋紡績■製）等がある。Commercially available polyester thermoplastic elastomers include, for example, Hytrel (manufactured by Toshi Depon),
There are product names such as Pelprene (manufactured by Toyobo ■).
ポリアミド系熱可塑性エラストマーの市販品としては、
例えば、商品名グリラックス（大日本インキ■製）、商
品名ツバミツト（三菱化成■製）、商品名ダイアミド−
ＰＡＥ（ダイセル・ヒュルス社製）等がある。Commercially available polyamide thermoplastic elastomers include:
For example, the product name Glilux (manufactured by Dainippon Ink ■), the product name Tsubamitsu (manufactured by Mitsubishi Kasei ■), and the product name Diamid.
There are PAE (manufactured by Daicel-Hüls), etc.
１．２−ポリブタジェン系熱可塑性エラストマーの市販
品としては、例えば、商品名ＪＳＲＲＢ（日本合成ゴム
■製）等がある。Commercially available 1.2-polybutadiene thermoplastic elastomers include, for example, the trade name JSRRB (manufactured by Japan Synthetic Rubber).
フッ素系熱可塑性エラストマーの市販品としては、例え
ば、商品名ダイエルＴＰＥ （ダイキンエ業■製）等が
ある。Commercially available fluorine-based thermoplastic elastomers include, for example, Daiel TPE (trade name) (manufactured by Daikin Industries, Ltd.).
アイオノマー熱可望性エラストマーの市販品としては、
例えば、商品名サーリン（デュポン社製）等がある。Commercially available ionomer thermoplastic elastomers include:
For example, there is the trade name Surlyn (manufactured by DuPont).
本発明において、上記の熱可塑性エラストマーの中で、
スチレン系のエラストマーが最も好ましい。In the present invention, among the above thermoplastic elastomers,
Styrenic elastomers are most preferred.
本発明では、上記成分（ｃ）を、成分（ａ）及び（ｂ）
とから構成される組成物１００重量部に対し、１〜６０
重量部、好ましくは３〜４０重量部重量部会加配樹脂組
成物を構成することができる。添加配合は、通常の溶融
混練加工機を用いて行うことができる。In the present invention, the above component (c) is replaced with components (a) and (b).
1 to 60 parts by weight per 100 parts by weight of the composition consisting of
Parts by weight, preferably 3 to 40 parts by weight, may constitute the additive resin composition. Addition and blending can be performed using a normal melt-kneading processing machine.
本発明において、上記の成分（ａ）及び■）、または成
分（ａ）、（ｂ）及び（ｃ）から構成される樹脂組成物
に、その成形性、物性を損なわない範囲において、繊維
状、マット状等の各種形状の強化材や充填剤を添加する
ことができる。In the present invention, fibrous, Reinforcing materials and fillers in various shapes such as mat shapes can be added.
それら強化剤、充填剤としては、ガラス繊維、アスベス
ト繊維、カーボン繊維、シリカ繊維、シリカ・アルミナ
繊維、アルミナ繊維、ジルコニア繊維、窒化ホウ素繊維
、窒化ケイ素繊維、ホウ素繊維、ステンレス、アルミニ
ウム、チタン、銅、真鍮またはマグネシウム等の金属繊
維及びポリアミド、フッ素樹脂、ポリエステルまたはア
クリル樹脂等の有機質繊維等の各種繊維、銅、鉄、ニッ
ケル、亜鉛、スズ、鉛、ステンレス、アルミニウム、金
または銀等の各種金属粉末、ヒユームドシリカ、ケイ酸
アルミニウム、ガラスピーズ、カーボンブラック、石英
粉末、タルク、酸化チタン、酸化鉄、炭酸カルシウム、
ケイソウ土等がある。These reinforcing agents and fillers include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica/alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, stainless steel, aluminum, titanium, and copper. , various fibers such as metal fibers such as brass or magnesium and organic fibers such as polyamide, fluororesin, polyester or acrylic resin, various metals such as copper, iron, nickel, zinc, tin, lead, stainless steel, aluminum, gold or silver. Powder, fumed silica, aluminum silicate, glass beads, carbon black, quartz powder, talc, titanium oxide, iron oxide, calcium carbonate,
There is diatomaceous earth, etc.
繊維状強化剤、充填剤は、平均繊維径が０．５〜３０
ｐ ｍ ％繊維長さが５０μｍ〜３０１１１１Ｏものが
使用できる。The fibrous reinforcing agent and filler have an average fiber diameter of 0.5 to 30.
Those having a p m % fiber length of 50 μm to 301111O can be used.
これら強化材、充填材は単独、または２種以上を混合し
て用いることができ、また、シランカップリング剤やチ
タネート系カップリング剤等の公知のカップリング剤で
表面処理して用いることもできる。These reinforcing materials and fillers can be used alone or in combination of two or more, and can also be used after surface treatment with a known coupling agent such as a silane coupling agent or a titanate coupling agent. .
更に、本発明の樹脂組成物に、本発明の目的を損なわな
い範囲内で、ヒンダードフェノール、ハイドロキノン、
チオエーテル、ホスファイト類、これらの置換体、銅化
合物等の酸化防止剤や熱安定剤、レゾルシノール、サリ
シレート、ベンゾトリアゾール、ペンゾフヱノン等の紫
外線吸収剤、ステアリン酸及びその塩、ステアリルアル
コール等の離形剤、ハロゲン系、リン酸エステル系、メ
ラミンあるいはシアヌル酸系等の難燃剤または難燃助剤
、ドデシルベンゼンスルフオン酸ナトリウム、ポリアル
キレングリコール等の帯電防止剤、結晶促進剤、染料、
顔料等の添加剤を１種以上添加することもできる。Furthermore, hindered phenol, hydroquinone,
Thioethers, phosphites, substituted products thereof, antioxidants and heat stabilizers such as copper compounds, ultraviolet absorbers such as resorcinol, salicylate, benzotriazole, penzophenone, etc., mold release agents such as stearic acid and its salts, stearyl alcohol, etc. , halogen-based, phosphoric acid ester-based, melamine or cyanuric acid-based flame retardants or flame retardant aids, sodium dodecylbenzenesulfonate, antistatic agents such as polyalkylene glycol, crystallization promoters, dyes,
One or more types of additives such as pigments can also be added.
また、本発明の目的を損なわない範囲内で、例えばポリ
エチレン、ポリプロピレン、エチレン・酢酸ビニル共重
合体、ポリアミド、ポリエステル、ポリカーボネート、
ポリスルホン等の熱可塑性樹脂や、例えばフェノール樹
脂、メラミン樹脂、シリコーン樹脂、エポキシ樹脂等熱
硬化性樹脂を少量を添加してもよく、更にＰＰＳを添加
配合することもできる。In addition, within a range that does not impair the purpose of the present invention, for example, polyethylene, polypropylene, ethylene/vinyl acetate copolymer, polyamide, polyester, polycarbonate,
A small amount of thermoplastic resin such as polysulfone or thermosetting resin such as phenol resin, melamine resin, silicone resin, or epoxy resin may be added, and PPS may also be added.
本発明のポリフェニレンサルファイド系樹脂組成物は、
前記したように各成分を押出機、バンバリーミキサ−、
ニーダ−等の通常の溶融混練加工装置を用いて配合混合
混練することにより製造でき、更に、射出成形、圧縮成
形、押出成形等により各種用途の成形品に加工すること
ができる。The polyphenylene sulfide resin composition of the present invention is
As mentioned above, each component was processed using an extruder, a Banbury mixer,
It can be manufactured by blending, mixing, and kneading using an ordinary melt-kneading processing device such as a kneader, and can be further processed into molded products for various uses by injection molding, compression molding, extrusion molding, and the like.
以下に、本発明の実施例について詳しく説明する。但し
、本発明は、本実施例に限定されるものでない。Examples of the present invention will be described in detail below. However, the present invention is not limited to this example.
実株例及び比較例に記載する引張強度、伸び、衝撃強度
及び平均分散粒子径の測定法は下記の方法で行った。The tensile strength, elongation, impact strength, and average dispersed particle diameter described in the actual plant examples and comparative examples were measured by the following methods.
■引張強度及び伸び： ＡＳＴＭ Ｄ６３８に準じて測定した。■Tensile strength and elongation: Measured according to ASTM D638.
単位： ｋｇｆ／ｃｓ＋１ ■曲げ強度及び曲げ弾性率： ＡＳＴＭ Ｄ７９０に準じて測定した。Unit: kgf/cs+1 ■Bending strength and bending modulus: Measured according to ASTM D790.
単位： ｋｇｆ／ｃｎ”
■衝撃強度（ノツチ付アイゾツト衝撃強度）：ＡＳＴＭ
Ｄ２５６に準じて測定した。Unit: kgf/cn” ■Impact strength (Notched Izot impact strength): ASTM
Measured according to D256.
なお、試験片の厚みは、１７８インチで行った。Note that the thickness of the test piece was 178 inches.
単位： ｋｇｆ −ｃｍ／ｃｍ ■平均分散粒子径： ＴＥＭ写真から分散成分の粒子径を測定した。Unit: kgf -cm/cm ■Average dispersed particle size: The particle size of the dispersed components was measured from a TEM photograph.
単位＝μｍ
［エポキシ基を有するポリスチレン系樹脂の製造法１
攪拌機を備えたセパラブルフラスコに、スチレンモノマ
ー２１６ ｇ、グリシジルメタクリレート２４ｇ、トル
エン１６０ｇ及びアゾビスイソブチロニトリル２ｇを入
れ、２５°Ｃで２０分間窒素を吹き込みながら均一に混
合した。その後、セパラブルフラスコを８５°Ｃのオイ
ルバス中に設置し、窒素雰囲気中、８５°Ｃで６０分間
撹拌した後、更に温度を１０５°Ｃに昇温し、４５分間
攪拌反応させた。Unit = μm [Method for producing polystyrene resin having epoxy groups 1 In a separable flask equipped with a stirrer, put 216 g of styrene monomer, 24 g of glycidyl methacrylate, 160 g of toluene, and 2 g of azobisisobutyronitrile, and heat at 25°C. The mixture was uniformly mixed while blowing nitrogen for 20 minutes. Thereafter, the separable flask was placed in an oil bath at 85°C, and after stirring at 85°C for 60 minutes in a nitrogen atmosphere, the temperature was further raised to 105°C, and the mixture was reacted with stirring for 45 minutes.
反応後、放冷し強攪拌下のメタノール中に反応重合液を
滴下し分別した。その後乾燥してエポキシ基濃度６．８
６ Ｘ １０−’ｍｏｌ／ｇ、数平均分子ｆｆ１１１６
００のエポキシ基を有するポリスチレン樹脂Ｃ−１を得
た。収率は約５０％であった。After the reaction, the reaction polymerization solution was allowed to cool and was added dropwise to methanol under strong stirring and fractionated. After that, it is dried and the epoxy group concentration is 6.8.
6 X 10-'mol/g, number average molecule ff1116
A polystyrene resin C-1 having 00 epoxy groups was obtained. The yield was about 50%.
スチレンモノーとグリシジルメタクリレートの配合比を
９５＝５にし、同様にして、エポキシ基濃度３．４５
Ｘ １０−’ｍｏｌ／ｇ、数平均分子量５２９００のエ
ポキシ基を有するポリスチレン樹脂Ｃ−２を得た。The blending ratio of styrene mono and glycidyl methacrylate was set to 95=5, and the epoxy group concentration was 3.45.
A polystyrene resin C-2 having an epoxy group having a number average molecular weight of 52,900 and a number average molecular weight of 52,900 was obtained.
］（ａ）成分の製造１
ＰＰＳとしてトープレン社製の商品名トーブレンＴ−４
（融点２９５°Ｃ，溶融粘度５６００ボイズ）９０重量
部を３００°Ｃで溶融し、上記で得たエポキシ基を有す
るポリスチレン系樹脂Ｃ−１を１０重量部添加し、ブラ
ベンダータイプの混練機を用いて、窒素ガス雰囲気中で
均一に攪拌混合しながら２０分間反応させた。反応物を
冷却後粉砕しアセトンで十分洗浄後、乾燥して反応生成
物り−ｌを得た。生成物Ｄ−１は、融点２８１℃、溶融
粘度８８００ボイズであった。] (a) Manufacture of component 1 As PPS, trade name Toblen T-4 manufactured by Toplen Co., Ltd.
(Melting point 295°C, melt viscosity 5600 voids) 90 parts by weight were melted at 300°C, 10 parts by weight of the polystyrene resin C-1 having epoxy groups obtained above was added, and a Brabender type kneader was added. The mixture was reacted for 20 minutes while being uniformly stirred and mixed in a nitrogen gas atmosphere. After cooling, the reaction product was pulverized, thoroughly washed with acetone, and dried to obtain a reaction product R-1. Product D-1 had a melting point of 281° C. and a melt viscosity of 8,800 voids.
商品名トープレンＴ−４を９５重量部、Ｃ−１を５重量
部として同様にして反応生成物Ｄ−２を得た。生成物Ｄ
−２は、融点２８０ ’Ｃ１溶融帖度１００００ポイズ
であった。A reaction product D-2 was obtained in the same manner using 95 parts by weight of Toprene T-4 and 5 parts by weight of C-1. Product D
-2 had a melting point of 280' C1 melting strength of 10,000 poise.
商品名トーブレンＴ−４を８０重量部、Ｃ−２を２０重
量部として同様にして反応生成物Ｄ−３を得た。生成物
Ｄ−３は、融点２８１”Ｃ，溶融粘度３５００ポイズで
あった。Reaction product D-3 was obtained in the same manner using 80 parts by weight of Toublen T-4 (trade name) and 20 parts by weight of C-2. Product D-3 had a melting point of 281''C and a melt viscosity of 3500 poise.
なお、融点は示差走査性熱量計（ＤＳＣ）にて測定した
ピーク温度を示した。また、溶融粘度は東洋精機製作所
■製キャビログラフ２Ｂを用い、温度３００°Ｃで、剪
断速度１２０５ｅｃ−’で測定した。Note that the melting point is the peak temperature measured with a differential scanning calorimeter (DSC). Further, the melt viscosity was measured at a temperature of 300° C. and a shear rate of 1205 ec-' using a Cabilograph 2B manufactured by Toyo Seiki Seisakusho ■.
［ＰＰＰの製造１
酸素吹き込み装置、冷却用コイル及び撹拌機を備えた反
応器内を窒素ガスにて置換した後、反応器に臭化第２
ｔｊ４３２．２ ｇ、ジ−ｎ−ブチルアミン６６６ｇ及
びトルエン２４ｆに２６−キシレノール５．２６ ｋ
ｇを溶解したものを混合添加して、均一に攪拌溶解した
後、攪拌して酸素を急激に吹き込みながら３０℃で９０
分間重合させた。その後、トルエン１８２、エチレンジ
アミン四酢酸の２０％水溶液を加えて重合反応を停止さ
せた。遠心分離にて重合生成物溶解相を分離取得し、メ
タノールを攪拌添加して重合生成物を分別し、乾燥しＰ
ＰＥを得た。得られたＰＰＰの極限粘度〔η〕 （クロ
ロホルム溶液として３０°Ｃで測定）は０．５０であっ
た。[Production of PPP 1 After purging the inside of the reactor equipped with an oxygen blowing device, a cooling coil, and a stirrer with nitrogen gas, the reactor was filled with second bromide.
26-xylenol 5.26 k in tj432.2 g, di-n-butylamine 666 g and toluene 24f
After mixing and adding the dissolved g, stir and dissolve uniformly, stir and rapidly blow in oxygen while heating at 30℃ to 90℃.
Polymerization was carried out for minutes. Thereafter, toluene 182 and a 20% aqueous solution of ethylenediaminetetraacetic acid were added to stop the polymerization reaction. The dissolved phase of the polymerization product is separated and obtained by centrifugation, and methanol is stirred and added to separate the polymerization product, which is dried and P.
Got PE. The intrinsic viscosity [η] of the obtained PPP (measured as a chloroform solution at 30°C) was 0.50.
［（ｂ）成分の製造１
（１）ポリスチレン系ポリマーとＰＰＥとの混合物上記
の製造で得られたＰＰＰ７０重量部とポリスチレン系ポ
リマーとして電気化学工業■製画品名デンカ スチロー
ル ＣＰ−１を３０重量部とを、■型タンブラーで均一
に混合後、シリンダーを２８０°Ｃに加熱した３０ｍｍ
押出機に供給し、ストランド状に引き出して、冷却後切
断してベレット状の混合物Ｅを得た。[Production of component (b) 1 (1) Mixture of polystyrene polymer and PPE 70 parts by weight of PPP obtained in the above production and 30 parts by weight of Denka Styrene CP-1 manufactured by Denki Kagaku Kogyo (Product name: Denka Styrol CP-1) as a polystyrene polymer. After mixing uniformly in a ■ type tumbler, a 30mm cylinder heated to 280°C
The mixture was fed into an extruder, drawn out into strands, cooled, and then cut to obtain a pellet-shaped mixture E.
（２）スチレン系ポリマーグラフトＰＰＰ温度針、窒素
吹き込み管及びコンデンサーを備えた５００ｄのセパラ
ブルフラスコにエチルベンゼン５０ｇ及び〔η〕が０．
６２のポリ（２，６−シメチルフエニレンー１．４−エ
ーテル）５０ｇを加え、１２０°Ｃに加熱撹拌して溶解
した。その後窒素ガスを吹き込み、反応器内を窒素ガス
で置換した後、ジーｔｅｒｔ−ブチルパーオキサイド４
ｇを加え１２０°Ｃで２時間撹拌し、次いでスチレンモ
ノマー８０ｇを加え１３０°Ｃで２時間反応させ、重合
させた。(2) Styrenic polymer graft PPP 50 g of ethylbenzene and 0.0 g of [η] were placed in a 500 d separable flask equipped with a temperature needle, a nitrogen blowing tube, and a condenser.
50 g of poly(2,6-dimethylphenylene-1,4-ether) No. 62 was added thereto, and the mixture was heated and stirred at 120°C to dissolve. After that, nitrogen gas was blown into the reactor, and after replacing the inside of the reactor with nitrogen gas, di-tert-butyl peroxide 4
Then, 80 g of styrene monomer was added and reacted at 130°C for 2 hours to polymerize.
反応物を取り出しエチルベンゼン及び未反応のスチレン
モノマーを除去して、ポリスチレングラフトＰＰＥのＦ
を得た。得られたＦのポリスチレンの含有量は５２重量
％であった。The reactant was taken out, ethylbenzene and unreacted styrene monomer were removed, and the F of polystyrene grafted PPE was removed.
I got it. The polystyrene content of the obtained F was 52% by weight.
実施例１〜４
上記で得られたＤ−１と、ＥまたはＦを第１表に示した
割合で配合し、３００°Ｃに設定したスクリュー径が３
０ｍｍの二軸混練機を用い溶融混練してペレットを製造
した。Examples 1 to 4 D-1 obtained above and E or F were blended in the proportions shown in Table 1, and the screw diameter was set at 300°C.
Pellets were produced by melt-kneading using a 0 mm twin-screw kneader.
得られたベレットを用いて、成形温度３００°Ｃ１金型
温度１４５°Ｃで射出成形にて物性測定用の試験片を得
た。測定結果を第１表に示した。Using the obtained pellet, test pieces for measuring physical properties were obtained by injection molding at a molding temperature of 300°C and a mold temperature of 145°C. The measurement results are shown in Table 1.
比較例１
前記の商品名トープレンＴ−４を用い実施例１と同様に
３００°Ｃに設定したスクリュー径が３０ｍｍの二軸混
練機を用い溶融混練してペレットを製造し、同様に物性
測定用試験片を作成した。測定結果を第１表に示した。Comparative Example 1 The above-mentioned product name Toprene T-4 was melt-kneaded using a twin-screw kneader with a screw diameter of 30 mm and set at 300°C in the same manner as in Example 1 to produce pellets, which were also used for physical property measurement. A test piece was prepared. The measurement results are shown in Table 1.
比較例２
前記の商品名トープレンＴ−４と上記で製造したＰＰＥ
を第１表の割合で配合し、実施例１と同様にして物性測
定用試験片を作成した。測定結果を第１表に示した。Comparative Example 2 The above-mentioned trade name Toprene T-4 and the above-manufactured PPE
were mixed in the proportions shown in Table 1, and test pieces for measuring physical properties were prepared in the same manner as in Example 1. The measurement results are shown in Table 1.
比較例３
前記の商品名トープレンＴ−４と上記で製造したＦとを
第１表の割合で配合し、実施例１と同様にして物性測定
用試験片を作成した。測定結果を第１表に示した。Comparative Example 3 The above-mentioned trade name Toprene T-4 and F produced above were blended in the proportions shown in Table 1, and a test piece for measuring physical properties was prepared in the same manner as in Example 1. The measurement results are shown in Table 1.
比較例４及び５
前記の商品名トーブレンＴ−４、上記で製造したＰＰＥ
及び商品名モディパ−Ａ４１００（日本油脂■製のグリ
シジルメタクリレート、スチレン及びエチレンの共重合
体）または商品名エビクロン３０５０ （大日本インキ
化学工業■製のビスフェノールＡ型エポキシ樹脂）をそ
れぞれ第１表に示した割合で配合し、実施例１と同様に
して物性測定用試験片を作成した。測定結果を第１表に
示した。Comparative Examples 4 and 5 The above-mentioned trade name Torblen T-4, the above-manufactured PPE
and the trade name MODIPER A4100 (a copolymer of glycidyl methacrylate, styrene and ethylene manufactured by NOF ■) or the trade name Evicron 3050 (bisphenol A type epoxy resin manufactured by Dainippon Ink & Chemicals ■) are shown in Table 1, respectively. A test piece for measuring physical properties was prepared in the same manner as in Example 1. The measurement results are shown in Table 1.
（以下、余白）
実施例５〜９
上記で製造したＤ−１、Ｄ−２、Ｄ−３及びＦと、商品
名トープレンＴ−１（トーブレン社製のメルトフローレ
ート２７００ ｇ／１０分ＰＰ５）、熱可塑性エラスト
マーとして商品名タフチックＭ１９１３及びタフチック
Ｈ１０４１（旭化成■製のスチレン・エチレン・ブチレ
ン・スチレンブロンクコポリマー）及びガラス繊維（旭
ファイバーグラス■製Ｃ３−０３−ＭＡ−４１１）を第
２表に示した割合で配合し、実施例Ｉと同様にして物性
測定用試験片を作成した。測定結果を第２表に示した。(Hereinafter, blank spaces) Examples 5 to 9 D-1, D-2, D-3, and F produced above and the product name Toprene T-1 (melt flow rate 2700 g/10 min PP5 manufactured by Toblen) , as thermoplastic elastomers, trade names Tufftic M1913 and Tufftic H1041 (styrene-ethylene-butylene-styrene bronc copolymer manufactured by Asahi Kasei ■) and glass fiber (C3-03-MA-411 manufactured by Asahi Fiberglass ■) are shown in Table 2. A test piece for measuring physical properties was prepared in the same manner as in Example I by blending the ingredients in the proportions shown. The measurement results are shown in Table 2.
これらの結果より、本発明のポリスチレン系樹脂付加の
ＰＰＳを用いる樹脂組成物は、比較例で示したＰＰＳ単
独、ＰＰＳとＰＰＥ、ＰＰＳと本発明で用いるスチレン
系ポリマーグラフトＰＰＥ等を用いる樹脂組成物に比し
て、伸び及び衝撃強度が極めて高く、平均分散粒子径は
小さくなり、更に引張強度、曲げ強度等もＰＰＳ単独樹
脂の物性値とそれほど変化しないことが分かる。From these results, the resin composition using PPS added with polystyrene resin of the present invention is different from the resin composition using PPS alone, PPS and PPE, PPS and styrene polymer graft PPE used in the present invention, etc. shown in the comparative example. It can be seen that the elongation and impact strength are extremely high, the average dispersed particle size is small, and the tensile strength, bending strength, etc. do not change much from the physical properties of the PPS resin alone.
〔発明の効果］
本発明のポリスチレン系樹脂の付加したＰＰＳとスチレ
ン系ポリマーとＰＰＨの混合組成物または／及びポリス
チレングラフトＰＰＥとを含有するポリフェニレンサル
ファイド系樹脂組成物は、実質的にＰＰＳ樹脂の機械的
強度を損なうことなく、伸びや衝撃強度等の柔軟性が良
好で、且つ機械的特性をバランスよく保持し、ガラス繊
維等の強化材を配合せずに十分な衝撃強度を有するため
成形用材料として工業的に極めて有用である。[Effects of the Invention] The polyphenylene sulfide resin composition containing the mixed composition of PPS, styrene polymer, and PPH or/and polystyrene grafted PPE to which polystyrene resin of the present invention has been added can substantially improve the mechanical properties of PPS resin. It is a molding material because it has good flexibility such as elongation and impact strength without sacrificing physical strength, maintains well-balanced mechanical properties, and has sufficient impact strength without adding reinforcing materials such as glass fiber. It is extremely useful industrially.
Claims (2)
サルファイドを４０〜９８重量部、（ｂ）スチレン系ポ
リマー５〜７重量部とポリフェニレンエーテル９５〜３
０重量部との混合組成物または／及びスチレン系ポリマ
ーとポリフェニレンエーテルとのグラフト共重合体を６
０〜２重量部含むことを特徴とするポリフェニレンサル
ファイド系樹脂組成物。(1) (a) 40 to 98 parts by weight of polyphenylene sulfide added with polystyrene resin, (b) 5 to 7 parts by weight of styrene polymer and 95 to 3 parts by weight of polyphenylene ether
6 parts by weight of a mixed composition or/and a graft copolymer of a styrenic polymer and polyphenylene ether.
A polyphenylene sulfide resin composition containing 0 to 2 parts by weight.
イド系樹脂組成物１００重量部に対し、更に（ｃ）熱可
塑性エラストマーを１〜６０重量部含むことを特徴とす
るポリフェニレンサルファイド系樹脂組成物。(2) A polyphenylene sulfide resin composition further comprising 1 to 60 parts by weight of (c) a thermoplastic elastomer based on 100 parts by weight of the polyphenylene sulfide resin composition according to claim (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29435089A JPH03153757A (en) | 1989-11-13 | 1989-11-13 | Polyphenylene sulfide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29435089A JPH03153757A (en) | 1989-11-13 | 1989-11-13 | Polyphenylene sulfide resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03153757A true JPH03153757A (en) | 1991-07-01 |
Family
ID=17806574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29435089A Pending JPH03153757A (en) | 1989-11-13 | 1989-11-13 | Polyphenylene sulfide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03153757A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5504165A (en) * | 1995-03-17 | 1996-04-02 | General Electric Company | Poly(phenylene ether)-poly(arylene sulfide)resin compositions. |
| US5612401A (en) * | 1995-03-17 | 1997-03-18 | General Electric Company | Compositions of poly(phenylene ether) poly(arylene sulfide) polyester resins and compatibilizer compound |
| US5837758A (en) * | 1995-06-07 | 1998-11-17 | General Electric Company | Compositions of poly (phenylene ether), poly (arylene sulfide) and ortho ester compounds |
| US6303708B1 (en) | 1995-03-17 | 2001-10-16 | General Electric Company | Functional poly(phenylene ether)/poly(arylene sulfide)/epoxy function alpha olefin elastomer/elastomeric block copolymer/metal salt compositions and process for making thereof |
| WO2003035760A2 (en) * | 2001-10-25 | 2003-05-01 | Asahi Kasei Chemicals Corporation | Polyphenylene sulfide resin composition |
-
1989
- 1989-11-13 JP JP29435089A patent/JPH03153757A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5504165A (en) * | 1995-03-17 | 1996-04-02 | General Electric Company | Poly(phenylene ether)-poly(arylene sulfide)resin compositions. |
| US5612401A (en) * | 1995-03-17 | 1997-03-18 | General Electric Company | Compositions of poly(phenylene ether) poly(arylene sulfide) polyester resins and compatibilizer compound |
| US6303708B1 (en) | 1995-03-17 | 2001-10-16 | General Electric Company | Functional poly(phenylene ether)/poly(arylene sulfide)/epoxy function alpha olefin elastomer/elastomeric block copolymer/metal salt compositions and process for making thereof |
| US5837758A (en) * | 1995-06-07 | 1998-11-17 | General Electric Company | Compositions of poly (phenylene ether), poly (arylene sulfide) and ortho ester compounds |
| WO2003035760A2 (en) * | 2001-10-25 | 2003-05-01 | Asahi Kasei Chemicals Corporation | Polyphenylene sulfide resin composition |
| WO2003035760A3 (en) * | 2001-10-25 | 2004-12-23 | Asahi Kasei Chemicals Corp | Polyphenylene sulfide resin composition |
| US7173090B2 (en) | 2001-10-25 | 2007-02-06 | Asahi Kasei Chemicals Corporation | Polyphenylene sulfide resin composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0374461A (en) | Thermoplastic resin composition and production thereof | |
| JPH01103653A (en) | Compatible polyphenylene ether-linear polyester compound containing mica reinforcing agent | |
| US4526923A (en) | Polyethylene terephthalate blends | |
| JP3889122B2 (en) | Polyarylene sulfide resin composition | |
| EP0042724B1 (en) | Polyethylene terephthalate blends | |
| JPH03153757A (en) | Polyphenylene sulfide resin composition | |
| JPH0940865A (en) | Polyarylene sulfide resin composition | |
| JP2855272B2 (en) | Flame retardant polyamide resin composition | |
| JPH03265661A (en) | Flame-retardant resin composition | |
| JPH03244661A (en) | Polyphenylene sulfide resin composition | |
| JPH0459870A (en) | Polyphenylene sulfide resin composition | |
| JPH03252455A (en) | Thermoplastic resin composition | |
| JP3034569B2 (en) | Polyphenylene sulfide resin composition | |
| JPH0286653A (en) | Thermoplastic resin composition | |
| JP2001172499A (en) | Thermoplastic resin composition | |
| JPH0326748A (en) | Thermoplastic resin composition having improved impact resistance | |
| JPH0286652A (en) | Thermoplastic resin composition | |
| JP2502840B2 (en) | Thermoplastic resin composition | |
| JPH0284462A (en) | Thermoplastic resin composition | |
| JPH02227446A (en) | Resin composition | |
| JPH051213A (en) | Thermoplastic resin composition | |
| KR100550932B1 (en) | Polyphenylene ether resin composition | |
| JPH08165422A (en) | Polyphenylene ether resin composition | |
| JPS60258249A (en) | Resin composition | |
| JPH02182756A (en) | Resin composition |