JP2004217832A - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- JP2004217832A JP2004217832A JP2003008679A JP2003008679A JP2004217832A JP 2004217832 A JP2004217832 A JP 2004217832A JP 2003008679 A JP2003008679 A JP 2003008679A JP 2003008679 A JP2003008679 A JP 2003008679A JP 2004217832 A JP2004217832 A JP 2004217832A
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- JP
- Japan
- Prior art keywords
- weight
- resin composition
- component
- resin
- 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.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 56
- 239000011256 inorganic filler Substances 0.000 claims abstract description 48
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 47
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 45
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 26
- 230000003287 optical effect Effects 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- -1 vinyl aromatic compound Chemical class 0.000 claims description 37
- 229920001400 block copolymer Polymers 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 22
- 229920002554 vinyl polymer Polymers 0.000 claims description 20
- 238000004898 kneading Methods 0.000 claims description 19
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 239000012765 fibrous filler Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical group 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 24
- 230000001070 adhesive effect Effects 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 18
- 238000000465 moulding Methods 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 14
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 238000006073 displacement reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 238000011144 upstream manufacturing Methods 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
- 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 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-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
- 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 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 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
- 239000002253 acid Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000412 polyarylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000002002 slurry Substances 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
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 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
- OQEBBZSWEGYTPG-UHFFFAOYSA-N 3-aminobutanoic acid Chemical compound CC(N)CC(O)=O OQEBBZSWEGYTPG-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
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- NGNBLQAYJAKWKR-UHFFFAOYSA-N 5-methyl-3-phenyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound O1C=2C(C)=CC1=CC=2C1=CC=CC=C1 NGNBLQAYJAKWKR-UHFFFAOYSA-N 0.000 description 1
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical group C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Chemical class 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
- 244000043261 Hevea brasiliensis Species 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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Abstract
Description
【０００１】
【産業上の利用分野】
本発明は電気・電子分野、自動車分野、その他の各種工業材料分野で利用できる耐油性、耐薬品性、耐熱性、耐衝撃性、剛性に優れた樹脂組成物に関し、さらには、成形加工材料としての成形流動性に優れ、温度による寸法変化および光軸のずれが少なく、かつＵＶ硬化性接着剤の接着性に優れる樹脂組成物に関するものである。
【０００２】
【従来の技術】
従来、非強化のポリフェニレンスルフィドは、その結晶性に起因して流動特性が良好で、耐熱性、耐水性に優れるため電子分野で利用されているが成形材料として、靱性（衝撃強度）に劣る欠点を有するため各種成形品（特に大型成形品）に利用することが困難である。
このためポリフェニレンスルフィドのこれらの欠点を解消するため各種樹脂、各種熱可塑性エラストマー等とブレンドまたはアロイ化する試みが数多く提案されている。
【０００３】
例えば、ポリフェニレンオキサイド類とポリフェニレンスルフィド類から成る成形性、難燃性に優れた樹脂組成物が提案されている。（例えば、特許文献１参照）
また、ポリフェニレンスルフィドや他のエンジニアリング樹脂とα，β−不飽和カルボン酸の誘導体で変性した水添ブロック共重合体からなる、耐衝撃性、耐界面剥離性に優れた変性ブロック共重合体組成物が提案されている。（例えば、特許文献２参照）
さらにポリフェニレンスルフィドや他のエンジニアリング樹脂とα，β−不飽和カルボン酸の誘導体で変性した水添ブロック共重合体およびエポキシ基含有重合体から成る耐衝撃性に優れた熱可塑性グラフト共重合体組成物が提案されている。（例えば、特許文献３参照）
【０００４】
そしてポリアリレーンサルファイドとα−オレフィン／α，β−不飽和酸のグリシジルエステル共重合体からなる耐衝撃性、成形加工性に優れたポリアリレーンサルファイド樹脂組成物が提案されている。（例えば、特許文献４参照）
また、ポリフェニレンスルフィドと不飽和カルボン酸またはその無水物またはその誘導体をグラフト共重合したポリオレフィンおよびエポキシ樹脂からなる耐衝撃性に優れた組成物が提案されている。（例えば、特許文献５参照）
さらに特定のポリフェニレンスルフィドとα−オレフィン／α，β−不飽和酸のグリシジルエステル共重合体からなる耐衝撃性に優れたポリフェニレンスルフィド樹脂組成物が提案されている。（例えば、特許文献６、特許文献７、特許文献８参照）
【０００５】
そしてさらに特定のポリフェニレンスルフィドと不飽和カルボン酸またはその無水物またはその誘導体をグラフト共重合したポリオレフィンからなる耐衝撃性に優れたポリフェニレンスルフィド樹脂組成物が提案されている。（例えば、特許文献９〜１１参照）
同様に、酸変性ポリフェニレンエーテルと変性ポリフェニレンスルフィドの混和性改良にスチレンとオキサゾニル基を有するエチレン性不飽和モノマーとの共重合体を用いる方法が提案されている。（例えば、特許文献１２〜１３参照）
また、ポリフェニレンスルフィドとポリフェニレンエーテルの混和性改良にスチレンとオキサゾニル基を有するエチレン性不飽和モノマーとの共重合体を用いる方法が提案されている。（例えば、特許文献１４参照）
【０００６】
さらに、ポリフェニレンスルフィドとポリフェニレンエーテル樹脂組成物に、無機フィラーを用いて機械的強度、寸法安定性を向上させた樹脂組成物が提案されている。（例えば、特許文献１５〜２８参照）
本出願人も特定の無機フィラーを使用し、機械的強度、寸法安定性を向上させた樹脂組成物を提案している。（例えば、特許文献２９〜３０参照）
しかし、これらに提案されている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フィラーからなる樹脂組成物は機械的物性および寸法安定性の改良はなされているものの、これら樹脂組成物では近年のＣＤ−Ｒ、ＣＤ−ＲＷ、ＤＶＤ−Ｒ、ＤＶＤ−ＲＷ等の光学系機器部品における小型精密化に伴うより高いレベルの温度変化に対する寸法安定性および光軸特性の改良要求やＵＶ硬化性接着剤による接着性の要求を満足するものではなかった。
【０００７】
【特許文献１】
特公昭５６−３４０３２号公報
【特許文献２】
特開昭５８−２７７４０号公報
【特許文献３】
特開昭５８−４０３５０号公報
【特許文献４】
特開昭５８−１５４７５７号公報
【特許文献５】
特開昭５９−２０７９２１号公報
【特許文献６】
特開昭６２−１５３３４３号公報
【特許文献７】
特開昭６２−１５３３４４号公報
【特許文献８】
特開昭６２−１５３３４５号公報
【特許文献９】
特開昭６２−１６９８５４号公報
【特許文献１０】
特開昭６２−１７２０５６号公報
【特許文献１１】
特開昭６２−１７２０５７号公報
【特許文献１２】
特開平０１−２６６１６０号公報
【特許文献１３】
特開平０２−７５６５６号公報
【特許文献１４】
特開平０３−２０３５６号公報
【特許文献１５】
特開平０５−３３９５００号公報
【特許文献１６】
特開平９−１５７５２５号公報
【特許文献１７】
特開平９−２９６１０９号公報
【特許文献１８】
特開平９−２９６１１０号公報
【特許文献１９】
特開平１１−１０６６５２号公報
【特許文献２０】
特開平１１−１０６６５３号公報
【特許文献２１】
特開平１１−１０６６５４号公報
【特許文献２２】
特開平１１−１０６６５５号公報
【特許文献２３】
特開平１１−１５８３７４号公報
【特許文献２４】
特開平１１−１９９７７４号公報
【特許文献２５】
特開２０００−１９８９２４号公報
【特許文献２６】
特開２００２−０６９２９８号公報
【特許文献２７】
特開２００２−１２１３８３号公報
【特許文献２８】
特開２００２−１７９９１５号公報
【特許文献２９】
特開２００２−０１２７６４号公報
【特許文献３０】
特開２００２−２４９６６１号公報
【０００８】
【発明が解決しようとする課題】
本発明は、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フィラーからなる樹脂組成物の優れた機械的物性を損なうことなく、成形流動性に優れ、温度による寸法変化および光軸のずれが少なく、かつＵＶ硬化性接着剤による接着性に優れた樹脂組成物および光ディスクドライブ用樹脂製構造部品を提供することにある。
【０００９】
【課題を解決するための手段】
本発明者らは、このような現状に鑑み、ポリフェニレンスルフィド樹脂とポリフェニレンエーテル樹脂および無機フィラーからなる樹脂組成物において、鋭意検討の結果、無機フィラー添加量の多い組成領域において従来問題であった成形流動性、ＵＶ硬化性接着剤による接着性、機械的物性を改良し、同時に温度による寸法変化および光軸のずれをも少なくできることを見いだし、本発明に到達した。
【００１０】
すなわち、本発明は、
１．（ａ）塩化メチレンによる抽出量が０．７重量％以下であり、かつ−ＳＸ基（Ｓはイオウ原子、Ｘはアルカリ金属または水素原子である）が１５μｍｏｌ／ｇ以上であるポリフェニレンスルフィド樹脂３０〜７０重量％、
（ｂ）ポリフェニレンエーテル樹脂１００重量部に対してポリスチレン樹脂を４５〜１５０重量部含んでなるポリフェニレンエーテル系樹脂７０〜３０重量％であって、
（ａ）成分と（ｂ）成分の合計１００重量部に対し、
（ｃ）エポキシ基およびまたはオキサゾニル基を有する不飽和モノマーを０．３〜２０重量％の割合でスチレンを主たる成分とするモノマーと共重合してなる共重合体１〜２０重量部、
さらに、（ａ）成分と（ｂ）成分の合計１００重量部に対して、
（ｄ）ビニル芳香族化合物を主体とする少なくとも１個の重合体ブロックＡと共役ジエン化合物を主体とする少なくとも１個の重合体ブロックＢとからなるブロック共重合体および／または該ブロック共重合体を水素添加してなる水添ブロック共重合体０〜４０重量部、
さらにまた、（ａ）成分と（ｂ）成分の合計１００重量部に対して、
（ｅ）板状および繊維状である無機フィラーであり、かつ板状／繊維状フィラーの重量比が１以上である無機フィラー１００〜４００重量部を含む樹脂組成物、を提供するものである。
【００１１】
さらには、この樹脂組成物において、
２．（ａ）〜（ｄ）成分の全量を溶融混練し、次いで（ｅ）成分を供給し、さらに溶融混練を続けて行う樹脂組成物の製造方法。
３．（ａ）〜（ｄ）成分の全量および（ｅ）成分の板状無機フィラーの２０〜１００重量％を溶融混練し、次いで（ｅ）成分の繊維状無機フィラーおよび板状無機フィラーの残量を供給し、さらに溶融混練を続けて行う樹脂組成物の製造方法。
４．（ａ）〜（ｄ）成分の全量を溶融混練し、次いで（ｅ）成分の板状無機フィラーを供給し、さらに（ｅ）成分の繊維状無機フィラーを供給し、溶融混練を続けて行う樹脂組成物の製造方法。
を用いて製造された樹脂組成物にて構成された光ディスクドライブ用樹脂製構造部品に関するものである。
【００１２】
本発明の（ａ）成分のポリフェニレンスルフィド樹脂（以下ＰＰＳと略記する）は、基本的にはパラフェニレンスルフィド骨格を７０モル％以上、好ましくは９０モル％以上からなるポリフェニレンスルフィドである。
これら上記した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。なお、これら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号公報および米国特許第３２７４１６５号明細書、英国特許第１１６０６６０号明細書さらに特公昭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得ることが出来る。
【００１３】
さらに本発明の（ａ）成分であるポリフェニレンスルフィド樹脂の塩化メチレンによるオリゴマー抽出量は０．７重量％以下であり、かつ−ＳＸ基（Ｓはイオウ原子、Ｘはアルカリ金属または水素原子である）が１５μｍｏｌ／ｇ以上であるポリフェニレンスルフィドである。
この塩化メチレンによるオリゴマー抽出量と−ＳＸ基（Ｓはイオウ原子、Ｘはアルカリ金属または水素原子である）濃度を共に満たすポリフェニレンスルフィド樹脂を用いることで、本発明の無機フィラーを多量に含む樹脂組成物においては、ポリフェニレンスルフィドとポリフェニレンエーテルとの混和性および樹脂組成物から得られる成形品の引張強度・アイゾット衝撃強度・成形品の表面濡れ性の改善効果によるＵＶ硬化性接着剤の接着強度を改善できる。しかし、上記オリゴマー抽出量と−ＳＸ基濃度の少なくともいずれか一方が範囲外の場合、これらを改善することはできない。
【００１４】
上記オリゴマー抽出量の範囲が上記範囲にあるということは、ＰＰＳ中におけるオリゴマー（約１０〜３０量体）の量が少ないことを意味する。
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行うことができる。すなわち、ＰＰＳ粉末５ｇを塩化メチレン８０ｍｌに加え、４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。
【００１５】
また、−ＳＸ基の定量は以下の方法により行うことができる。すなわち、ＰＰＳ粉末を予め１２０℃で４時間乾燥した後、この乾燥ＰＰＳ粉末２０ｇをＮ−メチル−２−ピロリドン１５０ｇに加えて粉末凝集塊がなくなるように室温で３０分間激しく撹拌混合しスラリー状態にする。
かかるスラリーを濾過した後、毎回約８０℃の温水１リットルを用いて７回洗浄を繰り返す。得た濾過ケーキを純水２００ｇ中に再度スラリー化した後、１Ｎの塩酸を加えて該スラリーのＰＨを４．５に調整する。次に、２５℃で３０分間撹拌し、濾過した後、約８０℃の温水１リットルを用いて６回洗浄を繰り返す。得られた濾過ケーキを純水２００ｇ中に再度スラリー化し、次いで、１Ｎの水酸化ナトリウムにより滴定し、消費した水酸化ナトリウム量よりＰＰＳ中に存在する−ＳＸ基の量を求める。
【００１６】
ここで、塩化メチレンによるオリゴマー抽出量が０．７重量％以下であり、かつ−ＳＸ基が２０μｍｏｌ／ｇ以上であるＰＰＳの具体的な製造方法としては、特開平８−２５３５８７号公報の実施例１および２に記載された製造方法（段落番号００４１〜００４４）や特開平１１−１０６６５６号公報の合成例１および２に記載された製造方法（段落番号００４６〜００４８）等が挙げられる。
さらに、本発明で用いるＰＰＳは３２０℃における溶融粘度（フローテスターを用いて、３００℃、荷重１９６Ｎ、Ｌ／Ｄ＝１０／１で６分間保持した値）は、好ましくは１〜１０，０００ポイズであり、さらに好ましくは１００〜１０，０００ポイズである。
かかる（ａ）成分の配合量は、耐熱性、成形流動性、耐溶剤性および成形品の表面濡れ性の改善効果によるＵＶ硬化性接着剤の接着性改良の観点から３０〜７０重量％である。
【００１７】
つぎに本発明の（ｂ）成分はポリフェニレンエーテル樹脂１００重量部に対してポリスチレン樹脂を４５〜１５０重量部の割合で混合したものをいう。
かかるポリスチレン樹脂の混合量は、無機フィラーを多量に含む本発明の樹脂組成物では、成形流動性が著しく悪化することから４５重量部以上であり、得られる成形品の温度変化に対する寸法安定性および光軸のずれ、成形品の表面濡れ性の改善効果によるＵＶ硬化性接着剤の接着強度、引張強度、アイゾット衝撃強度、荷重たわみ温度を考慮すると１５０重量部以下である。
この本発明の（ｂ）成分の構成要素であるポリフェニレンエーテル樹脂（以下、単にＰＰＥと略記）は、本発明のポリマーアロイおいて耐熱性（荷重撓み温度：ＤＴＵＬ）、および難燃性を付与するうえで必須な成分であり、
該ＰＰＥは、結合単位（式１）
【００１８】
【化１】
（ここで、Ｒ１，Ｒ２，Ｒ３および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、互いに同一でも異なっていてもよい）からなり、還元粘度（０．５ｇ／ｄｌ，クロロホルム溶液，３０℃測定）が、０．１５〜２．０の範囲であることが好ましく、さらに好ましくは０．２０〜１．０の範囲にあるホモ重合体および／または共重合体である。
【００２０】
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。
【００２１】
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号明細書記載の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号明細書、同第３２５７３５７号および同第３２５７３５８号明細書、特公昭５２−１７８８０号公報および特開昭５０−５１１９７号公報および同６３−１５２６２８号公報等に記載された方法で容易に製造できる。
【００２２】
つぎに、本発明の（ｂ）成分のポリスチレン樹脂とは、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それら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が挙げられ、これら２種以上の混合物も好適に用いることができる。
スチレン系化合物とは、次の一般式（２）で表される化合物を意味する。
【００２３】
【化２】
（式中、Ｒは水素、炭素数１〜４の低級アルキルまたはハロゲンを示し、Ｚはビニル、水素、ハロゲン及び炭素数１〜４の低級アルキルよりなる群から選択される基を表し、ｑは０〜５の整数である。）
これらの具体例としては、スチレンのほか、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、モノクロロスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、α−エチルスチレン等が挙げられる。 これらはその２種以上を併用しても良いが、好ましくは、スチレンの単独重合体である。
【００２５】
本発明におけるポリスチレン樹脂の還元粘度ηｓｐ／ｃは、好ましくは０．７０ｄｌ／ｇ以上、より好ましくは０．８ｄｌ／ｇ以上である。ここで、還元粘度ηｓｐ／ｃとは、溶液濃度０．５ｇ／１００ｍｌのトルエン溶液を３０℃で測定して求めた値である。なお、ポリスチレン樹脂のηｓｐ／ｃの上限は特にないが、あまりηｓｐ／ｃが高くなりすぎると押出加工が困難となる。
本発明のポリスチレン樹脂の製造方法は特に限定されるものではなく、当業者に良く知られている塊状重合、溶液重合、乳化重合、懸濁重合のいずれの方法を用いても良い。ポリスチレン樹脂の分子量分布は、組成物中で１．５〜５が好ましい。また、このスチレン樹脂の分子の立体構造については、アタクチック、アイソタクチック、シンジオタクチックが挙げられるが、いずれでも好適に用いることができる。
【００２６】
またさらに、本発明で用いる事が出来るゴム変性スチレン樹脂とは、一般的にはゴム状重合体をスチレン系化合物単量体（および不活性溶媒を加えた液）に溶解し、攪拌下、塊状重合、塊状懸濁重合または溶液重合を行い、ゴム状重合体を析出し、粒子化することにより得られるが、重合法に限定されるものではない。また、前記ゴム状重合体としては、ポリブタジエン、スチレン・ブタジエン共重合体、ポリイソプレン，ブタジエン・イソプレン共重合体、天然ゴム、エチレン・プロピレン共重合体を挙げることができるが、一般的には、ポリブタジエン、スチレン・ブタジエン共重合体が好ましく、また、これらを部分水素添加したものがさらに好ましい。
【００２７】
上記ゴム変性スチレン樹脂については特に制約はないが、一般的には４〜１５重量％、より好ましくは６〜１３重量％である。さらにゴム変性スチレン樹脂のゴム状重合体粒子の平均粒子径は、０．５〜６．０μｍの範囲であることが好ましい。また、前記ゴム変性スチレン樹脂のゲル含量（トルエン不溶分）は、常法の１５〜４０重量％に調整されるが、より好ましくは２０〜３５重量％である。かかる（ｂ）成分の配合量は、耐熱性、成形流動性、耐溶剤性および成形品の表面濡れ性の改善効果によるＵＶ硬化性接着剤の接着性の観点から７０〜３０重量％である。
【００２８】
つぎに本発明の（ｃ）成分は、（ａ）成分のＰＰＳと（ｂ）成分のＰＰＥを混合する際の相溶化剤として作用し、本発明の樹脂組成物に優れた機械的物性を与える効果を奏するものである。
かかる（ｃ）成分としては、エポキシ基および／またはオキサゾニ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であり、ここで言うスチレンを主たる成分とするモノマーとは、スチレンモノマーと共重合可能な他のモノマーであれば何ら問題なく使用でき、その割合が少なくともスチレンモノマーを６５重量％以上含むことを意味するものである。
【００２９】
具体的には、エポキシ基および／またはオキサゾニ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／またはオキサゾニ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％の共重合体が挙げられる。
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、上記のオキサゾニル基含有不飽和モノマーとしては、下記一般式（式３）
【００３０】
【化３】
（ここでＲは、水素原子または炭素数１〜６のアルキル基またはアルコキシ基）である。）この構造を示すビニルオキサゾリン化合物であり、中でもＲが水素原子またはメチル基を示す化合物が好ましい。その中でも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。
これら、エポキシ基および／またはオキサゾニ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、スチレン等のビニル芳香族化合物、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、かかる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、相溶化効果、機械的物性の観点から エポキシ基および／またはオキサゾニ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％である。
【００３２】
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。
【００３３】
この（ｃ）成分の配合量は、相溶化剤としての混和効果および未溶融物発生、成形品の表面濡れ性の改善効果によるＵＶ硬化性接着剤の接着強度の観点から（ａ）成分と（ｂ）成分１００重量部に対して１〜２０重量部である。
つぎに本発明で（ｄ）成分として用いるビニル芳香族化合物を主体とする少なくとも１個の重合体ブロックＡと共役ジエン化合物を主体とする少なくとも１個の重合体ブロックＢとからなるブロック共重合体および該ブロック共重合体を水素添加してなる水添ブロック共重合体は、（ｂ）成分のポリフェニレンエーテル樹脂中に分散し、ポリフェニレンスルフィド樹脂組成物の靱性付与に大きな効果を奏するものである。
【００３４】
この本発明における（ｄ）成分として用いるビニル芳香族化合物を主体とする少なくとも１個の重合体ブロックＡと共役ジエン化合物を主体とする少なくとも１個の重合体ブロックＢとからなるブロック共重合体および該ブロック共重合体を水素添加してなる水添ブロック共重合体とは、例えばＡ−Ｂ、Ａ−Ｂ−Ａ、Ｂ−Ａ−Ｂ−Ａ、（Ａ−Ｂ−）４−Ｓｉ、Ａ−Ｂ−Ａ−Ｂ−Ａ等の構造を有し、結合したビニル芳香族化合物を５〜９５重量％、好ましくは１０〜８０重量％含んだブロック共重合体およびこれを水素添加してなる水添ブロック共重合体である。
【００３５】
またブロック構造に言及すると、ビニル芳香族化合物を主体とする重合体ブロックＡとは、ビニル芳香族化合物のホモ重合体ブロックまたはビニル芳香族化合物を好ましくは５０重量％を超え、更に好ましくは７０重量％以上含有するビニル芳香族化合物と共役ジエン化合物との共重合体ブロックの構造を有しており、そしてさらに、共役ジエン化合物を主体とする重合体ブロックＢとは、共役ジエン化合物のホモ重合体ブロックまたは共役ジエン化合物を好ましくは５０重量％を超え、更に好ましくは７０重量％以上含有する共役ジエン化合物とビニル芳香族化合物との共重合体ブロックの構造を有するものである。
【００３６】
これらのビニル芳香族化合物を主体とする重合体ブロックＡ、共役ジエン化合物を主体とする重合体ブロックＢは、それぞれの重合体ブロックにおける分子鎖中の共役ジエン化合物またはビニル芳香族化合物の分布がランダム、テーパード（分子鎖に沿ってモノマー成分が増加または減少するもの）、一部ブロック状またはこれらの任意の組み合わせで成っていてもよく、該ビニル芳香族化合物を主体とする重合体ブロックおよび該共役ジエン化合物を主体とする重合体ブロックがそれぞれ２個以上ある場合は、各重合体ブロックはそれぞれ同一構造であってもよく、異なる構造であってもよい。
【００３７】
このブロック共重合体を構成するビニル芳香族化合物としては、例えば、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−ｔｅｒｔ−ブチルスチレン、ジフェニルエチレン等のうちから１種または２種以上を選択でき、中でもスチレンが好ましい。また、共役ジエン化合物としては、例えば、ブタジエン、イソプレン、１，３−ペンタジエン、２，３−ジメチル−１，３−ブタジエン等のうちから１種または２種以上が選ばれ、中でも、ブタジエン、イソプレンおよびこれらの組み合わせが好ましい。そして共役ジエン化合物を主体とする重合体ブロックは、そのブロックにおける結合形態のミクロ構造を任意に選ぶことができ、例えば、ブタジエンを主体とする重合体ブロックにおいては、１，２−ビニル結合が２〜９０％が好ましく、より好ましくは８〜８０％である。また、イソプレンを主体とする重合体ブロックにおいては、１，２−ビニル結合と３，４−ビニル結合の合計量が２〜８０％、より好ましくは３〜７０％である。
【００３８】
本発明で用いる（ｄ）成分のブロック共重合体および／または水添ブロック共重合体の数平均分子量は、５，０００〜１，０００，０００であるものが好ましく、特に好ましくは２０，０００〜５００，０００の範囲のものであり、分子量分布〔ゲルパーミエーションクロマトグラフィで測定しポリスチレン換算した重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比〕は１０以下であるものが好ましい。さらに、このブロック共重合体および／または水添ブロック共重合体の分子構造は、直鎖状、分岐状、放射状あるいはこれらの任意の組み合わせのいずれであってもよい。
【００３９】
このような構造をもつ水添ブロック共重合体は、上記したブロック共重合体の共役ジエン化合物を主体とした重合体ブロックＢの脂肪族系二重結合を水素添加反応を実施し、本発明で用いる（ｄ）成分の水添ブロック共重合体として利用できる。かかる脂肪族系二重結合の水素添加率は、少なくとも２０％を超えることが好ましく、更に好ましくは５０％以上、特に好ましくは８０％以上である。
かかる水素添加率は例えば核磁気共鳴装置（ＮＭＲ）等を用いて知ることができる。
【００４０】
この（ｄ）成分の配合量は、耐衝撃性および機械的物性の観点から（ａ）成分と（ｂ）成分１００重量部に対し０〜４０重量部、好ましくは、０〜２０重量部の範囲より選ばれることが好ましい。
さらに、本発明で（ｅ）成分として用いる板状および繊維状の無機フィラーは形状が板状および繊維状であり、その配合比率は板状／繊維状フィラーの重量比が１以上である組み合わせの無機物ならば公知の無機フィラーを使用でき、これらを２種類以上併用してもよい。
かかる（ｅ）成分の無機フィラーは、板状および繊維状無機フィラーを併用したものであり、その配合比率は成形流動性および樹脂組成物から得られる成形品の温度変化に対する寸法安定性および光軸のずれ・ＵＶ硬化性接着剤の接着性の観点から、板状無機フィラー／繊維状無機フィラーの重量比で１以上が好ましく、より好ましくは１．５以上より選ばれることが好ましい。
【００４１】
また、本発明の（ｅ）成分は、（ａ）成分および（ｃ）成分に合わせた表面処理、例えばシラン系やチタネート系等の種々のカップリング剤で処理を施したものを用いることが好ましい。繊維状の無機フィラーの一例として、ガラス繊維、炭素繊維、ワラストナイト、チタン酸カリウムおよび炭酸カルシウムのウイスカー類等が挙げられる。これらの繊維状の無機フィラーはその補強効果の観点から、繊維の平均直径（Ｄ）と平均長さ（Ｌ）の比で表されるＬ／Ｄが５以上であることが好ましい。つぎに板状の無機フィラーの一例としては、ガラスフレーク、マイカ、鱗片状黒鉛、タルク等が挙げられる。これらの板状の無機フィラーはその補強効果の観点から、板の平均厚み（Ｈ）と平均板径（Ｒ）の比で表されるＲ／Ｈが５以上であることが好ましい。
【００４２】
この（ｅ）成分の配合量は機械的物性、成形流動性、温度による寸法変化および光軸のずれ、成形品の表面濡れ性の改善効果によるＵＶ硬化性接着剤の接着性の観点から（ａ）成分と（ｂ）成分１００重量部に対し１００〜４００重量部であり、好ましくは、１５０重量部を超え４００重量部、より好ましくは１５０重量部を超え３５０重量部の範囲より選ばれることが好ましい。
本発明では、上記の成分の他に本発明の特徴及び効果を損なわない範囲で必要に応じて他の付加的成分、例えば、酸化防止剤、金属不活性化剤、難燃剤（有機リン酸エステル系化合物、縮合有機リン酸エステル系化合物、ポリリン酸アンモニウム系化合物、芳香族ハロゲン系難燃剤、シリコーン系難燃剤など）、フッ素系ポリマー、可塑剤（低分子量ポリエチレン、エポキシ化大豆油、ポリエチレングリコール、脂肪酸エステル類等）、三酸化アンチモン等の難燃助剤、耐候（光）性改良剤、造核剤、スリップ剤、無機または有機の充填材や強化材（ポリアクリロニトリル繊維、カーボンブラック、酸化チタン、導電性金属繊維、導電性カーボンブラック等）、各種着色剤、離型剤等を添加してもかまわない。
【００４３】
本発明の樹脂組成物の製造法は、種々の溶融混機を用いて製造することができ、これらの方法を行う溶融混練機として例えば、単軸押出機、二軸押出機を含む多軸押出機、ロール、ニーダー、ブラベンダープラストグラフ、バンバリーミキサー等による加熱溶融混練機が挙げられるが、中でも二軸押出機を用いた溶融混練方法が最も好ましい。具体的には、ＷＥＲＮＥＲ＆ＰＦＬＥＩＤＥＲＥＲ社製のＺＳＫシリーズ、東芝機械（株）製のＴＥＭシリーズ、日本製鋼所（株）製のＴＥＸシリーズなどが挙げられる。
【００４４】
押出機を用いた本発明の好ましい態様を以下に述べる。押出機のＬ／Ｄ（バレル有効長／バレル内径）は２０以上６０以下の範囲であり、好ましくは３０以上５０以下の範囲である。押出機は原料の流れ方向に対し上流側に第１原料供給口、これより下流に第１真空ベント、その下流に第２〜第４原料供給口を設け、さらにその下流に第２真空ベントを設けたものが好ましい。なかでも、第１真空ベントの上流にニーディングセクションを設け、第１真空ベントと第２原料供給口の間にニーディングセクションを設け、また第２〜第４原料供給口と第２真空ベントの間にニーディングセクションを設けたものがより好ましい。第２〜第４原料供給口への原材料供給方法は、特に限定されるものでは無いが、押出機第２〜第４原料供給口開放口よりの単なる添加供給よりも、押出機サイド開放口から強制サイドフィーダーを用いて供給する方が安定で好ましい。
【００４５】
特に、本発明の樹脂組成物のように粉体、フィラー等が非常に多く含まれる場合は、押出機サイドから供給する強制サイドフィーダーの方がより好ましく、強制サイドフィーダーを第２〜第４原料供給口に設け、これら粉体、フィラー等を分割して供給するのがより好ましい。そして、押出機第２〜第４原料供給口の上部開放口は同搬する空気を抜くため開放とすることもできる。この際の溶融混練温度、スクリュー回転数は特に限定されるものではないが、通常溶融混練温度３００〜３５０℃、スクリュー回転数１００〜１２００ｒｐｍの中から任意に選ぶことができる。
【００４６】
本発明の樹脂組成物の製造方法としては、
１．上記した（ａ）成分〜（ｄ）成分を第一供給口より供給し、次いで（ｅ）成分の繊維状無機フィラーおよび板状無機フィラーを第二供給口より溶融混練状態下に供給し、さらに溶融混練を続けて行う方法。
２．（ａ）成分〜（ｄ）成分の全量および（ｅ）成分の板状無機フィラーの２０〜１００重量％を第一原料供給口より供給し、次いで（ｅ）成分の繊維状無機フィラーおよび板状無機フィラーの残量を第二原料供給口より溶融混練状態下に供給し、さらに溶融混練を続けて行う方法。
３．（ａ）成分〜（ｄ）成分の全量を第１原料供給口より供給し、次いで（ｅ）成分の板状無機フィラーを第２原料供給口より溶融混練状態下に供給し、さらに（ｅ）成分の繊維状無機フィラーを第３原料供給口より溶融混練状態下に供給し、溶融混練を続けて行う樹脂組成物の製造方法が挙げられる。
【００４７】
このような製法を取ることにより、得られる樹脂組成物は（ａ）成分〜（ｅ）成分が各々優れた均一分散形態を得ることができ、これらの相溶化剤である（ｃ）成分の配合効果を最も顕著に発現させ、さらに（ｅ）成分中の繊維状フィラーの溶融混練中の破砕を抑えることで、優れた機械的物性を損なうことなく、成形流動性、温度による寸法変化および光軸のずれ、ＵＶ硬化性接着剤による接着性が優れる樹脂組成物を得ることが出来る。この製法を取ることは、本発明の樹脂組成物を得るにあたり、非常に重要である。
【００４８】
このようにして得られる本発明の樹脂組成物は、従来の多量の無機フィラーを含むポリフェニレンスルフィド系樹脂組成物の欠点であった成形流動性および機械的物性を著しく改善し、さらに温度による寸法変化および光軸のずれ、ＵＶ硬化性接着剤による接着性に優れる。
特に、上記２，３の製造方法で得られる樹脂組成物は１の製造方法と比べ、流動性に優れた樹脂組成物が得られることが最大の特徴である。
このため、本発明の樹脂組成物は、広く射出成形、押出成形、押出異形成形、中空成形、圧縮成形により目的に応じた各種部品の成形体として成形できる。
【００４９】
本発明の樹脂組成物は、例えばコンピューター、ＣＤ−ＲＯＭ、ＣＤ−Ｒ、ＤＶＤ−ＲＯＭ、ＤＶＤ−ＲＡＭ、ＤＶＤ−Ｒ、ＤＶＤ−ＲＷ等の各種ディスクプレーヤー等のディスクを記録媒体として用い、光または磁気で書き込みまたは読み取りを行う機器に用いられる機構部品等で利用でき、中でも光ディスクドライブ用機構部品としてのピックアップベース、トラバースベース、サブシャーシ、ベースシャーシ等のシャーシ類やディスクトレー、チェンジャートレー等のトレー類、ディスクガイド、フレーム等、付随部品等の樹脂製機構部品に適する。特に温度等使用環境の厳しい車載用のＣＤプレーヤー、ＤＶＤビデオ、ＤＶＤナビゲーション、ＭＤプレイヤー等向けピックアップベース類、シャーシ類やトレー類等の光ディスクドライブ用機構部品用として、本発明の樹脂組成物を使用する効果は大きい。
【００５０】
さらにその他の用途、例えば電気機器の内外装部品として好適に使用でき、具体的には各種コンピューターおよびその周辺機器、その他のＯＡ機器、テレビ、ビデオ、冷蔵庫、工業用部品用途では各種ポンプケーシング等の部品用途に適している。また、自動車部品が挙げられ、具体的には、バンパー、フェンダー、ドアーパネル、各種モール、エンブレム、エンジンフード、ホイールキャップ、ルーフ、スポイラー、各種エアロパーツ等の外装品や、インストゥルメントパネル、コンソールボックス、トリム等の内装部品、さらに自動車、電気自動車およびハイブリッド電気自動車等に搭載される二次電池電槽部品に適している。
【００５１】
【発明の実施の形態】
本発明を実施例によって、さらに詳細に説明するが、これらの実施例により限定されるものではない。
（ａ）成分の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／＝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オリゴマー抽出量が０．４重量％、−ＳＸ基量が２９μｍｏｌ／ｇのＰＰＳ。
ａ−２：溶融粘度が６００ポイズ、塩化メチレンによるオリゴマー抽出量が１．８重量％、−ＳＸ基量が３０μｍｏｌ／ｇのＰＰＳ。
ａ−３：溶融粘度が５００ポイズ、塩化メチレンによるオリゴマー抽出量が０．５重量％、−ＳＸ基量が９μｍｏｌ／ｇのＰＰＳ。
【００５２】
（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０．５４のＰＰＥ。
ｂ−２：アタクチックポリスチレン。（Ａ＆Ｍ社製 ポリスチレン６８５）
ｂ−３：ゴム変性ポリスチレン樹脂。（Ａ＆Ｍ社製 ポリスチレンＨ９４０５）
（ｃ）成分の相溶化剤
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）
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）
【００５３】
（ｄ）成分のブロック共重合体、水添ブロック共重合体
ｄ−１：ポリスチレン−水素添加されたポリブタジエン−ポリスチレンの構造であり、結合スチレン量が３５重量％、数平均分子量が１７８，０００、水素添加する前のポリブタジエン部の１，２−ビニル結合量が４８％である水添ブロック共重合体。
【００５４】
（ｅ）成分の無機フィラー
ｅ−１：平均直径１３μ、平均長さ３ｍｍ、アミノシラン系カップリング剤で表面処理した、ガラス繊維。
ｅ−２：平均板径９０μ、平均厚み２μ、アミノシラン系カップリング剤で表面処理した、マイカ。
ｅ−３：平均板径６００μ、平均厚み５μ、アミノシラン系カップリング剤で表面処理した、ガラスフレーク。
ｅ−４：平均粒子径７μ（平均Ｌ／Ｄ＝１．６）である炭酸カルシウム。
ｅ−５：平均粒子径７μ（平均Ｌ／Ｄ＝１．６）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重量部を予めブレンダーを用いてブレンドした物。
ｅ−６：平均粒子径１．６μ、平均厚み０．４ミクロンであるタルク。
ｅ−７：平均粒子径０．５μ（球の扁平率＝１．０４）であるガラスビーズ。
【００５５】
【実施例１〜１７および比較例１〜１７】
二軸押出機ＺＳＫ−４０（ＷＥＲＮＥＲ＆ＰＦＬＥＩＤＥＲＥＲ社製）を用い原料の流れ方向に対し上流側に第１原料供給口、これより下流に第２原料供給口および第３原料供給口を設け、さらにその下流に真空ベントを設けた。また、第２供給口および第３原料供給口への原材料供給方法は、押出機サイド開放口から強制サイドフィーダーを用いて供給する。上記のように設定した押出機を用い、（ａ）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、（ｃ）相溶化剤、（ｄ）ブロック共重合体、水添ブロック共重合体、（ｅ）無機フィラーを表１および表２に示した組成で配合し、押出温度３００〜３２０℃、スクリュー回転数３００ｒｐｍ、吐出量８０ｋｇ／時間の条件にて溶融混練しペレットとして得た。
【００５６】
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、金型温度１３０℃の条件でＡＳＴＭ−Ｄ６３８−１号ダンベル試験片金型を用いてその試験片の成形下限圧（ゲージ圧力）を測定し、成形流動性の評価とした。
さらに、上記の射出成形機を用い、同様の条件で引張試験用テストピース、アイゾット衝撃試験用テストピース、荷重撓み温度測定用テストピースおよび３インチ角×厚み１／８インチの平板を射出成形した。
【００５７】
つぎに、３インチ角×厚み１／８インチの平板を用い、中心に４ｍｍΦの穴を開け、１０ｍｍ角×厚み２ｍｍのアルミニウム板の中心を穴の中心に合わせＵＶ硬化性接着剤（東亞合成（株）製 ラックストラックＬＣＲ０６４１）５ｍｇを２点塗布し、ＵＶ照射器（浜松ホトニクス（株）製 ＬＣ５）を用いて５００ｍＷ／ｃｍ２、１２秒の条件で硬化接着した。この試験片を温度２３℃、湿度５０％に管理された恒温室内で押し抜き試験機（島津製作所（株）製 ＧＳ−５００Ｄ）を用いて１０ｍｍ／分の条件で測定を行い、ＵＶ硬化性接着剤の接着強度とした。
【００５８】
また、光ディスク用ピックアップシャーシ試験片を３１０℃に設定したスクリューインライン型射出成形機にて金型温度１３０℃の条件で成形した。次にこの試験片の中央孔部にハーフミラーを取り付け、恒温槽中で焦点距離１５０ｍｍ、波長６７０ｎｍ、出力０．３ｍＷの半導体コリメーターからレーザー光を発振し、ハーフミラーに対し直角に照射し、反射したレーザー光をＣＣＤカメラを用いて受光した。２３℃における反射レーザー光の位置を原点とし、１℃／分の速度で６０℃に昇温し１時間静置後の光軸ずれを測定した。その後、−３０℃まで１℃／分で降温し１時間静置後、光軸のずれを測定した。
【００５９】
さらに、引張試験用テストピースを用いて線膨張係数（ＡＳＴＭ Ｄ６９６に準拠：測定温度−３０〜６５℃）および引張強度（ＡＳＴＭ Ｄ−６３８に準拠：測定温度２３℃）を測定し、それぞれのテストピースでアイゾット（厚み１／８、ノッチ付き）衝撃強度（ＡＳＴＭ Ｄ−２５６に準拠：測定温度２３℃）および荷重撓み温度（ＡＳＴＭ Ｄ−６４８：１．８２ＭＰａ荷重）を測定した。これらの結果を成形流動性、ＵＶ硬化性接着剤の接着強度の評価と併せて表１および表２に載せた。
【００６０】
表１および表２より、本発明の樹脂組成物は引張強度、耐衝撃性および耐熱性を損なうことなく、成形流動性、温度による寸法変化および光軸のずれが少なく、かつＵＶ硬化性接着剤による接着性が同時に優れるが、本発明の組成が範囲外である場合、引張強度、耐衝撃性および耐熱性を損なうことなく成形流動性、温度による寸法変化および光軸のずれが少なく、かつＵＶ硬化性接着剤による接着性を同時に改良する事が出来ないことが明らかになった。
【００６１】
【表１】
【表２】
【発明の効果】
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、相溶化剤、ブロック共重合体及び無機フィラーからなる樹脂組成物において、特定の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樹脂と特定のポリスチレン樹脂、ならびに無機フィラーとして板状および繊維状であり、板状／繊維状フィラーの重量比が１以上である無機フィラーを用い、さらに特定の製造方法をとることにより、引張強度、耐衝撃性および耐熱性を損なうことなく成形流動性、温度による寸法変化および光軸のずれが少なく、ＵＶ硬化性接着剤による接着性に優れる樹脂組成物および光ディスクドライブ用樹脂製機構部品が得られる。[0001]
[Industrial applications]
The present invention relates to a resin composition having excellent oil resistance, chemical resistance, heat resistance, impact resistance, and rigidity which can be used in the fields of electric / electronics, automobiles, and various other industrial materials. The present invention relates to a resin composition which is excellent in molding fluidity, has little dimensional change due to temperature and deviation of an optical axis, and has excellent adhesiveness of a UV-curable adhesive.
[0002]
[Prior art]
Conventionally, unreinforced polyphenylene sulfide has been used in the electronics field because of its good crystallinity and excellent heat resistance and water resistance due to its crystallinity, but as a molding material, it has poor toughness (impact strength). Therefore, it is difficult to use it for various molded products (particularly, large molded products).
For this reason, many attempts have been made to blend or alloy polyphenylene sulfide with various resins, various thermoplastic elastomers, etc. in order to solve these drawbacks.
[0003]
For example, a resin composition comprising polyphenylene oxides and polyphenylene sulfides and having excellent moldability and flame retardancy has been proposed. (For example, see Patent Document 1)
In addition, a modified block copolymer composition comprising a hydrogenated block copolymer modified with polyphenylene sulfide or another engineering resin and a derivative of α, β-unsaturated carboxylic acid, and having excellent impact resistance and interfacial peel resistance. Has been proposed. (For example, see Patent Document 2)
Further, a thermoplastic graft copolymer composition having excellent impact resistance comprising a hydrogenated block copolymer and an epoxy group-containing polymer modified with polyphenylene sulfide or another engineering resin and a derivative of α, β-unsaturated carboxylic acid Has been proposed. (For example, see Patent Document 3)
[0004]
A polyarylene sulfide resin composition comprising polyarylen sulfide and a glycidyl ester copolymer of α-olefin / α, β-unsaturated acid and having excellent impact resistance and moldability has been proposed. (For example, see Patent Document 4)
Further, there has been proposed a composition excellent in impact resistance, comprising a polyolefin obtained by graft copolymerizing polyphenylene sulfide and an unsaturated carboxylic acid or an anhydride or a derivative thereof and an epoxy resin. (For example, see Patent Document 5)
Further, a polyphenylene sulfide resin composition excellent in impact resistance comprising a glycidyl ester copolymer of a specific polyphenylene sulfide and an α-olefin / α, β-unsaturated acid has been proposed. (For example, see Patent Documents 6, 7, and 8)
[0005]
Further, a polyphenylene sulfide resin composition excellent in impact resistance comprising a polyolefin obtained by graft copolymerizing a specific polyphenylene sulfide and an unsaturated carboxylic acid or an anhydride or a derivative thereof has been proposed. (See, for example, Patent Documents 9 to 11)
Similarly, a method using a copolymer of styrene and an ethylenically unsaturated monomer having an oxazonyl group has been proposed for improving the miscibility of acid-modified polyphenylene ether and modified polyphenylene sulfide. (See, for example, Patent Documents 12 and 13)
Further, a method using a copolymer of styrene and an ethylenically unsaturated monomer having an oxazonyl group has been proposed for improving the miscibility of polyphenylene sulfide and polyphenylene ether. (For example, see Patent Document 14)
[0006]
Further, a resin composition in which mechanical strength and dimensional stability are improved by using an inorganic filler in a polyphenylene sulfide and polyphenylene ether resin composition has been proposed. (See, for example, Patent Documents 15 to 28)
The present applicant has also proposed a resin composition using a specific inorganic filler and having improved mechanical strength and dimensional stability. (For example, see Patent Documents 29 to 30)
However, although the resin compositions comprising polyphenylene sulfide, polyphenylene ether and an inorganic filler proposed therein have been improved in mechanical properties and dimensional stability, these resin compositions have recently used CD-R and CD-R. Demands for improvement of dimensional stability and optical axis characteristics for higher level of temperature change due to miniaturization and precision of optical equipment parts such as RW, DVD-R, DVD-RW, etc. I was not satisfied.
[0007]
[Patent Document 1]
JP-B-56-34032
[Patent Document 2]
JP-A-58-27740
[Patent Document 3]
JP-A-58-40350
[Patent Document 4]
JP-A-58-154775
[Patent Document 5]
JP-A-59-207921
[Patent Document 6]
JP-A-62-153343
[Patent Document 7]
JP-A-62-153344
[Patent Document 8]
JP-A-62-153345
[Patent Document 9]
JP-A-62-169854
[Patent Document 10]
JP-A-62-172056
[Patent Document 11]
JP-A-62-172057
[Patent Document 12]
JP-A-01-266160
[Patent Document 13]
JP-A-02-75656
[Patent Document 14]
JP-A-03-20356
[Patent Document 15]
JP 05-339500 A
[Patent Document 16]
JP-A-9-157525
[Patent Document 17]
JP-A-9-296109
[Patent Document 18]
JP-A-9-296110
[Patent Document 19]
JP-A-11-106652
[Patent Document 20]
JP-A-11-106665
[Patent Document 21]
JP-A-11-106654
[Patent Document 22]
JP-A-11-106655
[Patent Document 23]
JP-A-11-158374
[Patent Document 24]
JP-A-11-199774
[Patent Document 25]
JP 2000-198924 A
[Patent Document 26]
JP-A-2002-069298
[Patent Document 27]
JP 2002-121383 A
[Patent Document 28]
JP 2002-179915 A
[Patent Document 29]
JP-A-2002-012764
[Patent Document 30]
JP-A-2002-249661
[0008]
[Problems to be solved by the invention]
The present invention provides excellent molding fluidity without impairing the excellent mechanical properties of a resin composition comprising polyphenylene sulfide, polyphenylene ether, and an inorganic filler, has small dimensional change and optical axis shift due to temperature, and has UV curability. An object of the present invention is to provide a resin composition having excellent adhesiveness with an adhesive and a resin structural component for an optical disk drive.
[0009]
[Means for Solving the Problems]
In view of this situation, the present inventors have conducted intensive studies on a resin composition comprising a polyphenylene sulfide resin, a polyphenylene ether resin, and an inorganic filler. The present inventors have found that it is possible to improve the fluidity, the adhesiveness by a UV-curable adhesive, and the mechanical properties, and at the same time, to reduce the dimensional change due to temperature and the deviation of the optical axis.
[0010]
That is, the present invention
1. (A) a polyphenylene sulfide resin having an extraction amount with methylene chloride of 0.7% by weight or less and containing -SX groups (S is a sulfur atom, X is an alkali metal or a hydrogen atom) of 15 µmol / g or more; 70% by weight,
(B) 70 to 30% by weight of a polyphenylene ether-based resin containing 45 to 150 parts by weight of a polystyrene resin with respect to 100 parts by weight of the polyphenylene ether resin,
For a total of 100 parts by weight of the components (a) and (b),
(C) 1 to 20 parts by weight of a copolymer obtained by copolymerizing an unsaturated monomer having an epoxy group and / or an oxazonyl group with a monomer containing styrene as a main component at a ratio of 0.3 to 20% by weight;
Further, based on a total of 100 parts by weight of the components (a) and (b),
And (d) a block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound, and / or the block copolymer. A hydrogenated block copolymer obtained by hydrogenating 0 to 40 parts by weight,
Furthermore, with respect to a total of 100 parts by weight of the component (a) and the component (b),
(E) A resin composition comprising 100 to 400 parts by weight of an inorganic filler which is a plate-like or fibrous inorganic filler and has a weight ratio of the plate-like / fibrous filler of 1 or more.
[0011]
Furthermore, in this resin composition,
2. A method for producing a resin composition in which all of the components (a) to (d) are melt-kneaded, the component (e) is supplied, and the melt-kneading is continued.
3. The total amount of the components (a) to (d) and 20 to 100% by weight of the plate-like inorganic filler of the component (e) are melt-kneaded, and then the remaining amounts of the fibrous inorganic filler and the plate-like inorganic filler of the component (e) are reduced. A method for producing a resin composition, wherein the resin composition is supplied and further melt-kneaded.
4. A resin obtained by melt-kneading the entire amount of the components (a) to (d), then supplying the plate-like inorganic filler of the component (e), and further supplying the fibrous inorganic filler of the component (e), and continuing the melt-kneading. A method for producing the composition.
The present invention relates to a resin-made structural part for an optical disk drive, which is made of a resin composition manufactured by using the method described above.
[0012]
The polyphenylene sulfide resin (hereinafter abbreviated as PPS) as the component (a) of the present invention is basically a polyphenylene sulfide having a paraphenylene sulfide skeleton of at least 70 mol%, preferably at least 90 mol%.
The above-mentioned method for producing PPS is usually carried out by polymerizing a halogen-substituted aromatic compound such as p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrogen sulfide and sodium hydroxide in a polar solvent. Or polymerization in the presence of hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate; self-condensation of p-chlorothiophenol; and amide solvents such as N-methylpyrrolidone and dimethylacetamide, and sulfolane. A suitable method is to react sodium sulfide with p-dichlorobenzene in a sulfone solvent. The production method is not particularly limited as long as it can be obtained by a known method. For example, U.S. Pat. No. 2,513,188, JP-B-44-27671, and JP-B-45-3368 are disclosed. JP-B-52-12240, JP-A-61-225217 and US Pat. No. 3,274,165, British Patent No. 1160660, JP-B-46-27255, Belgian Patent No. 29437, It can be obtained by the method described in JP-A-5-222196 or the like or the prior art method exemplified in these patents and the like.
[0013]
Further, the polyphenylene sulfide resin as the component (a) of the present invention has an oligomer extraction amount of 0.7% by weight or less with methylene chloride, and has an -SX group (S is a sulfur atom, X is an alkali metal or a hydrogen atom). Is polyphenylene sulfide of 15 μmol / g or more.
By using a polyphenylene sulfide resin that satisfies both the amount of oligomer extracted by methylene chloride and the concentration of -SX groups (S is a sulfur atom, X is an alkali metal or a hydrogen atom), the resin composition containing a large amount of the inorganic filler of the present invention In the case of products, it improves the miscibility of polyphenylene sulfide and polyphenylene ether and the adhesive strength of UV-curable adhesives by improving the tensile strength, Izod impact strength, and surface wettability of molded products obtained from resin compositions. it can. However, when at least one of the oligomer extraction amount and the -SX group concentration is out of the range, these cannot be improved.
[0014]
When the range of the oligomer extraction amount is within the above range, it means that the amount of the oligomer (about 10 to 30 mer) in the PPS is small.
Here, the measurement of the oligomer extraction amount with methylene chloride can be performed by the following method. That is, 5 g of PPS powder is added to 80 ml of methylene chloride, soxhlet extraction is performed for 4 hours, then 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 three times with a total of 60 ml of methylene chloride, and the washing liquid is collected in the weighing bottle. Next, the mixture is heated to about 80 ° C., the methylene chloride in the weighing bottle is removed by evaporation, the residue is weighed, and the proportion of the oligomer present in the PPS can be determined from the residue.
[0015]
The quantification of the -SX group can be performed by the following method. That is, after the PPS powder was previously dried at 120 ° C. for 4 hours, 20 g of the dried PPS powder was added to 150 g of N-methyl-2-pyrrolidone, and the mixture was vigorously stirred and mixed at room temperature for 30 minutes so as to eliminate powder agglomerates. I do.
After filtering such a slurry, washing is repeated seven times each time using 1 liter of warm water at about 80 ° C. After the obtained filter cake is again slurried in 200 g of pure water, 1N hydrochloric acid is added to adjust the pH of the slurry to 4.5. Next, the mixture is stirred at 25 ° C. for 30 minutes, filtered, and then washed six times using 1 liter of hot water at about 80 ° C. The obtained filter cake is slurried again in 200 g of pure water, then titrated with 1N sodium hydroxide, and the amount of -SX groups present in the PPS is determined from the amount of sodium hydroxide consumed.
[0016]
Here, a specific method for producing PPS in which the amount of oligomers extracted by methylene chloride is 0.7% by weight or less and the -SX group is 20 μmol / g or more is described in Examples in JP-A-8-253587. Examples include the production methods described in Paragraphs Nos. 1 and 2 (paragraph numbers 0041 to 0044) and the production methods described in Synthesis Examples 1 and 2 of JP-A-11-106656 (paragraph numbers 0046 to 0048).
Further, the PPS used in the present invention preferably has a melt viscosity at 320 ° C. (value held at 300 ° C., load of 196 N, L / D = 10/1 for 6 minutes using a flow tester) of preferably 1 to 10,000 poise. And more preferably 100 to 10,000 poise.
The compounding amount of the component (a) is 30 to 70% by weight from the viewpoint of improving the adhesiveness of the UV-curable adhesive by the effect of improving heat resistance, molding fluidity, solvent resistance and surface wettability of the molded article. .
[0017]
Next, the component (b) of the present invention refers to a mixture obtained by mixing 45 to 150 parts by weight of a polystyrene resin with respect to 100 parts by weight of a polyphenylene ether resin.
In the resin composition of the present invention containing a large amount of an inorganic filler, the mixing amount of the polystyrene resin is 45 parts by weight or more because the molding fluidity is significantly deteriorated. It is 150 parts by weight or less in consideration of the adhesive strength, tensile strength, Izod impact strength, and deflection temperature under load of the UV curable adhesive due to the shift of the optical axis and the effect of improving the surface wettability of the molded product.
The polyphenylene ether resin (hereinafter simply referred to as PPE) which is a component of the component (b) of the present invention imparts heat resistance (load deflection temperature: DTUL) and flame retardancy to the polymer alloy of the present invention. It is an essential ingredient above,
The PPE is a bonding unit (formula 1)
[0018]
Embedded image
(Where R1, R2, R3 and R4 are each hydrogen, halogen, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, Or a halohydrocarbon oxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom, and may be the same or different from each other), and have a reduced viscosity (0 0.5 g / dl, chloroform solution, measured at 30 ° C.) is preferably in the range of 0.15 to 2.0, and more preferably in the range of 0.20 to 1.0. It is a polymer.
[0020]
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 -6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like. Further, 2,6-dimethylphenol and other phenols (for example, Polyphenylene ether copolymers such as copolymers with 3,6-trimethylphenol and 2-methyl-6-butylphenol). Among them, 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) is more preferable. , 4-phenylene ether) are preferred.
[0021]
The method for producing such a PPE is not particularly limited as long as it can be obtained by a known method.For example, using a complex of a cuprous salt and an amine according to Hay described in U.S. Pat. For example, it can be easily produced by oxidative polymerization of 2,6-xylenol, and in addition, U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, JP-B-52-17880 and JP-A-52-18880. It can be easily produced by the method described in JP-A-50-51197 and JP-A-63-152628.
[0022]
Next, the polystyrene resin as the component (b) of the present invention refers to a homopolymer of a styrene-based compound, a copolymer of two or more styrene-based compounds, and a rubber-like matrix in a matrix comprising the polymer of the styrene-based compound. A rubber-modified styrene resin in which a polymer is dispersed in the form of particles is exemplified, and a mixture of two or more of these resins can also be suitably used.
The styrene-based compound means a compound represented by the following general formula (2).
[0023]
Embedded image
(Wherein, R represents hydrogen, lower alkyl having 1 to 4 carbon atoms or halogen, Z represents a group selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl having 1 to 4 carbon atoms, and q represents It is an integer of 0 to 5.)
Specific examples of these include, in addition to styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, 2,4-dimethylstyrene, Monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, α-ethylstyrene and the like can be mentioned. These may be used in combination of two or more thereof, but are preferably styrene homopolymers.
[0025]
The reduced viscosity ηsp / c of the polystyrene resin in the present invention is preferably 0.70 dl / g or more, more preferably 0.8 dl / g or more. Here, the reduced viscosity ηsp / c is a value obtained by measuring a toluene solution having a solution concentration of 0.5 g / 100 ml at 30 ° C. There is no particular upper limit for ηsp / c of the polystyrene resin, but if ηsp / c is too high, extrusion becomes difficult.
The method for producing the polystyrene resin of the present invention is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization well known to those skilled in the art may be used. The molecular weight distribution of the polystyrene resin is preferably from 1.5 to 5 in the composition. The three-dimensional structure of the molecule of the styrene resin includes atactic, isotactic and syndiotactic, and any of them can be suitably used.
[0026]
Further, the rubber-modified styrene resin that can be used in the present invention generally means that a rubber-like polymer is dissolved in a styrene-based compound monomer (and a liquid to which an inert solvent has been added), and the resulting mixture is agglomerated under stirring. It is obtained by performing polymerization, bulk suspension polymerization or solution polymerization, and precipitating and granulating a rubber-like polymer, but is not limited to the polymerization method. Examples of the rubbery polymer include polybutadiene, styrene / butadiene copolymer, polyisoprene, butadiene / isoprene copolymer, natural rubber, and ethylene / propylene copolymer. Polybutadiene and styrene-butadiene copolymer are preferred, and those obtained by partially hydrogenating them are more preferred.
[0027]
The rubber-modified styrene resin is not particularly limited, but is generally 4 to 15% by weight, more preferably 6 to 13% by weight. Furthermore, the average particle diameter of the rubber-like polymer particles of the rubber-modified styrene resin is preferably in the range of 0.5 to 6.0 μm. The gel content (toluene-insoluble content) of the rubber-modified styrene resin is adjusted to 15 to 40% by weight according to a conventional method, and is more preferably 20 to 35% by weight. The compounding amount of the component (b) is 70 to 30% by weight from the viewpoint of the adhesiveness of the UV-curable adhesive due to the effect of improving heat resistance, molding fluidity, solvent resistance and surface wettability of the molded article.
[0028]
Next, the component (c) of the present invention acts as a compatibilizer when mixing the PPS of the component (a) and the PPE of the component (b), and gives the resin composition of the present invention excellent mechanical properties. It is effective.
The component (c) is a copolymer of an unsaturated monomer having an epoxy group and / or an oxazonyl group and a monomer containing styrene as a main component. The monomer containing styrene as a main component is styrene. Any other monomer copolymerizable with the monomer can be used without any problem, and the ratio means that the styrene monomer contains at least 65% by weight or more.
[0029]
Specifically, a copolymer of an unsaturated monomer having an epoxy group and / or an oxazonyl group and a styrene monomer, and an unsaturated monomer having an epoxy group and / or an oxazonyl group and styrene / acrylonitrile = 90 to 75% by weight / 10 to 10% 25% by weight of the copolymer.
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, and glycidyl itaconate. Among them, glycidyl methacrylate is preferred. The oxazonyl group-containing unsaturated monomer is represented by the following general formula (formula 3)
[0030]
Embedded image
(Where R is a hydrogen atom or an alkyl or alkoxy group having 1 to 6 carbon atoms). ) A vinyloxazoline compound having this structure, and among them, a compound in which R represents a hydrogen atom or a methyl group is preferable. Among them, 2-isopropenyl-2-oxazoline is industrially available and can be preferably used.
Other unsaturated monomers copolymerized with the unsaturated monomer having an epoxy group and / or an oxazonyl group include vinyl aromatic compounds such as styrene, vinyl cyanide monomers such as acrylonitrile, vinyl acetate, and (meth) acrylic acid. Examples include esters and the like, but it is essential that the styrene monomer be contained in at least 65% by weight or more. Further, from the viewpoint of the compatibilizing effect and mechanical properties, the unsaturated monomer having an epoxy group and / or an oxazonyl group is contained in the copolymer (c) in an amount of 0.3 to 20% by weight, preferably 1 to 15% by weight. %, More preferably 3 to 10% by weight.
[0032]
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- Glycidyl methacrylate-acrylonitrile copolymer, styrene-vinyl oxazoline copolymer, styrene-vinyl oxazoline-acrylonitrile copolymer and the like can be mentioned.
[0033]
The amount of the component (c) is determined from the viewpoints of the admixing effect as a compatibilizer, the generation of unmelted material, and the adhesive strength of the UV-curable adhesive due to the effect of improving the surface wettability of the molded product. b) 1 to 20 parts by weight based on 100 parts by weight of the component.
Next, a block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound used as the component (d) in the present invention. The hydrogenated block copolymer obtained by hydrogenating the block copolymer is dispersed in the polyphenylene ether resin as the component (b), and has a great effect on imparting toughness of the polyphenylene sulfide resin composition.
[0034]
A block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound used as the component (d) in the present invention; The hydrogenated block copolymer obtained by hydrogenating the block copolymer includes, for example, AB, ABA, BABA, (AB-) 4-Si, A A block copolymer having a structure such as -BABA and containing a bound vinyl aromatic compound in an amount of 5 to 95% by weight, preferably 10 to 80% by weight, and water obtained by hydrogenating the block copolymer. It is an addition block copolymer.
[0035]
Further, referring to the block structure, the polymer block A mainly composed of a vinyl aromatic compound is preferably a homopolymer block of a vinyl aromatic compound or a vinyl aromatic compound in an amount exceeding 50% by weight, more preferably 70% by weight. % Of a copolymer block of a vinyl aromatic compound and a conjugated diene compound containing at least 10% by weight, and a polymer block B mainly composed of a conjugated diene compound is a homopolymer of a conjugated diene compound. It preferably has a structure of a copolymer block of a conjugated diene compound and a vinyl aromatic compound containing a block or a conjugated diene compound in an amount exceeding 50% by weight, more preferably 70% by weight or more.
[0036]
In these polymer blocks A mainly composed of vinyl aromatic compounds and polymer blocks B mainly composed of conjugated diene compounds, the distribution of the conjugated diene compound or vinyl aromatic compound in the molecular chain in each polymer block is random. , Tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped or any combination thereof, the polymer block mainly composed of the vinyl aromatic compound and the conjugate When there are two or more polymer blocks each containing a diene compound as a main component, the polymer blocks may have the same structure or different structures.
[0037]
As the vinyl aromatic compound constituting the block copolymer, for example, one or more kinds of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like can be selected, Among them, styrene is preferred. Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. And combinations thereof. The polymer block mainly composed of a conjugated diene compound can arbitrarily select a microstructure of a bonding form in the block. For example, in a polymer block mainly composed of butadiene, 1,2-vinyl bond has 2 It is preferably from 90 to 90%, more preferably from 8 to 80%. In a polymer block mainly composed of isoprene, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 2 to 80%, more preferably 3 to 70%.
[0038]
The number average molecular weight of the block copolymer and / or hydrogenated block copolymer of the component (d) used in the present invention is preferably from 5,000 to 1,000,000, and particularly preferably from 20,000 to 1,000,000. The molecular weight distribution is preferably in the range of 500,000, and the molecular weight distribution [the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography] is 10 or less. Further, the molecular structure of this block copolymer and / or hydrogenated block copolymer may be any of linear, branched, radial, or any combination thereof.
[0039]
The hydrogenated block copolymer having such a structure is obtained by performing a hydrogenation reaction on the aliphatic double bond of the polymer block B mainly composed of the conjugated diene compound of the block copolymer described above. It can be used as a hydrogenated block copolymer of the component (d) used. The hydrogenation rate of such an aliphatic double bond is preferably at least more than 20%, more preferably at least 50%, particularly preferably at least 80%.
Such a hydrogenation rate can be known using, for example, a nuclear magnetic resonance apparatus (NMR).
[0040]
The amount of the component (d) is in the range of 0 to 40 parts by weight, preferably 0 to 20 parts by weight based on 100 parts by weight of the components (a) and (b) from the viewpoint of impact resistance and mechanical properties. It is preferable to be selected from the following.
Further, the plate-like and fibrous inorganic fillers used as the component (e) in the present invention are plate-like and fibrous in shape, and the compounding ratio thereof is a combination of a plate-like / fibrous filler having a weight ratio of 1 or more. Known inorganic fillers can be used as long as they are inorganic substances, and two or more of them may be used in combination.
The inorganic filler of the component (e) is a combination of a plate-like and a fibrous inorganic filler, and its mixing ratio is determined by the molding fluidity, the dimensional stability of the molded product obtained from the resin composition against temperature change, and the optical axis. From the viewpoint of the deviation and the adhesiveness of the UV-curable adhesive, the weight ratio of the plate-like inorganic filler / fibrous inorganic filler is preferably 1 or more, more preferably 1.5 or more.
[0041]
The component (e) of the present invention is preferably one which has been subjected to a surface treatment suitable for the component (a) and the component (c), for example, a treatment with various coupling agents such as a silane type or a titanate type. . Examples of the fibrous inorganic filler include glass fibers, carbon fibers, wollastonite, whiskers of potassium titanate and calcium carbonate, and the like. From the viewpoint of the reinforcing effect, these fibrous inorganic fillers preferably have an L / D expressed by the ratio of the average diameter (D) to the average length (L) of the fibers of 5 or more. Next, examples of the plate-like inorganic filler include glass flake, mica, flaky graphite, talc and the like. From the viewpoint of the reinforcing effect, these plate-like inorganic fillers preferably have an R / H expressed by a ratio of the average thickness (H) of the plate to the average plate diameter (R) of 5 or more.
[0042]
The amount of the component (e) is selected from the viewpoints of mechanical properties, molding fluidity, dimensional change due to temperature, deviation of the optical axis, and the adhesiveness of the UV-curable adhesive due to the effect of improving the surface wettability of the molded article. The amount is from 100 to 400 parts by weight, preferably from more than 150 parts by weight to 400 parts by weight, more preferably from more than 150 parts by weight to 350 parts by weight based on 100 parts by weight of component (b). preferable.
In the present invention, in addition to the above components, other additional components such as an antioxidant, a metal deactivator, a flame retardant (organic phosphate, etc.) may be used as needed as long as the characteristics and effects of the present invention are not impaired. Compounds, condensed organophosphate compounds, ammonium polyphosphate compounds, aromatic halogen-based flame retardants, silicone-based flame retardants, etc.), fluoropolymers, plasticizers (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, Fatty acid esters, etc.), flame retardant aids such as antimony trioxide, weather (light) improvers, nucleating agents, slip agents, inorganic or organic fillers and reinforcing materials (polyacrylonitrile fiber, carbon black, titanium oxide) , Conductive metal fibers, conductive carbon black, etc.), various coloring agents, release agents and the like.
[0043]
The method for producing the resin composition of the present invention can be produced by using various melt mixers, and as a melt kneader for performing these methods, for example, a single screw extruder, a multi-screw extruder including a twin screw extruder. Melting and kneading machines using a machine, roll, kneader, Brabender plastograph, Banbury mixer, etc., among them, the melt kneading method using a twin screw extruder is most preferable. Specific examples include ZSK series manufactured by WERNER & PFLEIDERER, TEM series manufactured by Toshiba Machine Co., Ltd., and TEX series manufactured by Japan Steel Works, Ltd.
[0044]
A preferred embodiment of the present invention using an extruder will be described below. The L / D (barrel effective length / barrel inner diameter) of the extruder is in the range of 20 to 60, preferably 30 to 50. The extruder has a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a first vacuum vent downstream of the first raw material supply port, and second to fourth raw material supply ports downstream of the first vacuum supply vent. The one provided is preferred. In particular, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second material supply port, and a kneading section is provided between the second to fourth material supply ports and the second vacuum vent. It is more preferable to provide a kneading section between them. The method of supplying raw materials to the second to fourth raw material supply ports is not particularly limited, but rather than merely adding and supplying from the extruder second to fourth raw material supply opening ports, It is more stable and preferable to supply using a forced side feeder.
[0045]
In particular, when the resin composition of the present invention contains a very large amount of powders, fillers, etc., the forced side feeder supplied from the extruder side is more preferable, and the forced side feeder is used as the second to fourth raw materials. It is more preferable to provide these at the supply port and supply these powders, fillers and the like in a divided manner. The upper opening of the second to fourth raw material supply ports of the extruder may be opened to evacuate the carried air. The melt-kneading temperature and the screw rotation speed at this time are not particularly limited, but can be arbitrarily selected from a melt-kneading temperature of 300 to 350 ° C. and a screw rotation speed of 100 to 1200 rpm.
[0046]
As a production method of the resin composition of the present invention,
1. The components (a) to (d) are supplied from the first supply port, and then the fibrous inorganic filler and the plate-like inorganic filler of the component (e) are supplied from the second supply port in a melt-kneaded state. A method in which melt-kneading is continued.
2. The total amount of the components (a) to (d) and 20 to 100% by weight of the plate-like inorganic filler of the component (e) are supplied from the first raw material supply port, and then the fibrous inorganic filler of the component (e) and the plate-like inorganic filler. A method in which the remaining amount of the inorganic filler is supplied from the second raw material supply port under a melt-kneading state, and the melt-kneading is further continued.
3. The total amount of the components (a) to (d) is supplied from the first raw material supply port, and then the plate-like inorganic filler of the component (e) is supplied from the second raw material supply port in a melt-kneaded state. A method for producing a resin composition in which a fibrous inorganic filler as a component is supplied from a third raw material supply port in a melt-kneaded state and melt-kneading is continued.
[0047]
By adopting such a manufacturing method, the obtained resin composition can obtain an excellent uniform dispersion form of each of the components (a) to (e), and blending of the compatibilizer (c). The effect is most remarkably exhibited, and furthermore, by suppressing crushing of the fibrous filler in the component (e) during melt-kneading, excellent mechanical properties are not impaired, and molding fluidity, dimensional change due to temperature, and optical axis And a resin composition having excellent adhesiveness with a UV-curable adhesive can be obtained. Taking this manufacturing method is very important in obtaining the resin composition of the present invention.
[0048]
The resin composition of the present invention thus obtained significantly improves molding fluidity and mechanical properties, which were disadvantages of the conventional polyphenylene sulfide-based resin composition containing a large amount of an inorganic filler, and further has a dimensional change due to temperature. In addition, the optical axis shift and the adhesiveness by the UV curable adhesive are excellent.
In particular, the most characteristic feature of the resin composition obtained by the above-described production methods 2 and 3 is that a resin composition having excellent fluidity can be obtained as compared with the production method of 1.
For this reason, the resin composition of the present invention can be molded as a molded article of various parts according to the purpose by injection molding, extrusion molding, extrusion molding, hollow molding, and compression molding.
[0049]
The resin composition of the present invention uses, for example, a disc such as a computer, various disc players such as a CD-ROM, a CD-R, a DVD-ROM, a DVD-RAM, a DVD-R, and a DVD-RW as a recording medium, It can be used for mechanical parts used in devices that write or read magnetically, such as pickup bases, traverse bases, sub-chassis, base chassis and other chassis as optical disk drive mechanical parts, and trays such as disk trays and changer trays. Suitable for plastic mechanical parts such as accessories, disk guides, frames, and other accompanying parts. Particularly, the resin composition of the present invention is used as a mechanical component for an optical disk drive such as a pickup base, a chassis or a tray for a CD player, a DVD video, a DVD navigation, an MD player, etc. for an in-vehicle CD player, a DVD video, a DVD navigation, an MD player. The effect is great.
[0050]
Furthermore, it can be suitably used as interior / exterior parts of electric equipment, for example, various computers and their peripheral equipment, other OA equipment, televisions, videos, refrigerators, and various pump casings for industrial parts. Suitable for parts use. Also, there are automobile parts, specifically, exterior parts such as bumpers, fenders, door panels, various malls, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, instrument panels, consoles, and the like. It is suitable for interior parts such as boxes and trims, and secondary battery case parts mounted on automobiles, electric vehicles, hybrid electric vehicles and the like.
[0051]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will be described in more detail by way of examples, but is not limited by these examples.
(A) Component polyphenylene sulfide resin
a-1: Melt viscosity (measured after holding for 6 minutes at 300 ° C., load 196 N, L / = 10/1 using a flow tester) is 500 poise, and the amount of oligomer extracted by methylene chloride is 0.4. % By weight, -PS having an SX group content of 29 μmol / g.
a-2: PPS having a melt viscosity of 600 poise, an oligomer extraction amount with methylene chloride of 1.8% by weight, and an -SX group amount of 30 μmol / g.
a-3: PPS having a melt viscosity of 500 poise, an oligomer extraction amount with methylene chloride of 0.5% by weight, and an -SX group amount of 9 μmol / g.
[0052]
(B) Component polyphenylene ether resin
b-1: PPE having a reduced viscosity of 0.54 obtained by oxidative polymerization of 2,6-xylenol.
b-2: atactic polystyrene. (Polystyrene 685 manufactured by A & M)
b-3: rubber-modified polystyrene resin. (Polystyrene H9405 manufactured by A & M)
(C) Compatibilizer for component
c-1: a styrene-glycidyl methacrylate copolymer containing 5% by weight of glycidyl methacrylate. (Weight average molecular weight 110,000)
c-2: a styrene-2-isopropenyl-2-oxazoline copolymer containing 5% by weight of 2-isopropenyl-2-oxazoline. (Weight average molecular weight 146,000)
[0053]
(D) Component block copolymer, hydrogenated block copolymer
d-1: a structure of polystyrene-hydrogenated polybutadiene-polystyrene having a bound styrene content of 35% by weight, a number average molecular weight of 178,000, and a 1,2-vinyl bond content of a polybutadiene portion before hydrogenation. 48% hydrogenated block copolymer.
[0054]
(E) Component inorganic filler
e-1: a glass fiber having an average diameter of 13 μm and an average length of 3 mm and surface-treated with an aminosilane coupling agent.
e-2: Mica having an average plate diameter of 90 μm, an average thickness of 2 μm, and surface-treated with an aminosilane coupling agent.
e-3: glass flakes having an average plate diameter of 600 μm, an average thickness of 5 μm, and a surface treatment with an aminosilane coupling agent.
e-4: calcium carbonate having an average particle diameter of 7 μ (average L / D = 1.6).
e-5: a silane coupling agent (β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) per 100 parts by weight of calcium carbonate having an average particle diameter of 7 μ (average L / D = 1.6). 5 parts by weight previously blended using a blender.
e-6: Talc having an average particle diameter of 1.6 μm and an average thickness of 0.4 μm.
e-7: glass beads having an average particle size of 0.5 μm (flatness of sphere = 1.04).
[0055]
Examples 1 to 17 and Comparative Examples 1 to 17
Using a twin-screw extruder ZSK-40 (manufactured by Werner & Pleiderer), a first raw material supply port is provided on the upstream side with respect to the flow direction of the raw material, and a second raw material supply port and a third raw material supply port are provided downstream from the first raw material supply port, and further downstream thereof Was provided with a vacuum vent. In addition, in the method of supplying raw materials to the second supply port and the third raw material supply port, the raw material is supplied from the extruder side open port using a forced side feeder. Using the extruder set as described above, (a) polyphenylene sulfide resin, (b) polyphenylene ether-based resin, (c) compatibilizer, (d) block copolymer, hydrogenated block copolymer, (e) ) An inorganic filler was blended in the composition shown in Tables 1 and 2, and melt-kneaded under the conditions of an extrusion temperature of 300 to 320 ° C, a screw rotation speed of 300 rpm, and a discharge rate of 80 kg / hour to obtain pellets.
[0056]
The pellets are supplied to a screw in-line injection molding machine set at 310 ° C., and the lower limit pressure for molding the test pieces using an ASTM-D638-1 dumbbell test piece mold at a mold temperature of 130 ° C. ( Gage pressure) was measured and evaluated for molding fluidity.
Further, using the above-described injection molding machine, a test piece for tensile test, a test piece for Izod impact test, a test piece for measuring load deflection temperature, and a 3 inch square × 1/8 inch thick flat plate were injection molded under the same conditions. .
[0057]
Next, a 4 mmΦ hole was made at the center using a 3 inch square × 1/8 inch thick flat plate, and the center of the 10 mm square × 2 mm thick aluminum plate was aligned with the center of the hole, and a UV curable adhesive (Toagosei ( Co., Ltd., LUXTRACK LCR0641) (5 mg) was applied at two points, and 500 mW / cm was applied using a UV irradiator (LC5, manufactured by Hamamatsu Photonics KK). 2 , For 12 seconds. This test piece was measured in a thermostatic chamber controlled at a temperature of 23 ° C. and a humidity of 50% using a push-out tester (GS-500D, manufactured by Shimadzu Corporation) under the conditions of 10 mm / min, and UV-curable adhesive was applied. The adhesive strength of the agent.
[0058]
Further, the optical disk pickup chassis test piece was molded by a screw in-line type injection molding machine set at 310 ° C. at a mold temperature of 130 ° C. Next, a half mirror was attached to the center hole of the test piece, and a laser beam was oscillated from a semiconductor collimator having a focal length of 150 mm, a wavelength of 670 nm, and an output of 0.3 mW in a thermostat, and was irradiated at right angles to the half mirror. The reflected laser light was received using a CCD camera. With the position of the reflected laser beam at 23 ° C. as the origin, the temperature was raised to 60 ° C. at a rate of 1 ° C./min, and the optical axis shift after standing for 1 hour was measured. Thereafter, the temperature was lowered to -30 ° C at a rate of 1 ° C / minute, and allowed to stand for 1 hour, after which the deviation of the optical axis was measured.
[0059]
Further, the coefficient of linear expansion (according to ASTM D696: measurement temperature of −30 to 65 ° C.) and tensile strength (according to ASTM D-638: measurement temperature of 23 ° C.) were measured using a test piece for tensile test. The pieces were measured for Izod (thickness 1/8, notch) impact strength (according to ASTM D-256: measurement temperature 23 ° C.) and load deflection temperature (ASTM D-648: 1.82 MPa load). The results are shown in Tables 1 and 2 together with the evaluation of the molding fluidity and the adhesive strength of the UV curable adhesive.
[0060]
As shown in Tables 1 and 2, the resin composition of the present invention has a small amount of molding fluidity, small dimensional change due to temperature and deviation of optical axis without impairing tensile strength, impact resistance and heat resistance, and is a UV-curable adhesive. Is excellent simultaneously, but when the composition of the present invention is out of the range, the molding fluidity, the dimensional change due to temperature and the deviation of the optical axis are small without impairing the tensile strength, impact resistance and heat resistance, and UV It became clear that the adhesiveness of the curable adhesive could not be improved at the same time.
[0061]
[Table 1]
[Table 2]
【The invention's effect】
Polyphenylene sulfide resin, polyphenylene ether-based resin, compatibilizer, a resin composition comprising a block copolymer and an inorganic filler, a specific polyphenylene sulfide resin, polyphenylene ether resin and a specific polystyrene resin, and a plate-like and fiber as an inorganic filler By using an inorganic filler having a weight ratio of platy / fibrous filler of 1 or more and taking a specific manufacturing method, the molding fluidity without impairing the tensile strength, impact resistance and heat resistance, A resin composition and a resin mechanical component for an optical disk drive having a small dimensional change and a shift of an optical axis due to temperature and having excellent adhesiveness by a UV-curable adhesive can be obtained.
Claims (8)
（ｂ）ポリフェニレンエーテル樹脂１００重量部に対して、ポリスチレン樹脂を４５〜１５０重量部含んでなるポリフェニレンエーテル系樹脂７０〜３０重量％であって、
（ａ）成分と（ｂ）成分の合計１００重量部に対し、
（ｃ）エポキシ基およびまたはオキサゾニル基を有する不飽和モノマーを０．３〜２０重量％の割合でスチレンを主たる成分とするモノマーと共重合してなる共重合体１〜２０重量部、
さらに、（ａ）成分と（ｂ）成分の合計１００重量部に対して、
（ｄ）ビニル芳香族化合物を主体とする少なくとも１個の重合体ブロックＡと共役ジエン化合物を主体とする少なくとも１個の重合体ブロックＢとからなるブロック共重合体および／または該ブロック共重合体を水素添加してなる水添ブロック共重合体０〜４０重量部、
さらにまた、（ａ）成分と（ｂ）成分の合計１００重量部に対して、
（ｅ）板状および繊維状である無機フィラーであって、かつ板状／繊維状フィラーの重量比が１以上である無機フィラー １００〜４００重量部を含む樹脂組成物。(A) A polyphenylene sulfide resin 30 whose extraction amount with methylene chloride is 0.7% by weight or less and whose -SX group (S is a sulfur atom, X is an alkali metal or a hydrogen atom) is 15 μmol / g or more. ~ 70% by weight,
(B) 70 to 30% by weight of a polyphenylene ether-based resin containing 45 to 150 parts by weight of a polystyrene resin with respect to 100 parts by weight of the polyphenylene ether resin,
For a total of 100 parts by weight of the components (a) and (b),
(C) 1 to 20 parts by weight of a copolymer obtained by copolymerizing an unsaturated monomer having an epoxy group and / or an oxazonyl group with a monomer containing styrene as a main component at a ratio of 0.3 to 20% by weight;
Further, based on a total of 100 parts by weight of the components (a) and (b),
And (d) a block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound, and / or the block copolymer. A hydrogenated block copolymer obtained by hydrogenating 0 to 40 parts by weight,
Furthermore, with respect to a total of 100 parts by weight of the component (a) and the component (b),
(E) A resin composition containing 100 to 400 parts by weight of an inorganic filler which is a plate-like or fibrous inorganic filler and a weight ratio of the plate-like / fibrous filler is 1 or more.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006291054A (en) * | 2005-04-12 | 2006-10-26 | Asahi Kasei Chemicals Corp | 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 |
| CN101084273B (en) * | 2004-12-21 | 2010-12-08 | 旭化成化学株式会社 | Polyphenylene sulfide resin composition |
| JP2014114421A (en) * | 2012-12-12 | 2014-06-26 | Asahi Kasei Chemicals Corp | Resin composition |
| CN111849162A (en) * | 2019-04-24 | 2020-10-30 | 旭化成株式会社 | Thin-walled component and container |
| JP2021195447A (en) * | 2020-06-12 | 2021-12-27 | 味の素株式会社 | Resin composition |
-
2003
- 2003-01-16 JP JP2003008679A patent/JP4173377B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006316245A (en) * | 2004-12-21 | 2006-11-24 | Asahi Kasei Chemicals Corp | Polyphenylene sulfide resin composition |
| CN101084273B (en) * | 2004-12-21 | 2010-12-08 | 旭化成化学株式会社 | Polyphenylene sulfide resin composition |
| JP2006291054A (en) * | 2005-04-12 | 2006-10-26 | Asahi Kasei Chemicals Corp | Resin composition |
| JP4694243B2 (en) * | 2005-04-12 | 2011-06-08 | 旭化成ケミカルズ株式会社 | Resin composition |
| JP2007186672A (en) * | 2005-12-16 | 2007-07-26 | Toray Ind Inc | Polyphenylene sulfide resin composition and molding |
| JP2014114421A (en) * | 2012-12-12 | 2014-06-26 | Asahi Kasei Chemicals Corp | Resin composition |
| CN111849162A (en) * | 2019-04-24 | 2020-10-30 | 旭化成株式会社 | Thin-walled component and container |
| JP2021195447A (en) * | 2020-06-12 | 2021-12-27 | 味の素株式会社 | Resin composition |
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