JP2005264124A - Polyphenylene sulfide resin composition - Google Patents
Polyphenylene sulfide resin composition Download PDFInfo
- Publication number
- JP2005264124A JP2005264124A JP2004083221A JP2004083221A JP2005264124A JP 2005264124 A JP2005264124 A JP 2005264124A JP 2004083221 A JP2004083221 A JP 2004083221A JP 2004083221 A JP2004083221 A JP 2004083221A JP 2005264124 A JP2005264124 A JP 2005264124A
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- JP
- Japan
- Prior art keywords
- component
- resin composition
- weight
- polyphenylene sulfide
- sulfide resin
- 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
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- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 95
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 94
- 239000011342 resin composition Substances 0.000 title claims abstract description 58
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 61
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 41
- 239000011256 inorganic filler Substances 0.000 claims abstract description 21
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 21
- 238000004898 kneading Methods 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 84
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- 229920001577 copolymer Polymers 0.000 claims description 32
- 238000000465 moulding Methods 0.000 claims description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 19
- 238000000605 extraction Methods 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 6
- 239000010881 fly ash Substances 0.000 claims description 6
- 229960001545 hydrotalcite Drugs 0.000 claims description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 239000010883 coal ash Substances 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- CCLUUWFOQAVFKN-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole;styrene Chemical compound C=CC1=NCCO1.C=CC1=CC=CC=C1 CCLUUWFOQAVFKN-UHFFFAOYSA-N 0.000 claims 1
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 23
- 230000002087 whitening effect Effects 0.000 abstract description 12
- 230000003287 optical effect Effects 0.000 abstract description 9
- 230000007246 mechanism Effects 0.000 abstract description 6
- 239000013307 optical fiber Substances 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 125000002971 oxazolyl group Chemical group 0.000 description 9
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- -1 polyphenylene Polymers 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000003857 carboxamides Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000010943 off-gassing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 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
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-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
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- GRXOKDOOUFYKLX-UHFFFAOYSA-N 3,5-dichloro-7-oxabicyclo[2.2.1]hepta-1(6),2,4-triene Chemical compound ClC1=C(O2)C(Cl)=CC2=C1 GRXOKDOOUFYKLX-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
- KXRLIZRDCCQKDZ-UHFFFAOYSA-N 3-ethyl-5-methyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(CC)=CC2=C1 KXRLIZRDCCQKDZ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- 239000004698 Polyethylene Substances 0.000 description 1
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- 238000000944 Soxhlet extraction Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 239000006096 absorbing agent Substances 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
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- 125000004103 aminoalkyl group Chemical group 0.000 description 1
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
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- 125000004957 naphthylene group Chemical group 0.000 description 1
- UTOPWMOLSKOLTQ-UHFFFAOYSA-M octacosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O UTOPWMOLSKOLTQ-UHFFFAOYSA-M 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 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
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012207 quantitative assay Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 229910000679 solder Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005650 substituted phenylene group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
本発明は、光学機器機構部品、光ファイバ用コネクタフェルール、プリンター部品、コピー機部品、自動車ランプ部品、自動車エンジンルーム内部品等の成型品として成形した際に成型品表面に発生する成形白化を無くし優れた表面外観および優れた難燃性を与えるポリフェニレンスルフィド樹脂組成物に関する。 The present invention eliminates molding whitening that occurs on the surface of molded products when molded as molded products such as optical device mechanism parts, optical fiber connector ferrules, printer parts, copier parts, automobile lamp parts, automobile engine compartment parts, etc. The present invention relates to a polyphenylene sulfide resin composition that provides excellent surface appearance and excellent flame retardancy.
ポリフェニレンスルフィド樹脂は、耐熱性の高い結晶性樹脂の一つとしてガラス繊維等のフィラーを配合し、耐熱性、耐薬品性、剛性および難燃性に優れた樹脂成形材料として、電気・電子・ＯＡ部品、自動車電装系部品として利用されている。
中でも、光学機器機構部品の一つであるコンパクトディスクなどに内蔵されている光ピックアップベースや、コピー機の光学系ハウジングは、アルミニウム、亜鉛等の金属ダイキャストにより製造されていたが、近年、軽量化、生産性向上の観点より、樹脂化への転換がなされており、特にポリフェニレンスルフィド樹脂組成物が多く用いられてきている。
Polyphenylene sulfide resin is blended with fillers such as glass fiber as one of crystalline resins with high heat resistance, and is a resin molding material with excellent heat resistance, chemical resistance, rigidity and flame resistance. It is used as parts and automotive electrical parts.
Among them, the optical pickup base built in a compact disk, which is one of the optical device mechanism parts, and the optical system housing of the copying machine were manufactured by metal die casting such as aluminum and zinc. From the viewpoint of improvement in productivity and productivity, conversion to resinization has been made, and in particular, polyphenylene sulfide resin compositions have been frequently used.
しかしながら、ポリフェニレンスルフィド樹脂は樹脂性能として優れた耐熱性、加工性を有するものの、成形時は酸素雰囲気下で高温状態で溶融するため成形金型の金属を腐食させたり、ガス発生に伴い金型表面や成型品表面にシミ焼けやヤニ状の物質が付着したり、ウエルド部を有する成形金型ではガス抜けが悪化すると黒着色成型品のウエルド部周辺が外観として白化した状態になる等、成形時に多くの問題点を引き起こす樹脂であることが周知となっている。これらの問題点は、ポリフェニレンスルフィドおよびポリフェニレンエーテルで構成されているポリマーアロイでも同様な問題点を引き起こしている。そしてさらに、このポリフェニレンスルフィドとポリフェニレンエーテルからなるポリマーアロイにおいては、ポリフェニレンスルフィド中にポリフェニレンエーテルを含むことにより成形時のバリ発生を抑制する利点が認められるものの、欠点として特に無機系充填剤を含んだポリマーアロイにおいて難燃性が極度に悪化する現象が起こっている。 However, although polyphenylene sulfide resin has excellent heat resistance and workability as resin performance, it melts at high temperature in an oxygen atmosphere at the time of molding, so it corrodes the metal of the molding die or the surface of the die due to gas generation When molding, such as spot burns or grime-like substances adhering to the surface of the molded product, or when the outgassing worsens in a molding die with a welded part, the welded part periphery of the black colored molded product becomes whitened as an appearance. It is well known that the resin causes many problems. These problems cause similar problems even in polymer alloys composed of polyphenylene sulfide and polyphenylene ether. In addition, in this polymer alloy composed of polyphenylene sulfide and polyphenylene ether, an advantage of suppressing the generation of burrs during molding by the inclusion of polyphenylene ether in the polyphenylene sulfide is recognized, but an inorganic filler is particularly included as a drawback. There is a phenomenon in which flame retardancy is extremely deteriorated in polymer alloys.
これら問題点のうち、成形時の成形金型の金属を腐食させたり、ガス発生に伴い金型表面や成型品表面にシミ焼けやヤニ状の物質が付着したり、ウエルド部を有する成形金型ではガス抜けが悪化すると黒着色成型品のウエルド部周辺が外観として白化する等のポリフェニレンスルフィド樹脂組成物に関して材料面からの改良工夫が数多く提案されている。
これらの技術としては、ポリフェニレンスルフィド樹脂に無機質のガススカベンジャーを配合した組成物（例えば、特許文献１〜３参照）が提案されている。また、さらに成形時の金型へのヤニ付着防止やガス発生に伴う外観改良効果を得るために、ポリフェニレンスルフィドと特定の化合物や無機充填剤からなる樹脂組成物（例えば、特許文献４〜６参照）が提案されている。
Among these problems, the metal mold of the mold during molding is corroded, the mold surface and the surface of the molded product adhere to the surface of the mold and the molded product accompanying the generation of gas, or the mold having a weld part However, many improvements have been proposed in terms of materials regarding the polyphenylene sulfide resin composition, such as the appearance of the periphery of the welded portion of the black colored molded product whitening as the outgassing worsens.
As these techniques, a composition (for example, see Patent Documents 1 to 3) in which an inorganic gas scavenger is blended with a polyphenylene sulfide resin has been proposed. Further, in order to prevent the adhesion of the resin to the mold at the time of molding and to improve the appearance accompanying gas generation, a resin composition comprising polyphenylene sulfide and a specific compound or inorganic filler (for example, see Patent Documents 4 to 6). ) Has been proposed.
これら文献には、ベースとなるポリフェニレンサルファイド樹脂の欠点を解消するために他の添加剤を配合することにより、欠点である金型の金属表面腐食防止、金型表面や成型品表面にシミ焼けやヤニ状の物質の付着を防止し、成型品の外観改良を試みているが、これらの方法は単なる原因物質を隠蔽する手段に留まっており、ガス抜けが悪い成形条件で長時間成形した場合、特にウエルド部においては依然としてシミ焼けや、黒着色品においては白化現象が起こり成型品外観が顕著に悪化するなど、成型品とした場合未だ解決されていない問題点を数多く有しているのが実状である。
もう一つの問題点として、ポリフェニレンサルファイドとポリフェニレンエーテルからなるポリマーアロイの難燃性悪化に関してはこれら樹脂の特徴である耐熱性を維持した状態で難燃性を改良する技術は未だに提案されていないのが実状である。
In these documents, in order to eliminate the disadvantages of the base polyphenylene sulfide resin, by adding other additives, the metal surface corrosion prevention of the mold, which is a defect, and the surface of the mold and the molded product can be burnt. We try to improve the appearance of molded products by preventing the adhesion of spear-like substances, but these methods are merely a means to conceal the causative substances, and when molding for a long time under molding conditions where gas escape is bad, In particular, there are still a number of problems that have not been solved in the case of molded products, such as spot burns in the welds and whitening in black-colored products, resulting in a marked deterioration in the appearance of the molded products. It is.
Another problem is that regarding the flame retardancy deterioration of polymer alloys composed of polyphenylene sulfide and polyphenylene ether, no technology has been proposed to improve the flame retardancy while maintaining the heat resistance characteristic of these resins. Is real.
本発明の解決課題は、光学機器機構部品、映像機器内部部品、光ファイバ用コネクタフェルール、プリンター部品、コピー機部品、自動車ランプ部品、自動車エンジンルーム内部品等のウエルド部を有する成型品として長期間成型した際にウエルド部分の白化現象を大幅に改良し、成型品の外観が優れ、さらには難燃性に優れたポリフェニレンサルファイドとポリフェニレンエーテルからなるポリフェニレンスルフィド樹脂組成物を提供することにある。 The problems to be solved by the present invention are long-term molding products having weld parts such as optical device mechanism parts, video equipment internal parts, optical fiber connector ferrules, printer parts, copier parts, automobile lamp parts, automobile engine room parts, etc. An object of the present invention is to provide a polyphenylene sulfide resin composition comprising polyphenylene sulfide and polyphenylene ether, which is greatly improved in the whitening phenomenon of the weld portion when molded, has an excellent appearance of the molded product, and is excellent in flame retardancy.
本発明は、上記課題を解決すべく、ポリフェニレンスルフィド樹脂、ポリフェニレンエーテル系樹脂およびこれら樹脂の混和性を改良するための混和剤、さらには無機系充填剤からなる樹脂組成物に関して鋭意検討した結果、特定の架橋型ポリフェニレンスルフィド樹脂を用いて特定の製造方法で得られるポリフェニレンスルフィド樹脂組成物が、成型品として長期間成型した際にウエルド部分の白化現象を大幅に改良し、成型品の外観が優れさらには難燃性に優れることを見いだし、本発明に至った。 In order to solve the above-mentioned problems, the present invention has been conducted as a result of diligent studies on a resin composition comprising a polyphenylene sulfide resin, a polyphenylene ether resin, an admixture for improving the miscibility of these resins, and further an inorganic filler. A polyphenylene sulfide resin composition obtained by a specific manufacturing method using a specific cross-linked polyphenylene sulfide resin greatly improves the whitening phenomenon of the weld part when molded as a molded product for a long time, and the appearance of the molded product is excellent Furthermore, it has been found that it has excellent flame retardancy, and has led to the present invention.
すなわち本発明は、
［１］ （ａ）塩化メチレンによるオリゴマー抽出量が１重量％以下、且つ、３２０℃溶融状態で捕集される揮発分が１０００ｐｐｍ以下の架橋型ポリフェニレンスルフィド樹脂 １〜９９重量部、（ｂ）ポリフェニレンエーテル系樹脂 ９９〜１重量部、ならびに（ａ）成分と（ｂ）成分の合計１００重量部あたり（ｃ）混和剤 １〜２０重量部よりなる基礎的樹脂組成物であり、該基礎的樹脂組成物１００重量部に対して、（ｄ）無機系充填剤を４０〜４００重量部含むことを特徴とするポリフェニレンスルフィド樹脂組成物、
［２］ （ａ）成分の架橋型ポリフェニレンスルフィド樹脂の溶融粘度が１〜１００００ポイズである上記［１］に記載のポリフェニレンスルフィド樹脂組成物（但し、溶融粘度はＪＩＳＫ−７２１０に準拠し、フローテスターを用いて、３００℃、荷重１９６Ｎ、ダイ長さ（Ｌ）／ダイ径（Ｄ）＝１０ｍｍ／１ｍｍで６分間保持した後の測定値）、
［３］ （ｂ）成分のポリフェニレンエーテル系樹脂が、ポリフェニレンエーテル１００重量％またはポリフェニレンエーテル／スチレン系樹脂＝１〜９９重量％／９９〜１重量％のいずれか１つの構成比率である上記［１］または［２］に記載のポリフェニレンスルフィド樹脂組成物、
［４］ （ｃ）成分の混和剤が、スチレン−グリシジルメタクリレート共重合体、スチレン−グリシジルメタクリレート−メチルメタクリレート共重合体、スチレン−グリシジルメタクリレート−アクリロニトリル共重合体、スチレン−ビニルオキサゾリン共重合体およびスチレン−ビニルオキサゾリン−アクリロニトリル共重合体からなる群の中から選ばれる少なくとも１種である上記１〜３のいずれかに記載のポリフェニレンスルフィド樹脂組成物、
［５］ （ｄ）成分の無機系充填剤が、ガラス繊維、炭素繊維、カーボンナノチューブ、アルミナ繊維、炭化珪素繊維、セラミック繊維、石膏繊維、金属繊維、チタン酸カリウムウィスカー、炭酸カルシウム、多孔質炭酸カルシウム、炭酸カルシウムウィスカー、ハイドロタルサイト、カオリン、クレー、ケイ酸カルシウム、カーボンブラック、酸化チタン、ハイドロタルサイト、酸化マグネシウム、酸化アルミニウム、酸化カルシウム、フライアッシュ（石炭灰）、ワラステナイト、ガラスフレーク、マイカ、タルク、グラファイト、窒化アルミニウム、窒化硼素および二硫化モリブデンからなる群の中から選ばれる少なくとも１種である上記［１］〜［４］のいずれかに記載のポリフェニレンスルフィド樹脂組成物、
［６］ 上記［１］〜［５］のいずれかに記載のポリフェニレンスルフィド樹脂組成物を成形してなる成型品。
［７］ 少なくとも２個のベント口および少なくとも１個のサイド供給口を有し、２８０℃以上に温度設定した二軸押出機を用いて、（ａ）オリゴマー量が１重量％以下、且つ、揮発分１０００ｐｐｍ以下の架橋型ポリフェニレンスルフィド樹脂、（ｂ）ポリフェニレンエーテル系樹脂および（ｃ）混和剤からなる基礎的樹脂組成物を溶融混練した後に、該二軸押出機の第一ベント口を絶対真空圧９５ｋＰａ以下で脱気し、該ベント口通過後に（ｄ）無機系充填剤を少なくとも１つ以上の該二軸押出機のサイド供給口より供給し（ａ）〜（ｃ）成分で構成される基礎的樹脂組成物と（ｄ）無機系充填剤を一緒に溶融混練し、さらに該二軸押出機の第二ベント口を絶対真空圧９５ｋＰａ以下で脱気して得られるポリフェニレンスルフィド樹脂組成物の製造方法、
That is, the present invention
[1] (a) 1 to 99 parts by weight of a crosslinked polyphenylene sulfide resin in which the amount of oligomer extracted with methylene chloride is 1% by weight or less and the volatile content collected in a molten state at 320 ° C. is 1000 ppm or less, (b) polyphenylene 99 to 1 part by weight of an ether-based resin, and (c) a basic resin composition comprising 1 to 20 parts by weight of an admixture per 100 parts by weight of the total of the components (a) and (b). (D) 40 to 400 parts by weight of an inorganic filler with respect to 100 parts by weight of the product, a polyphenylene sulfide resin composition,
[2] The polyphenylene sulfide resin composition according to the above [1], wherein the cross-linked polyphenylene sulfide resin as the component (a) has a melt viscosity of 1 to 10,000 poises (provided that the melt viscosity conforms to JISK-7210 and is a flow tester. , Measured value after holding for 6 minutes at 300 ° C., load 196 N, die length (L) / die diameter (D) = 10 mm / 1 mm),
[3] The above-mentioned [1], wherein the polyphenylene ether resin as the component (b) has a composition ratio of any one of 100% by weight of polyphenylene ether or polyphenylene ether / styrene resin = 1 to 99% by weight / 99 to 1% by weight. Or the polyphenylene sulfide resin composition according to [2],
[4] The admixture of component (c) is a styrene-glycidyl methacrylate copolymer, a styrene-glycidyl methacrylate-methyl methacrylate copolymer, a styrene-glycidyl methacrylate-acrylonitrile copolymer, a styrene-vinyl oxazoline copolymer, and styrene. -The polyphenylene sulfide resin composition according to any one of the above 1 to 3, which is at least one selected from the group consisting of a vinyloxazoline-acrylonitrile copolymer,
[5] Component (d) inorganic filler is glass fiber, carbon fiber, carbon nanotube, alumina fiber, silicon carbide fiber, ceramic fiber, gypsum fiber, metal fiber, potassium titanate whisker, calcium carbonate, porous carbonate Calcium, calcium carbonate whisker, hydrotalcite, kaolin, clay, calcium silicate, carbon black, titanium oxide, hydrotalcite, magnesium oxide, aluminum oxide, calcium oxide, fly ash (coal ash), wollastonite, glass flakes, The polyphenylene sulfide resin composition according to any one of the above [1] to [4], which is at least one selected from the group consisting of mica, talc, graphite, aluminum nitride, boron nitride, and molybdenum disulfide,
[6] A molded product obtained by molding the polyphenylene sulfide resin composition according to any one of [1] to [5].
[7] Using a twin screw extruder having at least two vent ports and at least one side supply port and set at a temperature of 280 ° C. or higher, (a) the amount of oligomer is 1% by weight or less and volatilization After melt-kneading a basic resin composition comprising a cross-linked polyphenylene sulfide resin having a content of 1000 ppm or less, (b) polyphenylene ether resin, and (c) an admixture, the first vent port of the twin screw extruder is subjected to absolute vacuum pressure. Deaerated at 95 kPa or less, and after passing through the vent port, (d) an inorganic filler is supplied from at least one side feed port of the twin-screw extruder and is composed of components (a) to (c) Polyphenylene sulfide resin composition obtained by melt-kneading together a mechanical resin composition and (d) an inorganic filler, and degassing the second vent port of the twin-screw extruder at an absolute vacuum pressure of 95 kPa or less Manufacturing method,
本発明のポリフェニレンスルフィド樹脂組成物は、成型品として長期間成型した際にウエルド部分の白化現象を大幅に改良し、成型品の外観が優れ、さらに難燃性が優れ、産業上、大いに有用である。 The polyphenylene sulfide resin composition of the present invention greatly improves the whitening phenomenon of the weld part when molded as a molded product for a long period of time, has an excellent appearance of the molded product, and has excellent flame retardancy, which is very useful industrially. is there.
以下、本発明について詳細に説明する。
本発明のポリフェニレンスルフィド樹脂組成物の樹脂成分となる基礎的樹脂組成物は、下記に示す（ａ）成分の架橋型ポリフェニレンスルフィド樹脂、（ｂ）成分のポリフェニレンエーテル系樹脂および（ｃ）混和剤より構成される。
本発明で用いられる（ａ）成分の架橋型ポリフェニレンスルフィド樹脂（以下ＰＰＳと略記する。）は、下記一般式（式１）で示されるアリーレンスルフィドの繰返し単位を通常５０モル％、好ましくは７０モル％更に好ましくは９０モル％以上を含む重合体とし、さらに酸素の存在下でポリアリーレンスルフィドの融点以下の温度で熱処理し酸化架橋を促進してポリマー分子量、粘度を適度に高めたものである。
Hereinafter, the present invention will be described in detail.
The basic resin composition that is the resin component of the polyphenylene sulfide resin composition of the present invention comprises the following (a) cross-linked polyphenylene sulfide resin of component (b), polyphenylene ether resin of component (b) and (c) admixture. Composed.
The cross-linked polyphenylene sulfide resin (hereinafter abbreviated as PPS) used in the present invention is usually 50 mol%, preferably 70 mol, of an arylene sulfide repeating unit represented by the following general formula (formula 1). %, More preferably a polymer containing 90 mol% or more, and further heat treatment at a temperature not higher than the melting point of polyarylene sulfide in the presence of oxygen to promote oxidative cross-linking, thereby appropriately increasing the polymer molecular weight and viscosity.
［−Ａｒ−Ｓ−］ （式１）
（ここで、Ａｒはアリーレン基を示し、アリーレン基として、例えばｐ−フェニレン基、ｍ−フェニレン基、置換フェニレン基（置換基としては炭素数１〜１０のアルキル基、フェニル基が好ましい。）、ｐ，ｐ′−ジフェニレンスルホン基、ｐ，ｐ′−ビフェニレン基、ｐ，ｐ′−ジフェニレンカルボニル基、ナフチレン基等が挙げられる。）
なお、ＰＰＳは構成単位であるアリーレン基が１種であるホモポリマーであっても良く、加工性や耐熱性の観点から、２種以上の異なるアリーレン基を混合して用いて得られるコポリマーであっても良い。中でも、主構成要素としてｐ−フェニレンスルフィドの繰り返し単位を有するポリフェニレンスルフィド樹脂が、加工性、耐熱性に優れ、かつ、工業的に入手が容易なことから好ましい。
[—Ar—S—] (Formula 1)
(Here, Ar represents an arylene group, and as the arylene group, for example, a p-phenylene group, an m-phenylene group, and a substituted phenylene group (the alkyl group having 1 to 10 carbon atoms and the phenyl group are preferable as the substituent), and p, p′-diphenylenesulfone group, p, p′-biphenylene group, p, p′-diphenylenecarbonyl group, naphthylene group, etc.).
PPS may be a homopolymer having one type of arylene group as a structural unit, and is a copolymer obtained by mixing two or more different arylene groups from the viewpoint of processability and heat resistance. May be. Among these, a polyphenylene sulfide resin having a repeating unit of p-phenylene sulfide as a main constituent element is preferable because it is excellent in processability and heat resistance and is easily available industrially.
本発明においては、３００℃における溶融粘度が１〜１００００ポイズのものが好適に使用できる。本発明において、溶融粘度とは、ＪＩＳＫ−７２１０を参考試験法とし、フローテスター（（株）島津製作所製ＣＦＴ−５００型）を用いて、ＰＰＳを３００℃、６分間予熱した後、荷重１９６Ｎ、ダイ長さ（Ｌ）／ダイ径（Ｄ）＝１０ｍｍ／１ｍｍで測定した値である。
これら構造を有する架橋型ＰＰＳの中で最も好ましい架橋型ＰＰＳは、塩化メチレンによるオリゴマー抽出量が１重量％以下であり、且つ、３２０℃溶融状態で捕集される揮発分が１０００ｐｐｍ以下の架橋型ポリフェニレンスルフィド樹脂である。
In the present invention, those having a melt viscosity of 1 to 10,000 poise at 300 ° C. can be suitably used. In the present invention, the melt viscosity is JISK-7210 as a reference test method, and after preheating PPS at 300 ° C. for 6 minutes using a flow tester (CFT-500 manufactured by Shimadzu Corporation), a load of 196 N, Die length (L) / die diameter (D) = 10 mm / 1 mm.
The most preferred cross-linked PPS among the cross-linked PPSs having these structures is a cross-linked type in which the amount of oligomer extracted with methylene chloride is 1% by weight or less and the volatile content collected in a molten state at 320 ° C. is 1000 ppm or less. Polyphenylene sulfide resin.
ここで、塩化メチレンによるオリゴマー抽出量の測定は以下の方法により求めることができる。すなわち、ＰＰＳ粉末５ｇを塩化メチレン８０ｍｌに加え、６時間ソクスレー抽出を実施した後、室温まで冷却し、抽出後の塩化メチレン溶液を秤量瓶に移す。更に、上記の抽出に使用した容器を塩化メチレン合計６０ｍｌを用いて、３回に分けて洗浄し、該洗浄液を上記秤量瓶中に回収する。次に、約８０℃に加熱して、該秤量瓶中の塩化メチレンを蒸発させて除去し、残渣を秤量し、この残渣量より塩化メチレンによる抽出量、すなわちＰＰＳ中に存在するオリゴマー量の割合を求めることができる。 Here, the measurement of the amount of oligomer extracted with methylene chloride can be determined by the following method. That is, 5 g of PPS powder is added to 80 ml of methylene chloride, subjected to Soxhlet extraction for 6 hours, cooled to room temperature, and the extracted methylene chloride solution is transferred to a weighing bottle. Further, the container used for the above extraction is washed in three portions with a total of 60 ml of methylene chloride, and the washing liquid is collected in the weighing bottle. Next, the methylene chloride in the weighing bottle is evaporated and removed by heating to about 80 ° C., the residue is weighed, and the amount extracted from the methylene chloride from the amount of the residue, that is, the proportion of the oligomer present in the PPS. Can be requested.
そしてここで言う３２０℃溶融状態で捕集される揮発分の定量は以下の方法により求めることができる。すなわち、架橋型ＰＰＳ粉末を０．５ｇを気流入り口と出口を有する密栓付き試験管に秤量し、３２０℃に加熱したハンダ浴に３０分間浸漬しながら、試験管の気流入り口より窒素ガスを１００ｃｃ／ｍｉｎの流速で注入し、試験管内に発生した架橋ＰＰＳに由来する揮発分を含むガスを試験管の気流出口よりパージし、パージされたガスはアセトンを入れた気流入り口と出口を有する密栓付き試験管の気流入り口より試験管内のアセトン中でバブリングさせ、揮発成分をアセトン中に溶解させる。アセトン中に溶解した架橋ＰＰＳの揮発分は、ガスクロマトグラフ質量分析器（ＧＣ−ＭＳ）を用いて、５０℃〜２９０℃の昇温分析して検出される全成分をモノクロロベンゼンと同一感度と仮定して定量し、架橋ＰＰＳ中の揮発分を知ることができる。 And the fixed_quantity | quantitative_assay of the volatile matter collected here by 320 degreeC molten state can be calculated | required with the following method. That is, 0.5 g of cross-linked PPS powder was weighed in a sealed tube with an air flow inlet and outlet and immersed in a solder bath heated to 320 ° C. for 30 minutes, while nitrogen gas was introduced at 100 cc / kg from the air flow inlet of the test tube. A gas containing volatile components derived from cross-linked PPS generated in the test tube is purged from the air flow outlet of the test tube, and the purged gas is a test with a sealed plug having an air flow inlet and outlet containing acetone. Bubbling is carried out in acetone in the test tube from the air flow inlet of the tube, and the volatile components are dissolved in acetone. The volatile content of crosslinked PPS dissolved in acetone is assumed to have the same sensitivity as that of monochlorobenzene for all components detected by temperature analysis at 50 ° C. to 290 ° C. using a gas chromatograph mass spectrometer (GC-MS). Thus, the amount of volatile components in the crosslinked PPS can be known.
上記したＰＰＳの製造方法は、通常、ハロゲン置換芳香族化合物、例えば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硫化水素ナトリウムと水酸化ナトリウムまたは硫化水素と水酸化ナトリウムあるいはナトリウムアミノアルカノエートの存在下で重合させる方法、ｐ−クロルチオフェノールの自己縮合等が挙げられるが、中でもＮ−メチルピロリドン、ジメチルアセトアミド等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。これらの製造方法は公知の方法であり、例えば、米国特許第２５１３１８８号明細書、特公昭４４−２７６７１号公報、特公昭４５−３３６８号公報、特公昭５２−１２２４０号公報、特開昭６１−２２５２１７号および米国特許第３２７４１６５号明細書、英国特許第１１６０６６０号さらに特公昭４６−２７２５５号公報、ベルギー特許第２９４３７号明細書、特開平５−２２２１９６号公報、等に記載された方法やこれら特許等に例示された先行技術の方法で上記ＰＰＳを得ることが出来る。 The above PPS production method is usually a method in which a halogen-substituted aromatic compound such as p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrogen sulfide and sodium hydroxide in a polar solvent, or Examples include polymerization in the presence of hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate, and self-condensation of p-chlorothiophenol. Among them, amide solvents such as N-methylpyrrolidone and dimethylacetamide, sulfolane, etc. A method in which sodium sulfide and p-dichlorobenzene are reacted in a sulfone solvent is suitable. These production methods are known methods, for example, US Pat. No. 2,513,188, Japanese Examined Patent Publication No. 44-27671, Japanese Examined Patent Publication No. 45-3368, Japanese Examined Patent Publication No. 52-12240, Japanese Unexamined Patent Publication No. Sho 61-61. No. 225217 and US Pat. No. 3,274,165, British Patent No. 1160660, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, Japanese Patent Laid-Open No. 5-222196, etc. The above-mentioned PPS can be obtained by the prior art method exemplified in the above.
ここで、本発明で供する（ａ）成分の塩化メチレンによる抽出量が１重量％以下、３２０℃溶融状態で捕集される揮発分が１０００ｐｐｍ以下の架橋型ポリフェニレンスルフィド樹脂は、その前駆体であるリニア型ＰＰＳの重合段階、洗浄工程で不要な塩化メチレンによる抽出量および揮発分を減らす工夫が必要であり、例えば特開平８−２５３５８７号公報に記載されている、有機アミド系溶媒中でアルカリ金属硫化物とジハロ芳香族化合物とを反応させてリニア型ＰＰＳを得る際に、反応中、反応缶の気相部分を冷却することにより反応缶内の気相の一部を凝縮させ、これを反応溶液上部の液層に還流させることによりオリゴマー成分を減少させる方法により不要な塩化メチレンによる抽出量を減らしたり、重合後のリニア型ＰＰＳの有機アミド系溶媒（例えば、Ｎ−メチルピロリドン）による洗浄回数を増やすことにより不要な塩化メチレンによる抽出量やを減らすことができる。また、揮発分の減少化は、上記の有機アミド系溶媒による洗浄処理の他に、水洗浄処理、酸洗浄処理の回数を増やすことにより減少させることが出来るほかに、リニア型ＰＰＳを架橋型ＰＰＳとするため酸素含有ガス存在下でリニア型ＰＰＳを熱処理し酸化架橋を促進する工程でも加熱温度、時間を調整することにより揮発分を減少させることが可能である。 Here, the cross-linked polyphenylene sulfide resin having an extraction amount of methylene chloride of the component (a) provided in the present invention of 1% by weight or less and a volatile content collected in a molten state at 320 ° C. of 1000 ppm or less is a precursor thereof. It is necessary to devise a method for reducing the amount of extraction with methylene chloride and volatile matter unnecessary in the polymerization step and washing step of the linear PPS. For example, an alkali metal in an organic amide solvent described in JP-A-8-253588 When a linear PPS is obtained by reacting a sulfide with a dihaloaromatic compound, a part of the gas phase in the reaction vessel is condensed by cooling the gas phase portion of the reaction vessel during the reaction, and this is reacted. The amount of extraction with unnecessary methylene chloride is reduced by the method of reducing the oligomer component by refluxing to the liquid layer above the solution, or the presence of the linear PPS after polymerization. Amide solvents (e.g., N- methylpyrrolidone) can reduce the amount of extracted or due to unnecessary methylene chloride by increasing the number of washes by. The reduction of volatile matter can be reduced by increasing the number of water washing treatments and acid washing treatments in addition to the washing treatment using the organic amide solvent as described above. In addition, linear PPS can be cross-linked PPS. Therefore, even in the process of heat-treating linear PPS in the presence of an oxygen-containing gas to promote oxidative crosslinking, it is possible to reduce the volatile content by adjusting the heating temperature and time.
これらの方法以外にも、塩化メチレンによる抽出量が１重量％以上であったり、３２０℃溶融状態で捕集される揮発分が１０００ｐｐｍ以上有する架橋型ＰＰＳは積極的に塩化メチレンにて洗浄し、不要な塩化メチレンによる抽出量や揮発分を減らし、本発明の（ａ）成分である架橋型ポリフェニレンスルフィド樹脂として使用することができる。
このように、本願発明で供する（ａ）成分の架橋型ポリフェニレンスルフィド樹脂は、塩化メチレンによる抽出量が１重量％以下、３２０℃溶融状態で捕集される揮発分が１０００ｐｐｍ以下であれば、得られた樹脂組成物を成型品として長期間成型した際にウエルド部分の白化現象を大幅に改良し、成型品の外観が優れ、さらに困難であったポリフェニレンスルフィドとポリフェニレンエーテルからなる樹脂組成物の難燃性を大幅に改良することができる。
In addition to these methods, the cross-linked PPS having an extraction amount with methylene chloride of 1 wt% or more, or having a volatile content of 1000 ppm or more collected in a molten state at 320 ° C. is actively washed with methylene chloride, It can be used as a cross-linked polyphenylene sulfide resin, which is the component (a) of the present invention, by reducing the amount of volatile matter extracted by unnecessary methylene chloride.
Thus, the crosslinked polyphenylene sulfide resin of component (a) provided in the present invention can be obtained if the extraction amount with methylene chloride is 1% by weight or less and the volatile matter collected in a molten state at 320 ° C. is 1000 ppm or less. When the molded resin composition is molded as a molded product for a long period of time, the whitening phenomenon of the weld portion is greatly improved, the appearance of the molded product is excellent, and the difficulty of the resin composition comprising polyphenylene sulfide and polyphenylene ether, which has been difficult, has been difficult. The flammability can be greatly improved.
そして、上記したように本願発明で供する（ａ）成分の架橋型ポリフェニレンスルフィド樹脂は、塩化メチレンによる抽出量が１重量％以下、３２０℃溶融状態で捕集される揮発分が１０００ｐｐｍ以下であれば、いかなる製法で得られても構わない。
つぎに本発明の（ｂ）成分のポリフェニレンエーテル系樹脂は、下記の結合単位（式２）で示される繰返し単位からなり、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）を用いて測定したポリスチレン換算した数平均分子量が１０００以上、好ましくは１５００〜５００００、より好ましくは１５００〜３００００の範囲にあるホモ重合体及び／または共重合体であるポリフェニレンエーテル樹脂（以下、ＰＰＥと略記する。）
As described above, the cross-linked polyphenylene sulfide resin of the component (a) provided in the present invention has an extraction amount by methylene chloride of 1% by weight or less and a volatile content collected in a molten state at 320 ° C. of 1000 ppm or less. Any production method may be used.
Next, the polyphenylene ether resin of the component (b) of the present invention comprises a repeating unit represented by the following bond unit (Formula 2), and is a number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography). Is a polyphenylene ether resin (hereinafter abbreviated as PPE) which is a homopolymer and / or copolymer in the range of 1000 or more, preferably 1500 to 50000, more preferably 1500 to 30000.
（ここで、Ｒ１，Ｒ２，Ｒ３及びＲ４はそれぞれ、水素、ハロゲン、炭素数１〜７までの第一級または第二級低級アルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基または少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群から選択されるものであり、互いに同一であっても異なっていてもよい。）である。 (Where R 1 , R 2 , R 3 and R 4 are each hydrogen, halogen, primary or secondary lower alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group, aminoalkyl group, It is selected from the group consisting of a hydrocarbonoxy group or a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom, and may be the same or different. ).
このＰＰＥの具体的な例としては、例えばポリ（２，６−ジメチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−エチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−フェニル−１，４−フェニレンエーテル）、ポリ（２，６−ジクロロ−１，４−フェニレンエーテル）等が挙げられ、さらに２，６−ジメチルフェノールと他のフェノール類（例えば、２，３，６−トリメチルフェノールや２−メチル−６−ブチルフェノール）との共重合体のごときポリフェニレンエーテル共重合体も挙げられる。中でもポリ（２，６−ジメチル−１，４−フェニレンエーテル）、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体が好ましく、さらにポリ（２，６−ジメチル−１，４−フェニレンエーテル）が好ましい。 Specific examples of the PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl ether). -6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,6- Polyphenylene ether copolymers such as copolymers with 3,6-trimethylphenol and 2-methyl-6-butylphenol) may also be mentioned. Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1 , 4-phenylene ether).
かかるＰＰＥの製造方法は公知の方法で得られるものであれば特に限定されるものではなく、例えば、米国特許第３３０６８７４号記載のＨａｙによる第一銅塩とアミンのコンプレックスを触媒として用い、例えば２，６−キシレノールを酸化重合することにより容易に製造でき、そのほかにも米国特許第３３０６８７５号、同第３２５７３５７号および同第３２５７３５８号、特公昭５２−１７８８０号および特開昭５０−５１１９７号および同６３−１５２６２８号等に記載された方法で容易に製造できる。 The method for producing such PPE is not particularly limited as long as it can be obtained by a known method. For example, a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 is used as a catalyst, for example, 2 , 6-xylenol can be easily produced by oxidative polymerization. In addition, U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, JP-B-52-17880, and JP-A-50-51197 and It can be easily produced by the method described in 63-152628.
本発明で供する（ｂ）成分のポリフェニレンエーテル系樹脂は、上記したＰＰＥ成分１００重量％でも利用可能であるが、本発明では、ポリフェニレンエーテル（ＰＰＥ）／スチレン系樹脂＝１〜９９重量％／９９〜１重量％の割合で構成されたものが好ましく用いることができ、中でも、本発明の樹脂組成物において、後述する（ｄ）成分の無機系充填剤を併用する総量が全組成物中５０重量％を超える場合、樹脂組成物の加工性を改善する上で、かかるポリフェニレンエーテル（ＰＰＥ）／スチレン系樹脂の比率は、８０／２０〜２０／８０（単位は重量％）の比率で用いることが最も好ましい。かかるスチレン系樹脂とは、スチレン系化合物の単独重合体、２種以上のスチレン系化合物の共重合体およびスチレン系化合物の重合体よりなるマトリックス中にゴム状重合体が粒子状に分散してなるゴム変性スチレン樹脂（ハイインパクトポリスチレン）等があげられる。これら重合体をもたらすスチレン系化合物としては、例えばスチレン、ｏ−メチルスチレン、ｐ−メチルスチレン、ｍ−メチルスチレン、α−メチルスチレン、エチルスチレン、α−メチル−ｐ−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、ｐ−ｔｅｒｔ−ブチルスチレン等が挙げられる。 The polyphenylene ether resin of component (b) provided in the present invention can be used even with the above-mentioned PPE component of 100% by weight, but in the present invention, polyphenylene ether (PPE) / styrene resin = 1 to 99% by weight / 99. Those having a ratio of ˜1% by weight can be preferably used. In particular, in the resin composition of the present invention, the total amount of the inorganic filler as the component (d) described later is 50% by weight in the total composition. In the case of exceeding%, the ratio of such polyphenylene ether (PPE) / styrene resin should be 80/20 to 20/80 (unit is weight%) in order to improve the processability of the resin composition. Most preferred. Such a styrene resin is a rubber polymer dispersed in the form of a homopolymer of a styrene compound, a copolymer of two or more styrene compounds and a polymer of a styrene compound. Examples thereof include rubber-modified styrene resin (high impact polystyrene). Examples of the styrenic compound that gives these polymers include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, 2,4- Examples thereof include dimethyl styrene, monochloro styrene, and p-tert-butyl styrene.
これらスチレン系化合物は２種以上を併用して得られる共重合体でも良いが、中でもスチレンを単独で用いて重合して得られるポリスチレンが好ましい。これらの重合体はアタクチックポリスチレン、シンジオタクチックポリスチレン等の立体規則構造を有するポリスチレンが有効に利用できる。なお、このＰＰＥと併用して用いるスチレン系樹脂には、下記に示す（ｃ）成分の混和剤であるスチレン系共重合体は含まれない。
本発明では、上記した（ａ）成分の架橋型ポリフェニレンスルフィド樹脂と（ｂ）成分のポリフェニレンエーテル系樹脂の配合割合は、（ａ）／（ｂ）＝１〜９９重量部／９９〜１重量部であり、成形加工性および成型時のバリ発生抑制の観点から２０〜９０重量部／８０〜１０重量部が好ましく、さらに好ましくは４０〜８０重量部／６０〜２０重量部である。
These styrenic compounds may be copolymers obtained by using two or more kinds in combination, but among them, polystyrene obtained by polymerization using styrene alone is preferable. As these polymers, polystyrene having a stereoregular structure such as atactic polystyrene and syndiotactic polystyrene can be effectively used. The styrene resin used in combination with the PPE does not include a styrene copolymer that is an admixture of the component (c) shown below.
In the present invention, the blending ratio of the cross-linked polyphenylene sulfide resin as the component (a) and the polyphenylene ether-based resin as the component (b) is (a) / (b) = 1 to 99 parts by weight / 99 to 1 part by weight. From the viewpoint of molding processability and suppression of the occurrence of burrs during molding, 20 to 90 parts by weight / 80 to 10 parts by weight is preferable, and 40 to 80 parts by weight / 60 to 20 parts by weight is more preferable.
つぎに本発明の（ｃ）成分として用いる混和剤は、（ａ）成分の架橋型ＰＰＳと（ｂ）成分のポリフェニレンエーテル系樹脂を混合する際の乳化分散剤として作用し、本発明の樹脂組成物を成型した際に、成型品のバリ発生を顕著に低減化する効果を奏するものである。かかる（ｃ）成分の混和剤としては、（１）エポキシ樹脂、（２）シランカップリング剤、（３）エポキシ基を含有する化合物および／またはオキサゾリル基を含有する化合物が挙げられ、中でも、エポキシ基および／またはオキサゾリル基を有する不飽和モノマーとスチレンを主たる成分とするモノマーとの共重合体が好ましく利用できる。 Next, the admixture used as the component (c) of the present invention acts as an emulsifying dispersant when the cross-linked PPS of the component (a) and the polyphenylene ether resin of the component (b) are mixed, and the resin composition of the present invention. This has the effect of significantly reducing the occurrence of burrs in the molded product when the product is molded. Examples of the admixture of the component (c) include (1) an epoxy resin, (2) a silane coupling agent, (3) a compound containing an epoxy group and / or a compound containing an oxazolyl group. A copolymer of an unsaturated monomer having a group and / or an oxazolyl group and a monomer having styrene as a main component can be preferably used.
ここで言うスチレンを主たる成分とするモノマーとは、スチレン成分が１００重量％は何ら問題ないが、スチレンと共重合可能な他のモノマーが存在する場合は、その共重合体鎖が（ｂ）成分のポリフェニレンエーテル系樹脂との混和性を保持する上で、少なくともスチレンモノマーを６５重量％以上、より好ましくは７５〜９５重量％含むことが必要である。これらの例として具体的には、エポキシ基および／またはオキサゾリル基を有する不飽和モノマーとスチレンモノマーの共重合体。エポキシ基および／またはオキサゾリル基を有する不飽和モノマーとスチレン／アクリロニトリル＝９０〜７５重量％／１０〜２５重量％の共重合体等が挙げられる。 As used herein, the monomer having styrene as the main component has no problem if the styrene component is 100% by weight, but when there is another monomer copolymerizable with styrene, the copolymer chain is component (b). In order to maintain the miscibility with the polyphenylene ether-based resin, it is necessary to contain at least 65% by weight of styrene monomer, more preferably 75 to 95% by weight. Specifically, a copolymer of an unsaturated monomer having an epoxy group and / or an oxazolyl group and a styrene monomer. Examples thereof include an unsaturated monomer having an epoxy group and / or an oxazolyl group and a copolymer of styrene / acrylonitrile = 90 to 75% by weight / 10 to 25% by weight.
上記のエポキシ基含有不飽和モノマーとしては、グリシジルメタアクリレート、グリシジルアクリレート、ビニルグリシジルエーテル、ヒドロキシアルキル（メタ）アクリレートのグリシジルエーテル、ポリアルキレングリコール（メタ）アクリレートのグリシジルエーテル、グリシジルイタコネート等が挙げられ、中でもグリシジルメタアクリレートが好ましい。また、上記のオキサゾリル基含有不飽和モノマーとしては、例えば２−イソプロペニル−２−オキサゾリンが工業的に入手でき好ましく使用できる。 Examples of the epoxy group-containing unsaturated monomer include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, glycidyl itaconate, and the like. Of these, glycidyl methacrylate is preferred. Moreover, as said oxazolyl group containing unsaturated monomer, 2-isopropenyl-2-oxazoline is industrially available and can be used preferably, for example.
これら、エポキシ基および／またはオキサゾリル基を有する不飽和モノマーと共重合する他の不飽和モノマーとしては、必須成分のスチレン等のビニル芳香族化合物の他に、共重合成分としてアクリロニトリル等のシアン化ビニルモノマー、酢酸ビニル、（メタ）アクリル酸エステル等が挙げられるが、本発明ではエポキシ基および／またはオキサゾリル基を有する不飽和モノマーを除外した成分中にスチレンモノマーを少なくとも６５重量％以上含むことが必須である。また、エポキシ基および／またはオキサゾリル基を有する不飽和モノマーは（ｃ）成分の共重合体中に０．３〜２０重量％、好ましくは、１〜１５重量％、更に好ましくは３〜１０重量％含有しなければならない。かかる（ｃ）成分の共重合体のエポキシ基および／またはオキサゾリル基を有する不飽和モノマー量は、得られる樹脂組成物から得られる成型品の機械的物性の点から０．３重量％以上が必要であり、２０重量％以下であれば、（ｂ）成分のポリフェニレンエーテル系樹脂との混和性が保持され、これにより（ａ）成分と（ｂ）成分の混和性が良好となり、得られた樹脂組成物を用いて成型した成型品のバリ発生を大きく抑制することができる。 Other unsaturated monomers copolymerized with unsaturated monomers having an epoxy group and / or an oxazolyl group include vinyl aromatic compounds such as styrene as an essential component and vinyl cyanide such as acrylonitrile as a copolymer component. Monomer, vinyl acetate, (meth) acrylic acid ester, etc. are mentioned, but in the present invention, it is essential that at least 65% by weight or more of styrene monomer is contained in the component excluding unsaturated monomer having epoxy group and / or oxazolyl group. It is. The unsaturated monomer having an epoxy group and / or oxazolyl group is 0.3 to 20% by weight, preferably 1 to 15% by weight, more preferably 3 to 10% by weight in the copolymer of component (c). Must be contained. The amount of the unsaturated monomer having an epoxy group and / or an oxazolyl group of the copolymer of component (c) is required to be 0.3% by weight or more from the viewpoint of mechanical properties of a molded product obtained from the obtained resin composition. When the content is 20% by weight or less, the miscibility of the component (b) with the polyphenylene ether-based resin is maintained, whereby the miscibility of the component (a) and the component (b) is improved. Generation | occurrence | production of the burr | flash of the molded article shape | molded using the composition can be suppressed significantly.
これら共重合可能な不飽和モノマーを共重合して得られる（ｃ）成分の共重合体の例として、例えば、スチレン−グリシジルメタクリレート共重合体、スチレン−グリシジルメタクリレート−メチルメタクリレート共重合体、スチレン−グリシジルメタクリレート−アクリロニトリル共重合体、スチレン−ビニルオキサゾリン共重合体、スチレン−ビニルオキサゾリン−アクリロニトリル共重合体等が挙げられる。
この（ｃ）成分の配合量は、上記した（ａ）成分と（ｂ）成分の合計１００重量部に対して、１〜２０重量部、好ましくは２〜１５重量部、更に好ましくは３〜１０重量部が必要である。かかる（ｃ）成分の配合量が１重量部以上であれば、（ａ）成分と（ｂ）成分の混和性が良くなり、２０重量部以下であれば、得られた樹脂組成物を用いて成型した成型品のバリ発生を大きく抑制することができる。
Examples of the copolymer of component (c) obtained by copolymerizing these copolymerizable unsaturated monomers include, for example, styrene-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate-methyl methacrylate copolymer, styrene- Examples thereof include a glycidyl methacrylate-acrylonitrile copolymer, a styrene-vinyl oxazoline copolymer, and a styrene-vinyl oxazoline-acrylonitrile copolymer.
The compounding amount of the component (c) is 1 to 20 parts by weight, preferably 2 to 15 parts by weight, more preferably 3 to 10 parts by weight based on 100 parts by weight of the total of the components (a) and (b). Part by weight is required. If the blending amount of the component (c) is 1 part by weight or more, the miscibility of the component (a) and the component (b) is improved. If the blending amount is 20 parts by weight or less, the obtained resin composition is used. Generation of burrs in the molded product can be greatly suppressed.
本発明のポリフェニレンスルフィド樹脂組成物は、上記した（ａ）〜（ｃ）の樹脂成分で構成される基礎的樹脂組成物に対して、下記に示す（ｄ）成分の無機系充填剤を配合して得られる樹脂組成物である。以下に本発明で供する（ｄ）成分の無機系充填剤について説明する。
本発明の（ｄ）成分として用いる、無機系充填剤は、本発明の樹脂組成物を用いて成型した成型品の耐熱性を向上させたり、機械的強度を向上させたり、温度変化（−３０℃〜１００℃）による寸法精度を高く維持することができる効果をしたり、更には、成型品へ導電性や熱伝導性等の機能を付加させる効果を奏する。
The polyphenylene sulfide resin composition of the present invention is blended with the inorganic filler of the following component (d) to the basic resin composition composed of the resin components (a) to (c) described above. It is a resin composition obtained. The inorganic filler as the component (d) used in the present invention will be described below.
The inorganic filler used as the component (d) of the present invention improves the heat resistance of the molded product molded using the resin composition of the present invention, improves the mechanical strength, changes the temperature (-30). C. to 100.degree. C.), and the effect of adding functions such as conductivity and thermal conductivity to the molded product.
この（ｄ）成分の無機系充填剤としては、ガラス繊維、炭素繊維、カーボンナノチューブ、アルミナ繊維、炭化珪素繊維、セラミック繊維、石膏繊維、金属繊維、チタン酸カリウムウィスカー、炭酸カルシウム、多孔質炭酸カルシウム、炭酸カルシウムウィスカー、ハイドロタルサイト、カオリン、クレー、ケイ酸カルシウム、カーボンブラック、酸化チタン、ハイドロタルサイト、酸化マグネシウム、酸化アルミニウム、酸化カルシウム、フライアッシュ（石炭灰）、ワラステナイト、ガラスフレーク、マイカ、タルク、グラファイト、窒化アルミニウム、窒化硼素、二硫化モリブデン等が挙げられ、これらは少なくとも１種以上を（ｄ）成分として用いることができ、そしてこれらの無機系充填剤はさらに上記した（ａ）〜（ｃ）成分との親和性を高めるために、シラン系カップリング剤、チタネート系カップリング剤、脂肪族金属塩等の表面処理剤で処理した物や、インターカレーション法によりアンモニウム塩等による有機化処理した物や、ウレタン樹脂、エポキシ樹脂等の樹脂をバインダーとして処理した物でも構わない。 As the inorganic filler of component (d), glass fiber, carbon fiber, carbon nanotube, alumina fiber, silicon carbide fiber, ceramic fiber, gypsum fiber, metal fiber, potassium titanate whisker, calcium carbonate, porous calcium carbonate , Calcium carbonate whisker, hydrotalcite, kaolin, clay, calcium silicate, carbon black, titanium oxide, hydrotalcite, magnesium oxide, aluminum oxide, calcium oxide, fly ash (coal ash), wollastonite, glass flakes, mica , Talc, graphite, aluminum nitride, boron nitride, molybdenum disulfide, etc., and at least one of these can be used as component (d), and these inorganic fillers are further described above in (a). ~ (C) component and In order to increase the affinity, products treated with a surface treatment agent such as a silane coupling agent, titanate coupling agent, aliphatic metal salt, and the like, an organic treatment with an ammonium salt or the like by an intercalation method, The thing which processed resin, such as a urethane resin and an epoxy resin, as a binder may be used.
これらの無機系充填剤の配合量は、（ａ）〜（ｃ）成分からなる基礎的樹脂組成物１００重量部に対して、４０〜４００重量部、より好ましくは、５０〜２５０重量部、更に好ましくは６０〜２００重量部である。かかる配合量が４０重量部以上であれば、得られる樹脂組成物を用いて成型して得られる成型品の耐熱性および寸法精度が改良され、配合量が４００重量部以下において、得られる樹脂組成物を成型して得られる成型品は、ヒケが少なく、温度変化（−３０℃〜１００℃）による優れた寸法精度およびその異方性を保持した成型品となり得る。 These inorganic fillers are blended in an amount of 40 to 400 parts by weight, more preferably 50 to 250 parts by weight, based on 100 parts by weight of the basic resin composition comprising the components (a) to (c). Preferably it is 60-200 weight part. When such a blending amount is 40 parts by weight or more, the heat resistance and dimensional accuracy of a molded product obtained by molding using the resulting resin composition are improved, and when the blending amount is 400 parts by weight or less, the resulting resin composition A molded product obtained by molding an object has few sink marks and can be a molded product that retains excellent dimensional accuracy and anisotropy due to temperature change (-30 ° C to 100 ° C).
本発明では、上記成分の他に、本発明の特徴および効果を損なわない範囲で必要に応じて、他の熱可塑性エラストマー（水添ブロック共重合体やポリオレフィン系エラストマー）、熱安定剤、酸化防止剤、紫外線吸収剤等の安定剤、結晶核剤、帯電防止剤、難燃剤、顔料や染料等の着色剤、ポリエチレンワックス、ポリプロピレンワックス、モンタン酸塩ワックス、ステアリン酸塩ワックス等の公知の離型剤も適宜添加することができる。中でもエチレン−αオレフィン共重合体は優れた離型剤となり得る。 In the present invention, in addition to the above components, other thermoplastic elastomers (hydrogenated block copolymers and polyolefin-based elastomers), thermal stabilizers, antioxidants may be used as long as the characteristics and effects of the present invention are not impaired. Known release agents such as stabilizers, stabilizers such as UV absorbers, crystal nucleating agents, antistatic agents, flame retardants, colorants such as pigments and dyes, polyethylene wax, polypropylene wax, montanate wax, stearate wax Agents can also be added as appropriate. Among these, an ethylene-α olefin copolymer can be an excellent release agent.
本発明のポリフェニレンスルフィド樹脂組成物の製造方法は、上記した各成分を用いて、少なくとも２個のベント口および少なくとも１個のサイド供給口を有する２８０℃以上に設定した二軸押出機を用いて溶融混練する方法である。
より好ましい二軸押出機による本発明のポリフェニレンスルフィド樹脂組成物の具体的な製法態様の一つは、（ａ）成分の架橋型ポリフェニレンスルフィド樹脂と（ｂ）成分のポリフェニレンエーテル系樹脂および（ｃ）成分の混和剤を、二軸押出機の第一供給口に同時に供給し、スクリュー回転数１００〜１２００ｒｐｍ、好ましくは２００〜５００ｒｐｍにて溶融混練し、これら（ａ）〜（ｃ）成分で構成される基礎的樹脂組成物が溶融混練した状態で二軸押出機の第一ベント口を絶対真空圧９５ｋＰａ以下で吸引脱気し、さらに二軸押出機のサイド供給口より（ｄ）成分の無機系充填剤を供給し（ａ）〜（ｄ）成分を溶融混練し、そしてさらに二軸押出機の第二ベント口を絶対真空圧９５ｋＰａ以下で吸引脱気する方法である。ここで、（ｄ）成分の無機系充填剤の二軸押出機への供給方法は、上記した方法以外に、サイド供給口を２個以上に分割して供給することができる。
The method for producing the polyphenylene sulfide resin composition of the present invention uses a twin-screw extruder set to 280 ° C. or more having at least two vent ports and at least one side supply port, using each of the components described above. This is a method of melt kneading.
One of the specific methods for producing the polyphenylene sulfide resin composition of the present invention by a more preferred twin-screw extruder is as follows: (a) a crosslinked polyphenylene sulfide resin as the component, (b) a polyphenylene ether resin as the component, and (c) The component admixtures are simultaneously supplied to the first supply port of the twin screw extruder and melt kneaded at a screw rotation speed of 100 to 1200 rpm, preferably 200 to 500 rpm, and are composed of these components (a) to (c). In a state where the basic resin composition is melt-kneaded, the first vent port of the twin screw extruder is sucked and degassed at an absolute vacuum pressure of 95 kPa or less, and further, the inorganic component (d) is supplied from the side supply port of the twin screw extruder. In this method, the fillers are supplied, the components (a) to (d) are melted and kneaded, and the second vent port of the twin-screw extruder is sucked and deaerated at an absolute vacuum pressure of 95 kPa or less. Here, the method of supplying the inorganic filler of component (d) to the twin-screw extruder can be divided into two or more side supply ports and supplied in addition to the method described above.
このように本願発明のポリフェニレンスルフィド樹脂組成物は、
（イ）使用する（ａ）成分の架橋型ポリフェニレンスルフィドが塩化メチレンによるオリゴマー抽出量を１重量％以下、且つ、３２０℃溶融状態で捕集される揮発分を１０００ｐｐｍ以下とする。
（ロ）さらに二軸押出機による溶融混練中に少なくとも２箇所のベント口を絶対真空圧９５ｋＰａ以下で吸引脱気する。
を満足することにより、長期間成型した際のウエルド部分の白化現象を大幅に改良し、成型品の外観が優れるほかに、ポリフェニレンスルフィドとポリフェニレンエーテルおよび無機系充填剤で構成されるポリフェニレンスルフィド樹脂組成物に優れた難燃性を与える。
Thus, the polyphenylene sulfide resin composition of the present invention is
(A) The cross-linked polyphenylene sulfide as the component (a) to be used has an oligomer extraction amount of 1% by weight or less with methylene chloride, and a volatile content collected in a molten state at 320 ° C. is 1000 ppm or less.
(B) Further, at least two vent ports are sucked and deaerated at an absolute vacuum pressure of 95 kPa or less during melt-kneading by a twin-screw extruder.
In addition to greatly improving the whitening phenomenon of the weld part when molded for a long time, the appearance of the molded product is excellent, and the composition of polyphenylene sulfide resin composed of polyphenylene sulfide, polyphenylene ether and inorganic filler Gives excellent flame retardancy to objects.
このようにして得られる本発明のポリフェニレンスルフィド樹脂組成物は成形材料として、例えば、射出成形、金属インモールド成形、アウトサート成形、中空成形、押出成形、シート成形、熱プレス成形、回転成形、積層成形等の成形方法が適用できる。そして、光学機器機構部品、映像機器内部部品、光ファイバ用コネクタフェルール、プリンター部品、コピー機部品、自動車ランプ部品、自動車エンジンルーム内部品等のウエルド部を有する成型品として利用できるものである。 The polyphenylene sulfide resin composition of the present invention thus obtained is used as a molding material, for example, injection molding, metal in-mold molding, outsert molding, hollow molding, extrusion molding, sheet molding, hot press molding, rotational molding, lamination. A molding method such as molding can be applied. And it can be used as a molded product having a weld part such as an optical device mechanism component, an image device internal component, an optical fiber connector ferrule, a printer component, a copier component, an automobile lamp component, an automotive engine compartment component, and the like.
以下、実施例によって、本発明を説明する。
なお、使用した原料は下記の通りである。
（ａ）成分の架橋型ポリフェニレンスルフィド樹脂
ａ−１：溶融粘度（フローテスターを用いて、３００℃、荷重１９６Ｎ、Ｌ／Ｄ＝１０／１で６分間保持した後測定した値。）が５００ポイズ、塩化メチレンによる抽出量が０．７重量％、３２０℃溶融状態で捕集される揮発分が１６０ｐｐｍの架橋型ＰＰＳをａ−１とした。
ａ−２：溶融粘度が５００ポイズ、塩化メチレンによる抽出量が０．４重量％、３２０℃溶融状態で捕集される揮発分が３００ｐｐｍの架橋型ＰＰＳをａ−２とした。
ａ−３：溶融粘度が５００ポイズ、塩化メチレンによる抽出量が０．８重量％、３２０℃溶融状態で捕集される揮発分が７９０ｐｐｍの架橋型ＰＰＳをａ−３とした。
ａ−４：溶融粘度が５００ポイズ、塩化メチレンによる抽出量が２．１重量％、３２０℃溶融状態で捕集される揮発分が１８００ｐｐｍの架橋型ＰＰＳをソックスレイ抽出器を用いて塩化メチレンで６時間抽出し、抽出後の架橋型ＰＰＳを乾燥して得た。ここで得た架橋型ＰＰＳの塩化メチレンによる抽出量は０．０４重量％、３２０℃溶融状態で捕集される揮発分が４８ｐｐｍであった。この塩化メチレン抽出して得た架橋型ＰＰＳをａ−４とした。
ａ−５：溶融粘度が５００ポイズ、塩化メチレンによる抽出量が２．１重量％、３２０℃溶融状態で捕集される揮発分が１８００ｐｐｍの架橋型ＰＰＳをａ−５とした。
ａ−６：溶融粘度が５００ポイズ、塩化メチレンによる抽出量が１．２重量％、３２０℃溶融状態で捕集される揮発分が１２００ｐｐｍの架橋型ＰＰＳをａ−６とした。
Hereinafter, the present invention will be described by way of examples.
In addition, the used raw material is as follows.
Component (a) Crosslinked Polyphenylene Sulfide Resin a-1: Melt Viscosity (value measured after holding for 6 minutes at 300 ° C., load 196 N, L / D = 10/1 using a flow tester) is 500 poise Further, a cross-linked PPS having an extraction amount of 0.7% by weight with methylene chloride and 160 ppm of a volatile component collected in a molten state at 320 ° C. was defined as a-1.
a-2: Cross-linked PPS having a melt viscosity of 500 poise, an extraction amount by methylene chloride of 0.4% by weight, and a volatile content of 300 ppm collected in a molten state at 320 ° C. was defined as a-2.
a-3: A crosslinked PPS having a melt viscosity of 500 poise, an extraction amount by methylene chloride of 0.8% by weight, and a volatile content of 790 ppm collected in a molten state at 320 ° C. was defined as a-3.
a-4: Crosslinked PPS having a melt viscosity of 500 poise, an extraction amount by methylene chloride of 2.1% by weight, and a volatile content of 1800 ppm collected in a molten state at 320 ° C. using methylene chloride using a Soxhlet extractor Extraction was performed for 6 hours, and the crosslinked PPS after extraction was obtained by drying. The amount of the cross-linked PPS obtained here extracted with methylene chloride was 0.04% by weight, and the volatile matter collected in the molten state at 320 ° C. was 48 ppm. This cross-linked PPS obtained by extraction with methylene chloride was designated as a-4.
a-5: A cross-linked PPS having a melt viscosity of 500 poise, an extraction amount by methylene chloride of 2.1% by weight, and a volatile content of 1800 ppm collected in a molten state at 320 ° C. was defined as a-5.
a-6: A cross-linked PPS having a melt viscosity of 500 poise, an extraction amount with methylene chloride of 1.2% by weight, and a volatile content collected in a molten state at 320 ° C. of 1200 ppm was defined as a-6.
（ｂ）成分のポリフェニレンエーテル系樹脂
ｂ−１：２，６−キシレノールを酸化重合して得た、還元粘度が０．５４のポリフェニレンエーテルをｂ−１とした。
ｂ−２：ポリフェニレンエーテル系樹脂としてポリフェニレンエーテル／スチレン系樹脂の混合物とするため、用いたスチレン系樹脂のアタクチックポリスチレン（ＰＳジャパン社製 ポリスチレン６８５）をｂ−２とした。
(B) Component Polyphenylene Ether Resin b-1: Polyphenylene ether having a reduced viscosity of 0.54 obtained by oxidative polymerization of 2,6-xylenol was defined as b-1.
b-2: In order to make a polyphenylene ether / styrene resin mixture as the polyphenylene ether resin, atactic polystyrene (polystyrene 685 manufactured by PS Japan Co.) of the styrene resin used was defined as b-2.
（ｃ）成分の混和剤
ｃ−１：グリシジルメタクリレートを５重量％含有するスチレン−グリシジルメタクリレート共重合体（重量平均分子量１１０，０００）をｃ−１とした。
ｃ−２：２−イソプロペニル−２−オキサゾリンを５重量％含有するスチレン−２−イソプロペニル−２−オキサゾリン共重合体（重量平均分子量１４６，０００）をｃ−２とした。
Component (c) Admixture c-1: A styrene-glycidyl methacrylate copolymer (weight average molecular weight 110,000) containing 5% by weight of glycidyl methacrylate was defined as c-1.
c-2: A styrene-2-isopropenyl-2-oxazoline copolymer (weight average molecular weight 146,000) containing 5% by weight of 2-isopropenyl-2-oxazoline was defined as c-2.
（ｄ）成分の無機系充填剤
ｄ−１：平均直径１３μｍ、長さ３ｍｍ、アミノシラン系カップリング剤で表面処理し、さらにバインダーとしてエポキシ樹脂で処理した、ガラス繊維を（ｄ−１）とした。
ｄ−２：平均板径６００μｍ、アミノシラン系カップリング剤で表面処理し、さらにバインダーとしてエポキシ樹脂で処理した、ガラスフレークを（ｄ−２）とした。
ｄ−３：平均板系９０μｍ、平均板厚２μｍ、アミノシラン系カップリング剤で表面処理したマイカを（ｄ−３）とした。
ｄ−４：ＪＩＳ Ａ６２０１−１９９９の品質規格がフライアッシュＩＩ種であるフライアッシュ（（株）テクノ中部製 中部フライアッシュ）をｄ−４とした。
ｄ−５：平均粒子径７μｍである炭酸カルシウム１００重量部に対し、シランカップリング剤［β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン］１．５重量部を添加し、ブレンダーを用いてブレンドして得られた炭酸カルシウムをｄ−５とした
。
(D) Inorganic filler of component d-1: Glass fiber treated with an epoxy resin as a binder, which was surface treated with an average diameter of 13 μm, a length of 3 mm, and an aminosilane coupling agent, was defined as (d-1). .
d-2: Glass flakes having an average plate diameter of 600 μm, surface-treated with an aminosilane coupling agent, and further treated with an epoxy resin as a binder were defined as (d-2).
d-3: Mica whose surface was treated with an average plate system of 90 μm, an average plate thickness of 2 μm, and an aminosilane coupling agent was defined as (d-3).
d-4: Fly ash (medium part fly ash manufactured by Techno Chubu Co., Ltd.) whose quality standard of JIS A6201-1999 is fly ash type II was defined as d-4.
d-5: To 100 parts by weight of calcium carbonate having an average particle diameter of 7 μm, 1.5 parts by weight of a silane coupling agent [β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane] is added, and a blender is used. The calcium carbonate obtained by blending was d-5.
（ｅ）その他の添加剤
ｅ−１：着色剤として、カーボンブラック（三菱化学製：ＭＣＦ−８８）を用いた。
なお、上記成分より得られたポリフェニレンスルフィド樹脂組成物を用い、特にガス抜け部を設けていないウエルド金型（縦３８ｍｍ、横７９ｍｍ、厚み５ｍｍの板状で横中央にウェルド部を有し、そのウェルド部より左右８ｍｍの位置にゲート部を有する）を用いて３１０℃に設定したスクリューインライン型射出成形機に樹脂組成物を供給し、金型温度１３０℃の条件で連続成形を行い、成型品のウエルド部分が白化するまでの成形ショット数を求めた。成形ショット数が多いものほどウエルド白化が少ない材料である。また難燃性試験に関しては、ＵＬ９４に準拠し、厚み１．６ｍｍの燃焼用試験片を作成し燃焼試験を実施した。
(E) Other additives e-1: Carbon black (manufactured by Mitsubishi Chemical Corporation: MCF-88) was used as a colorant.
In addition, using the polyphenylene sulfide resin composition obtained from the above components, a weld mold (38 mm long, 79 mm wide, 5 mm thick with a weld portion in the horizontal center, in particular, without a gas escape portion, The resin composition is supplied to a screw in-line injection molding machine set at 310 ° C. using a gate part at a position 8 mm to the left and right of the weld part), and is continuously molded at a mold temperature of 130 ° C. The number of molding shots until the weld part was whitened was determined. A material having a larger number of molding shots has less weld whitening. Regarding the flame retardancy test, a combustion test piece having a thickness of 1.6 mm was prepared and a combustion test was performed in accordance with UL94.
［実施例１〜１０、比較例１〜１０］
（ａ）成分の架橋型ポリフェニレンスルフィド樹脂、（ｂ）成分のポリフェニレンエーテル系樹脂、（ｃ）成分の混和剤、（ｄ）成分の充填剤を表１および表２に示した組成で各成分を配合し、３１０℃に設定しスクリュー回転数３００ｒｐｍの条件下でベントポートおよびサイドフィード付き二軸押出機（ＺＳＫ−４０；ＣＯＰＥＲＩＯＮ ＷＥＲＮＥＲ＆ＰＦＬＥＩＤＥＲＥＲ社製、ドイツ国）を用いて、第一供給口より（ａ）〜（ｃ）成分の全量を供給しながら溶融混練し、第一ベント口にて真空度を変化させて脱気操作を行い、さらに該二軸押出機の第一ベント口の下流側に位置する第一のサイド供給口および第二のサイド供給口より（ｄ）成分の無機系充填剤を供給し溶融混練し、そしてさらに該二軸押出機の出口手前に位置する第二ベント口にて真空度を変化させて脱気操作を行い樹脂組成物をペレットとして得た。このペレットを用いて３１０℃に設定したスクリューインライン型射出成形機に供給し、ウエルド金型にて金型温度１３０℃の条件で連続成形を行い、成型品のウエルド部分が白化するまでの成形ショット数を求めた。なお、成形白化が起こらない材料は５０００ショットまで成形した。またＵＬ９４に準拠して厚み１．６ｍｍの試験片を燃焼させ燃焼レベルを測定した。これらの結果を併せて表１〜２に記載した。
[Examples 1 to 10, Comparative Examples 1 to 10]
(A) Crosslinkable polyphenylene sulfide resin of component, (b) component polyphenylene ether resin, (c) component admixture, (d) component filler with the compositions shown in Tables 1 and 2 Using a twin screw extruder with a vent port and side feed (ZSK-40; manufactured by COPERION WERNER & PFLIDELER, Germany) under the condition of 310 ° C. and screw rotation speed of 300 rpm, (a ) To (c) melting and kneading while supplying the total amount of components, changing the degree of vacuum at the first vent port, performing degassing operation, and further downstream of the first vent port of the twin screw extruder The inorganic filler of component (d) is supplied from the first side supply port and the second side supply port to be melt kneaded, and further, the first side supply port located before the outlet of the twin screw extruder. A degassing operation was performed by changing the degree of vacuum at the two vent port to obtain a resin composition as pellets. Using this pellet, it is supplied to a screw in-line injection molding machine set at 310 ° C, and is continuously molded in a weld mold at a mold temperature of 130 ° C until the weld part of the molded product is whitened. I asked for a number. In addition, the material in which molding whitening does not occur was molded up to 5000 shots. Also, a test piece having a thickness of 1.6 mm was burned in accordance with UL94, and the combustion level was measured. These results are shown in Tables 1-2.
本発明のポリフェニレンスルフィド樹脂組成物で成型される成形品は、長期間成型した際のウエルド部分の白化現象を大幅に改良し、成型品の外観が優れるほかに難燃性に優れるため、コンパクト・ディスク・リードオンリーメモリ（ＣＤＲＯＭ）、デジタル・バーサタイル・ディスク・リードオンリーメモリ（ＤＶＤＲＯＭ）、コンパクト・ディスク・レコーダブル（ＣＤＲ）、デジタル・バーサタイル・ディスク・レコーダブル・−Ｒ規格（ＤＶＤ−Ｒ）、デジタル・バーサタイル・ディスク・レコーダブル・＋Ｒ規格（ＤＶＤ＋Ｒ）、コンパクト・ディスク・リライタブル（ＣＤＲＷ）、デジタル・バーサタイル・ディスク・リライタブル・−Ｒ規格（ＤＶＤ−ＲＷ）、デジタル・バーサタイル・ディスク・リライタブル・＋Ｒ規格（ＤＶＤ＋ＲＷ）、デジタル・バーサタイル・ディスク・ランダムアクセスメモリ（ＤＶＤＲＡＭ）等のシャーシーやキャビネット、光ピックアップスライドベース等の光学機器機構部品、映像機器内部部品、光ファイバ用コネクタフェルール、レーザービームプリンター内部部品、インクジェットプリンター内部部品、液晶プロジェクター内部部品、コピー機内部部品、自動車ランプ部品および自動車エンジンルーム内部部品の少なくとも１つの部品として利用できる。 Molded products molded with the polyphenylene sulfide resin composition of the present invention greatly improve the whitening phenomenon of the weld part when molded for a long period of time, and in addition to the appearance of the molded product and excellent flame retardancy, Disc read only memory (CDROM), digital versatile disc read only memory (DVDROM), compact disc recordable (CDR), digital versatile disc recordable -R standard (DVD-R), Digital versatile disc recordable + R standard (DVD + R), compact disc rewritable (CDRW), digital versatile disc rewritable -R standard (DVD-RW), digital versatile disc rewritable + R standard( VD + RW), chassis, cabinet such as digital versatile disk random access memory (DVDRAM), optical equipment mechanism parts such as optical pickup slide base, video equipment internal parts, optical fiber connector ferrule, laser beam printer internal parts, inkjet It can be used as at least one of a printer internal part, a liquid crystal projector internal part, a copier internal part, an automobile lamp part, and an automobile engine room internal part.
Claims (7)
（但し、溶融粘度はＪＩＳＫ−７２１０に準拠し、フローテスターを用いて、３００℃、荷重１９６Ｎ、ダイ長さ（Ｌ）／ダイ径（Ｄ）＝１０ｍｍ／１ｍｍで６分間保持した後の測定値） 2. The polyphenylene sulfide resin composition according to claim 1, wherein the cross-linked polyphenylene sulfide resin as component (a) has a melt viscosity of 1 to 10,000 poise.
(However, melt viscosity is based on JISK-7210, and measured using a flow tester after holding for 6 minutes at 300 ° C., load 196 N, die length (L) / die diameter (D) = 10 mm / 1 mm) )
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| JP2004083221A JP2005264124A (en) | 2004-03-22 | 2004-03-22 | Polyphenylene sulfide resin composition |
| TW094132657A TWI304430B (en) | 2004-03-22 | 2005-09-21 | Polyphenylene sulfide resin composition |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006067902A1 (en) * | 2004-12-21 | 2006-06-29 | Asahi Kasei Chemicals Corporation | Polyphenylene sulfide resin composition |
| JP2006316245A (en) * | 2004-12-21 | 2006-11-24 | Asahi Kasei Chemicals Corp | Polyphenylene sulfide resin composition |
| JP2007186672A (en) * | 2005-12-16 | 2007-07-26 | Toray Ind Inc | Polyphenylene sulfide resin composition and molding |
| WO2007135749A1 (en) * | 2006-05-24 | 2007-11-29 | Polyplastics Co., Ltd. | Resin composition of high heat conduction |
| CN101851378A (en) * | 2010-03-05 | 2010-10-06 | 上海锦湖日丽塑料有限公司 | Extrusion grade ASA resin with easy processing and high apparent property and preparation method thereof |
| JP2013075997A (en) * | 2011-09-30 | 2013-04-25 | Dic Corp | Polyarylene sulfide resin composition |
| CN103224680A (en) * | 2013-04-17 | 2013-07-31 | 陕西理工学院 | Lightweight decorative acrylic sheet and its preparation method |
| CN103443205A (en) * | 2011-03-31 | 2013-12-11 | 东丽株式会社 | Polyphenylene sulfide resin composition and moldings thereof |
| WO2014136848A1 (en) * | 2013-03-07 | 2014-09-12 | 住友電気工業株式会社 | Optical connector |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006067902A1 (en) * | 2004-12-21 | 2006-06-29 | Asahi Kasei Chemicals Corporation | Polyphenylene sulfide resin composition |
| JP2006316245A (en) * | 2004-12-21 | 2006-11-24 | Asahi Kasei Chemicals Corp | Polyphenylene sulfide resin composition |
| US8044142B2 (en) | 2004-12-21 | 2011-10-25 | Asahi Kasei Chemicals Corporation | Polyphenylene sulfide resin composition |
| JP2007186672A (en) * | 2005-12-16 | 2007-07-26 | Toray Ind Inc | Polyphenylene sulfide resin composition and molding |
| WO2007135749A1 (en) * | 2006-05-24 | 2007-11-29 | Polyplastics Co., Ltd. | Resin composition of high heat conduction |
| CN101851378A (en) * | 2010-03-05 | 2010-10-06 | 上海锦湖日丽塑料有限公司 | Extrusion grade ASA resin with easy processing and high apparent property and preparation method thereof |
| CN101851378B (en) * | 2010-03-05 | 2012-10-03 | 上海锦湖日丽塑料有限公司 | Extrusion grade ASA resin with easy processing and high apparent property and preparation method thereof |
| CN103443205A (en) * | 2011-03-31 | 2013-12-11 | 东丽株式会社 | Polyphenylene sulfide resin composition and moldings thereof |
| JP2013075997A (en) * | 2011-09-30 | 2013-04-25 | Dic Corp | Polyarylene sulfide resin composition |
| WO2014136848A1 (en) * | 2013-03-07 | 2014-09-12 | 住友電気工業株式会社 | Optical connector |
| CN103224680A (en) * | 2013-04-17 | 2013-07-31 | 陕西理工学院 | Lightweight decorative acrylic sheet and its preparation method |
| CN103224680B (en) * | 2013-04-17 | 2015-04-15 | 陕西理工学院 | Lightweight decorative acrylic sheet and its preparation method |
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