JPH0361702B2 - - Google Patents
Info
- Publication number
- JPH0361702B2 JPH0361702B2 JP57142616A JP14261682A JPH0361702B2 JP H0361702 B2 JPH0361702 B2 JP H0361702B2 JP 57142616 A JP57142616 A JP 57142616A JP 14261682 A JP14261682 A JP 14261682A JP H0361702 B2 JPH0361702 B2 JP H0361702B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- pps
- composition
- weight
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 26
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 26
- 239000003822 epoxy resin Substances 0.000 claims description 24
- 229920000647 polyepoxide Polymers 0.000 claims description 24
- 239000011256 inorganic filler Substances 0.000 claims description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 description 18
- -1 alkali metal salt Chemical class 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 238000000034 method Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 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
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 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
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Chemical group 0.000 description 2
- 239000002184 metal Chemical group 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-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 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004604 Blowing Agent Substances 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920013632 Ryton Polymers 0.000 description 1
- 239000004736 Ryton® Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 239000006185 dispersion Substances 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052895 riebeckite 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、無機充填剤及びエポキシ樹脂を含有
するポリフエニレンスルフイド組成物に関するも
のであり、特に機械的強度、寸法安定性及び熱的
特性等に優れた性能を示し、エンジニアリングプ
ラスチツクスとして実用性の大きな樹脂組成物に
関するものである。
ポリフエニレンスルフイド(以下PPSと略す)
は耐熱性、成形性、耐薬品性、剛性等の優れた高
性能エンジニアリングプラスチツクスとして注目
されているが、PPS単独では伸びが少なく脆弱で
ある欠点を有しており、通常ガラス繊維等の各種
無機充填剤を配合されたものとして使用されてい
る。しかしながら、無機充填剤を多く配合するこ
とは成形加工性が低下して成形品外観を損なつた
りするので、その使用には制限がある。反面無機
充填剤の量が少ない場合には強化効果が低下する
ばかりか、成形品中にボイドが発生したりすると
言つた問題点を有しておりこれらの改善には数多
くの提案が行われている。
例えば、特公昭53−13391号では無機充填剤を
含有するPPSに未硬化のエポキシ樹脂を配合する
ことによつて機械的強度や熱変形温度等を改善す
ることが提案されている。しかし、この処方では
場合によつてはエポキシ樹脂自身の架橋三次元化
の進行に伴つて組成物の流動性が著しく低下し、
金型キヤビテイーへの樹脂の安定した定量供給が
不可能となつたり、50〜150℃程度の温度雰囲気
でも成形品表面へのエポキシ樹脂のブリード現象
が発生して成形品の外観を著しく損なう欠点があ
る。更にエポキシ樹脂を多く配合しても熱変形温
度の低下や高温下での剛性が失われる等の問題が
認められ実用性に於ては多くの改善の余地がある
ことが判明した。
又、PPSと種々の熱可塑性樹脂とのポリマーブ
レンドが提案されている。例えば、特公昭53−
13468号ではPPSにポリカーボネート樹脂をブレ
ンドして成形性と耐衝撃性を改良している。特公
昭53−13469号ではPPSにポリスチレンをブレン
ドして成形性と耐衝撃性の改良を提案している。
又、特開昭50−156561号ではPPSとポリフエニレ
ンオキサイドとかならなる成形加工性、難燃効果
に優れる樹脂組成物が提案されている。しかしな
がら、それらの提案に於いても耐溶剤性、熱的性
質、溶融流動特性等に関してPPS樹脂単独に比べ
て低下すると云つた問題点を有しており改善の余
地が残されていることが判明した。
本発明者等は鋭意研究の結果、前述のPPSの欠
点を大巾に改善し、かつ、機械的強度、寸法安定
性及び熱的特性等に優れた実用性の大きいPPS組
成物を見出した。
即ち、本発明はPPS30〜90重量部、無機充填剤
70〜10重量部及びエポキシ樹脂硬化物0.1〜100重
量部(PPS100重量部に対して)からなるPPS組
成物を提供するものである。
本発明の組成物はPPSの優れた特性が失われる
ことなく、機械的強度及び熱的特性が向上し、成
形加工性に優れており、かつ150℃でもブリード
現象がない外観の優れた成形品をもたらすことが
できるものである。
本発明に使用するPPSとしては一般式
The present invention relates to a polyphenylene sulfide composition containing an inorganic filler and an epoxy resin, which exhibits particularly excellent performance in mechanical strength, dimensional stability, thermal properties, etc., and is useful as an engineering plastic. This invention relates to a resin composition with high properties. Polyphenylene sulfide (hereinafter abbreviated as PPS)
PPS is attracting attention as a high-performance engineering plastic with excellent heat resistance, moldability, chemical resistance, and rigidity, but PPS alone has the disadvantage of low elongation and brittleness, and it is usually used with various materials such as glass fiber. It is used with inorganic fillers added. However, if a large amount of inorganic filler is blended, molding processability may deteriorate and the appearance of the molded product may be impaired, so there are limitations to its use. On the other hand, if the amount of inorganic filler is small, not only will the reinforcing effect be reduced, but there will also be problems such as voids occurring in the molded product, and many proposals have been made to improve these problems. There is. For example, Japanese Patent Publication No. 53-13391 proposes improving mechanical strength, heat distortion temperature, etc. by blending an uncured epoxy resin with PPS containing an inorganic filler. However, in some cases, with this formulation, the fluidity of the composition decreases significantly as the epoxy resin itself progresses to three-dimensional crosslinking.
The disadvantage is that it becomes impossible to supply a stable quantity of resin to the mold cavity, and that the epoxy resin bleeds onto the surface of the molded product even in an atmosphere with a temperature of about 50 to 150℃, which significantly impairs the appearance of the molded product. be. Furthermore, even if a large amount of epoxy resin is blended, problems such as a decrease in heat distortion temperature and loss of rigidity at high temperatures are observed, and it has been found that there is much room for improvement in terms of practicality. Polymer blends of PPS and various thermoplastic resins have also been proposed. For example, the
No. 13468 blends PPS with polycarbonate resin to improve moldability and impact resistance. Japanese Patent Publication No. 53-13469 proposes blending polystyrene with PPS to improve moldability and impact resistance.
Furthermore, JP-A-50-156561 proposes a resin composition which is made of PPS and polyphenylene oxide and has excellent moldability and flame retardant effect. However, it has been found that even these proposals have problems such as solvent resistance, thermal properties, melt flow characteristics, etc., which are lower than PPS resin alone, and there is still room for improvement. did. As a result of intensive research, the present inventors have discovered a highly practical PPS composition that greatly improves the above-mentioned drawbacks of PPS and has excellent mechanical strength, dimensional stability, thermal properties, etc. That is, the present invention uses 30 to 90 parts by weight of PPS and an inorganic filler.
A PPS composition comprising 70 to 10 parts by weight and 0.1 to 100 parts by weight of a cured epoxy resin (based on 100 parts by weight of PPS) is provided. The composition of the present invention does not lose the excellent properties of PPS, has improved mechanical strength and thermal properties, has excellent moldability, and has a molded product with an excellent appearance without bleeding even at 150°C. It is something that can bring about. The general formula for PPS used in the present invention is
【式】で示される構成単位を70モル%
以上含むものがすぐれた特性の組成物をもたらす
ので好ましい。PPSの重合方法としては、p−ジ
クロルベンゼンを硫黄と炭酸ソーダの存在下で重
合させる方法、極性溶媒中で硫化ナトリウムある
いは水硫化ナトリウムと水酸化ナトリウム又は硫
化水素と水酸化ナトリウムの存在下で重合させる
方法、p−クロルチオフエノールの自己縮合など
があげられるが、N−メチルピロリドン、ジメチ
ルアセトアミドなどのアミド系溶媒やスルホラン
等のスルホン系溶媒中で硫化ナトリウムとp−ジ
クロルベンゼンを反応させる方法が適当である。
こ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を添加したり、水酸化
アルカリを添加することは好ましい方法である。
共重合成分として30モル%未満であればメタ結合
A composition containing 70 mol% or more of the structural unit represented by the formula is preferable because it provides a composition with excellent properties. PPS polymerization methods include polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or polymerizing p-dichlorobenzene in the presence of sodium sulfide, sodium hydrosulfide and sodium hydroxide, or hydrogen sulfide and sodium hydroxide in a polar solvent. Polymerization methods include self-condensation of p-chlorothiophenol, but sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfonic solvent such as sulfolane. The method is appropriate.
At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide.
If it is less than 30 mol% as a copolymer component, it is a meta bond.
【式】オルト結合[Formula] Ortho bond
【式】エーテル結合[Formula] Ether bond
【式】スルホン結合[Formula] Sulfone bond
【式】ビフエニル 結合[Formula] biphenyl join
【式】置換フエニル スルフイド結合[Formula] Substituted phenyl sulfide bond
【式】ここでRはア
ルキル、ニトロ、フエニル、アルコキシ、カルボ
ン酸またはカルボン酸の金属塩基を示す)、3官
能フエニルスルフイド結合[Formula] where R represents alkyl, nitro, phenyl, alkoxy, carboxylic acid or a metal base of carboxylic acid), trifunctional phenyl sulfide bond
【式】な
どを含有していてもポリマーの結晶性に大きく影
響しない範囲でかまわないが、好ましくは共重合
成分は10モル%以下がよい。特に3官能性以上の
フエニル、ビフエニル、ナフチルスルフイド結合
などを共重合に選ぶ場合は3モル%以下、さらに
好ましくは1モル%以下がよい。
かかるPPSは一般的な製造法、例えば(1)ハロゲ
ン置換芳香族化合物と硫化アルカリとの反応(米
国特許第2513188号明細書、特公昭44−27671号お
よび特公昭45−3368号参照)(2)チオフエノール類
のアルカリ触媒又は銅塩等の共存下における縮合
反応(米国特許第3274165号、英国特許第1160660
号参照)(3)芳香族化合物を塩化硫黄とのルイス酸
触媒共存下に於ける縮合反応(特公昭46−27255
号、ベルギー特許第29437号参照)等により合成
されるものであり、目的に応じ任意に選択し得
る。
本発明に用いられる無機充填剤としては、ガラ
ス繊維、炭素素繊維、チタン酸カリウム、アスベ
スト、炭化ケイ素、セラミツク繊維、金属繊維、
窒化ケイ素などの繊維状強化剤;硫酸バリウム、
硫酸カルシウム、カオリン、クレー、パイロフイ
ライト、ベントナイト、セリサイト、ゼオライ
ト、マイカ、雲母、ネフエリンシナイト、タル
ク、アタルパルジヤイト、ウオラストナイト、
PMF、フエライト、硅酸カルシウム、炭酸カル
シウム、炭酸マグネシウム、ドロマイト、三酸化
アンモン、酸化亜鉛、酸化チタン、酸化マグネシ
ウム、酸化鉄、二硫化モリブデン、黒鉛、石コ
ウ、ガラスビーズ、ガラスバルーン、石英粉など
の無機充填剤を例示することができる。尚、これ
らの無機充填剤を加える場合、公知のシランカツ
プリング剤を併用するのが好ましい。
本発明の組成物に於けるPPSと無機充填剤との
配合割合は、PPS30〜90重量部に対して無機充填
剤70〜10重量部の範囲が一般的である。
本発明において使用されるエポキシ樹脂硬化物
はエポキシ樹脂とフエノール樹脂、アミン類、酸
無水物等の硬化剤との硬化反応によつて製造され
る。エポキシ樹脂としてはエポキシ基を1個以
上、特に2個以上含有するのが好ましく、代表的
なものとしてはビスフエノールAとエピクロルヒ
ドリンとの縮合体をはじめとし、ビスフエノール
Aの代りにハロゲン化ビスフエノールA、レゾル
シン、ビスフエノールF、ビスフエノールSと用
いたもの、あるいはノボラツク型のもの、前記以
外の多価アルコール型のもの等が例示される。
このエポキシ樹脂硬化物は前記エポキシ樹脂と
フエノール樹脂、アミン類、酸無水物等の硬化剤
とが必要に応じて第3級アミン等の通常の反応触
媒と共に溶融加熱して付加重縮合した後、冷却粉
砕によつて簡単に製造することができる。
エポキシ樹脂硬化物を添加する上で最も重要な
ことはエポキシ樹脂硬化物が組成物中に均一に分
散していることであり、粗砕したエポキシ樹脂硬
化物を用いてもPPS及び無機充填剤と混練ペレツ
ト化する段階あるいは成形機シリンダー内での混
練の段階で均一分散が進むと考えられるが、予め
300μm以下に微粉砕化して添加すると、容易に本
発明の目的を達成することができて合理的であ
る。尚、その際エポキシ樹脂硬化物の粒径を更に
100μm以下に微粉砕化すると本発明の目的を達成
するのにより好都合である。エポキシ樹脂硬化物
が組成物中で不均一分散又は粒径が大きすぎる場
合には成形品の外観及び機械的強度を損なう等、
いずれも本発明の目的に不都合である。
本発明において、エポキシ樹脂硬化物は
PPS100重量部に対して0.1〜100重量部、好まし
くは0.5〜50重量部の割合で使用される。この量
が少なすぎる場合には添加効果が少さくなり、逆
に多すぎる場合には成形品の高温特性や組成物の
流動性が悪くなりすぎるので、ともに不都合であ
る。
更に、本発明組成物には、本発明の目的を逸脱
しない範囲で四フツ化エチレン、ポリアミド、ポ
リカーボネート、、ポリサルホン、ポリアリルサ
ルホン、ポリエーテルサルホン、ポリイミド、ポ
リアミドイミド、エポキシ樹脂、ポリエチレン、
ポリプロピレン、ポリエステル、ポリフエニレン
オキシド、ポリスチレン等のポリマー及び少量の
離型剤、滑剤、耐熱安定剤、着色剤、耐候性安定
剤、発泡剤を添加してもよい。
本発明において前記組成物の調整は種々の公知
の方法で可能である。例えば、全ての原料を予め
タンブラー又はヘンシエルミキサーのような混合
機で均一混合した後、一軸又は二軸の押出機等に
供給し、280℃〜360℃で溶融混練した後ペレツト
として調整する。
以下に、本発明を実施例により具体的に説明す
るが、本発明はこれらの実施例のみに限定される
ものではない。
実施例 1
(エポキシ樹脂硬化物パウダーの製造)
ノボラツク型エポキシ樹脂、エピクロンN−
670(大日本インキ化学工業社製、融点73℃、エポ
キシ当量212)100重量部、ノボラツク型フエノー
ル−ホルムアルデヒド樹脂(バーカムTD−
2093、大日本インキ化学工業社製、融点100℃、
OH当量104)50重量部を各々100℃、120℃の温
度で均一に溶融し、硬化反応触媒2−メチルイミ
ダゾール(キシダ化学社製)2重量部と共に均一
融混合し、140℃で2時間、次いで180℃で4時間
硬化反応を行つた。得られた硬化物をハンマーミ
ルで粗粉砕した後ミクロパルペライザーで微粉砕
して200メツシユスクリーンをパスしたものをエ
ポキシ樹脂硬化物パウダーとした。
得られたエポキシ樹脂硬化物パウダーの粒径
は100μm以下、ASTM D−648によるその熱変
形温度は160℃及び10℃/分で測定したその5%
減量温度は320℃であつた。
実施例1〜3、比較例1〜6
PPS(フイリツプス社製、RYTON P−6及
びP−4)、充填剤としてガラスビーズ(東芝バ
ロテイーニ社製、EGB731B)、ガラス繊維(旭ガ
ラス社製、グラスロンCS03 MA497)及びポリ
マー添加剤としてエポキシ樹脂硬化物パウダー
(参照例1で調製)、エポキシ樹脂〔エピクロン
7050(ビスフエノール型)大日本インキ化学工業
社製〕エピクロンN−670、ポリカーボネート樹
脂(三菱化成社製、ノバレツクス7025)を表1に
示す割合で均一予備混合した後、同方向回転型
50m/mの2軸押出機にてスクリユー回転数
100rpm、バレル温度320℃で溶融混練してペレツ
トを得た。このペレツトをスクリユー式射出成形
機(東芝機械社製)にて温度320℃、金型温度130
℃、射出圧力(1次/2次)1700/600(Kg/cm2)
で曲げ強度及び外観変化測定用のテストピースを
成形した。又、組成物の流動安定性を評価するた
めにASTM D−1238に準じてペレツトのフロー
レイト(g/10分)を測定した(測定条件;300
℃/荷重5Kg)。さらに、成形品の耐熱ブリード
性及び耐溶剤性を測定するためにテストピースを
各々熱風乾燥中に150℃/時間、トルエン浸漬/
24時間のテストを行つた。それらの結果を表1に
まとめて示す。
表1に示すように本発明による組成物は機械的
強度、流動安定性、耐ブリード性及び耐溶剤性に
優れており、本発明以外の比較例では機械的強度
の低下や流動安定性が悪く、高温下での時間経過
に伴つて流動性の変化があることが認められた。
さらには高温下でのブリードもしくはトルエン
浸漬による成形品外観不良が目立つた。[Formula] and the like may be contained as long as they do not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is 10 mol% or less. In particular, when trifunctional or more functional phenyl, biphenyl, naphthyl sulfide bonds, etc. are selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less. Such PPS can be produced by common manufacturing methods, such as (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (see U.S. Pat. No. 2,513,188, Japanese Patent Publication No. 44-27671 and Japanese Patent Publication No. 45-3368) (2) ) Condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt (US Patent No. 3274165, British Patent No. 1160660)
(3) Condensation reaction of aromatic compounds with sulfur chloride in the coexistence of a Lewis acid catalyst (Special Publication No. 46-27255)
(see Belgian Patent No. 29437), and can be arbitrarily selected depending on the purpose. Inorganic fillers used in the present invention include glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal fiber,
Fibrous reinforcement such as silicon nitride; barium sulfate,
Calcium sulfate, kaolin, clay, pyrofluorite, bentonite, sericite, zeolite, mica, mica, nephelinsinite, talc, attalpargite, wollastonite,
PMF, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, ammonium trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass balloon, quartz powder, etc. Examples include inorganic fillers. In addition, when adding these inorganic fillers, it is preferable to use a known silane coupling agent together. The blending ratio of PPS and inorganic filler in the composition of the present invention is generally in the range of 70 to 10 parts by weight of inorganic filler to 30 to 90 parts by weight of PPS. The cured epoxy resin used in the present invention is produced by a curing reaction between an epoxy resin and a curing agent such as a phenolic resin, amines, or acid anhydride. The epoxy resin preferably contains one or more epoxy groups, especially two or more. Typical examples include a condensate of bisphenol A and epichlorohydrin, and a halogenated bisphenol instead of bisphenol A. Examples thereof include those using A, resorcinol, bisphenol F, and bisphenol S, novolac types, and polyhydric alcohol types other than those mentioned above. This epoxy resin cured product is obtained by melting and heating the epoxy resin and a curing agent such as a phenol resin, amines, acid anhydride, etc. together with a normal reaction catalyst such as a tertiary amine as needed, and then carrying out addition polycondensation. It can be easily produced by cooling and grinding. The most important thing when adding a cured epoxy resin is that the cured epoxy resin is uniformly dispersed in the composition. It is thought that uniform dispersion progresses at the stage of kneading into pellets or at the stage of kneading in the molding machine cylinder, but
It is reasonable to add it after pulverizing it to 300 μm or less, since the object of the present invention can be easily achieved. At this time, the particle size of the cured epoxy resin may be further increased.
It is more convenient to achieve the object of the present invention if it is pulverized to 100 μm or less. If the cured epoxy resin is unevenly dispersed in the composition or the particle size is too large, the appearance and mechanical strength of the molded product may be impaired.
Both are disadvantageous for the purpose of the present invention. In the present invention, the epoxy resin cured product is
It is used in a proportion of 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of PPS. If this amount is too small, the effect of the addition will be reduced, and if it is too large, the high temperature properties of the molded article and the fluidity of the composition will become too poor, both of which are disadvantageous. Furthermore, the composition of the present invention may contain tetrafluoroethylene, polyamide, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, polyimide, polyamideimide, epoxy resin, polyethylene,
Polymers such as polypropylene, polyester, polyphenylene oxide, polystyrene, and small amounts of mold release agents, lubricants, heat stabilizers, colorants, weather stabilizers, and blowing agents may be added. In the present invention, the composition can be prepared by various known methods. For example, all the raw materials are uniformly mixed in advance using a mixer such as a tumbler or Henschel mixer, then fed to a single or twin screw extruder, etc., melted and kneaded at 280°C to 360°C, and then prepared as pellets. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 (Production of cured epoxy resin powder) Novolac type epoxy resin, Epicron N-
670 (manufactured by Dainippon Ink and Chemicals, melting point 73°C, epoxy equivalent 212) 100 parts by weight, novolac type phenol-formaldehyde resin (Burcam TD-
2093, manufactured by Dainippon Ink and Chemicals, melting point 100℃,
50 parts by weight of OH equivalent (104) were uniformly melted at temperatures of 100°C and 120°C, respectively, and homogeneously melt-mixed with 2 parts by weight of the curing reaction catalyst 2-methylimidazole (manufactured by Kishida Chemical Co., Ltd.), and heated at 140°C for 2 hours. A curing reaction was then carried out at 180°C for 4 hours. The obtained cured product was coarsely pulverized with a hammer mill, then finely pulverized with a micropulperizer, and passed through a 200 mesh screen to obtain an epoxy resin cured product powder. The particle size of the obtained cured epoxy resin powder is 100 μm or less, and its heat distortion temperature according to ASTM D-648 is 5% of that measured at 160°C and 10°C/min.
The weight loss temperature was 320°C. Examples 1 to 3, Comparative Examples 1 to 6 PPS (manufactured by Philips Corporation, RYTON P-6 and P-4), glass beads as a filler (manufactured by Toshiba Balloteini, EGB731B), glass fiber (manufactured by Asahi Glass Co., Ltd., Glasslon CS03 MA497), epoxy resin cured powder (prepared in Reference Example 1) as a polymer additive, epoxy resin [Epiclon
7050 (bisphenol type) produced by Dainippon Ink & Chemicals Co., Ltd.] Epiclon N-670 and polycarbonate resin (manufactured by Mitsubishi Kasei Co., Ltd., Novarex 7025) were uniformly premixed in the proportions shown in Table 1, and then mixed in the same direction rotating type.
Screw rotation speed in a 50m/m twin screw extruder
Pellets were obtained by melt-kneading at 100 rpm and a barrel temperature of 320°C. The pellets were molded using a screw-type injection molding machine (manufactured by Toshiba Machine Co., Ltd.) at a temperature of 320℃ and a mold temperature of 130℃.
°C, injection pressure (primary/secondary) 1700/600 (Kg/cm 2 )
A test piece for measuring bending strength and appearance change was molded. In addition, in order to evaluate the flow stability of the composition, the flow rate (g/10 min) of the pellets was measured according to ASTM D-1238 (measurement conditions: 300
°C/load 5Kg). Furthermore, in order to measure the heat bleed resistance and solvent resistance of the molded products, each test piece was immersed in toluene at 150°C/hour during hot air drying.
I did a 24 hour test. The results are summarized in Table 1. As shown in Table 1, the composition according to the present invention has excellent mechanical strength, flow stability, bleed resistance, and solvent resistance, while the comparative examples other than the composition according to the present invention have decreased mechanical strength and poor flow stability. It was observed that there was a change in fluidity with the passage of time at high temperatures. Furthermore, poor appearance of the molded product was noticeable due to bleeding under high temperatures or immersion in toluene.
Claims (1)
機充填剤70〜10重量部及びエポキシ樹脂硬化物
0.1〜100重量部(ポリフエニレンスルフイド100
重量部に対して)からなるポリフエニレンスルフ
イド組成物。1 30 to 90 parts by weight of polyphenylene sulfide, 70 to 10 parts by weight of inorganic filler, and cured epoxy resin
0.1 to 100 parts by weight (polyphenylene sulfide 100
parts by weight).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14261682A JPS5933360A (en) | 1982-08-19 | 1982-08-19 | Polyphenylene sulfide composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14261682A JPS5933360A (en) | 1982-08-19 | 1982-08-19 | Polyphenylene sulfide composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5933360A JPS5933360A (en) | 1984-02-23 |
JPH0361702B2 true JPH0361702B2 (en) | 1991-09-20 |
Family
ID=15319469
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14261682A Granted JPS5933360A (en) | 1982-08-19 | 1982-08-19 | Polyphenylene sulfide composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5933360A (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62280258A (en) * | 1986-05-29 | 1987-12-05 | Dainippon Ink & Chem Inc | Polyphenylene sulfide resin composition and molded product obtained therefrom |
EP0423510A1 (en) * | 1989-10-20 | 1991-04-24 | General Electric Company | Highly dense thermoplastic molding compositions |
JP2754486B2 (en) * | 1997-01-27 | 1998-05-20 | 株式会社林原生物化学研究所 | Production method of food and drink using glycosyl transfer reaction |
JP5741036B2 (en) * | 2011-02-10 | 2015-07-01 | 東レ株式会社 | Polyphenylene sulfide resin composition and molded article comprising the same |
CN109535716A (en) * | 2018-10-18 | 2019-03-29 | 江苏澳盛复合材料科技有限公司 | A kind of and good polyphenylene sulfide/carbon fibre composite of metal adhesion |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5313391A (en) * | 1976-07-22 | 1978-02-06 | Agency Of Ind Science & Technol | Composite superconductive body |
-
1982
- 1982-08-19 JP JP14261682A patent/JPS5933360A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5313391A (en) * | 1976-07-22 | 1978-02-06 | Agency Of Ind Science & Technol | Composite superconductive body |
Also Published As
Publication number | Publication date |
---|---|
JPS5933360A (en) | 1984-02-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO1980000349A1 (en) | Heat-resistant molding resin composition | |
JPS6322224B2 (en) | ||
JPWO2017057558A1 (en) | Polyarylene sulfide resin composition, molded article and production method | |
JPH0379389B2 (en) | ||
JPH0579701B2 (en) | ||
JPH0361702B2 (en) | ||
JPH0372669B2 (en) | ||
JPS6011063B2 (en) | resin composition | |
JPH07742B2 (en) | Polyphenylene sulfide resin composition | |
JP2013075997A (en) | Polyarylene sulfide resin composition | |
JPH0524177B2 (en) | ||
EP0255370B1 (en) | Polyarylene sulfide resin compositions, and articles manufactured therefrom | |
JPH09157525A (en) | Polyphenylene sulfide resin composition for precision molding | |
JPS64991B2 (en) | ||
JPS5964657A (en) | Thermoplastic polyester resin composition | |
JP3478371B2 (en) | Polyphenylene sulfide resin composition for precision molding | |
JPH0586293A (en) | Polyphenylene sulfide resin composition | |
JPH04258668A (en) | Polyphenylene sulfide resin composition | |
JP3434681B2 (en) | Polyphenylene sulfide resin composition for precision molding | |
JP2001234053A (en) | Resin composition | |
JP3478372B2 (en) | Polyphenylene sulfide resin composition for precision molding | |
JP3434680B2 (en) | Polyphenylene sulfide resin composition for precision molding | |
JP3038794B2 (en) | Resin composition | |
JP2002188005A (en) | Polyphenylene sulfide resin composition | |
JPH01217063A (en) | Polyphenylene sulfide resin composition |