JP2005200562A - Reinforced polyphenylene ether-based resin composition - Google Patents
Reinforced polyphenylene ether-based resin composition Download PDFInfo
- Publication number
- JP2005200562A JP2005200562A JP2004008938A JP2004008938A JP2005200562A JP 2005200562 A JP2005200562 A JP 2005200562A JP 2004008938 A JP2004008938 A JP 2004008938A JP 2004008938 A JP2004008938 A JP 2004008938A JP 2005200562 A JP2005200562 A JP 2005200562A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- resin composition
- weight
- ether 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.)
- Pending
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 80
- 239000011342 resin composition Substances 0.000 title claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- -1 silane compound Chemical class 0.000 claims abstract description 55
- 239000011256 inorganic filler Substances 0.000 claims abstract description 30
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 30
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000003063 flame retardant Substances 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 9
- 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 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 8
- 239000002216 antistatic agent Substances 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 41
- 239000000203 mixture Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 15
- 230000000704 physical effect Effects 0.000 description 13
- 239000004793 Polystyrene Substances 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000004756 silanes Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920001890 Novodur Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- GBZVNKQWXLVYNG-UHFFFAOYSA-N (3-phosphonooxyphenyl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC=CC(OP(O)(O)=O)=C1 GBZVNKQWXLVYNG-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 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
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- KKDONKAYVYTWGY-UHFFFAOYSA-M sodium;2-(methylamino)ethanesulfonate Chemical compound [Na+].CNCCS([O-])(=O)=O KKDONKAYVYTWGY-UHFFFAOYSA-M 0.000 description 1
- RLJSXMVTLMHXJS-UHFFFAOYSA-M sodium;4-decylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 RLJSXMVTLMHXJS-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 description 1
- KBAFDSIZQYCDPK-UHFFFAOYSA-M sodium;octadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O KBAFDSIZQYCDPK-UHFFFAOYSA-M 0.000 description 1
- AYFACLKQYVTXNS-UHFFFAOYSA-M sodium;tetradecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCS([O-])(=O)=O AYFACLKQYVTXNS-UHFFFAOYSA-M 0.000 description 1
- ORLPWCUCEDVJNN-UHFFFAOYSA-N sodium;tetradecyl benzenesulfonate Chemical compound [Na].CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 ORLPWCUCEDVJNN-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Abstract
Description
本発明は、帯電防止性に優れると共に、成形体の表面平滑性や組成物中の無機質充填剤の樹脂密着性に優れ、耐熱性、剛性、流動性、耐衝撃性、摺動性に優れた強化ポリフェニレンエーテル系樹脂組成物およびその製造方法に関する。 The present invention is excellent in antistatic property, excellent in surface smoothness of a molded article and resin adhesion of an inorganic filler in the composition, and excellent in heat resistance, rigidity, fluidity, impact resistance, and slidability. The present invention relates to a reinforced polyphenylene ether resin composition and a method for producing the same.
ポリフェニレンエーテル系樹脂は機械的性質、成形加工性、耐熱性、寸法安定性あるいは電気特性等に優れるため、家電分野、事務機分野や情報機器分野、自動車分野等に広く用いられている。特に近年、事務機、情報機器分野における複写機、パソコン等の外装、内部部品、或いはその周辺機器の様々な部品に広く用いられつつある。これらの用途部品にはより高い剛性、耐熱性、寸法安定性等要求されることから無機質充填剤を配合した強化樹脂組成物が多く用いられている。このような無機質充填剤の配合で強化したポリフェニレンエーテル系樹脂組成物において、シラン化合物で表面処理した無機質充填剤を用いて、不飽和カルボン酸等で官能化されたポリフェニレンエーテル樹脂を配合することにより、無機質充填剤表面と樹脂成分との密着性が改良されて耐衝撃性、耐久性等に優れたポリフェニレンエーテル系強化樹脂組成物が得られることは既に知られている（例えば特許文献１参照）。 Polyphenylene ether-based resins are excellent in mechanical properties, molding processability, heat resistance, dimensional stability, electrical characteristics, and the like, and are therefore widely used in the home appliance field, office machine field, information equipment field, automobile field, and the like. In particular, in recent years, it has been widely used for various parts of the exterior, internal parts, and peripheral equipment of office machines, copying machines and personal computers in the field of information equipment. Since these parts are required to have higher rigidity, heat resistance, dimensional stability, etc., reinforced resin compositions containing an inorganic filler are often used. In a polyphenylene ether-based resin composition reinforced by blending such an inorganic filler, by blending a polyphenylene ether resin functionalized with an unsaturated carboxylic acid or the like using an inorganic filler surface-treated with a silane compound It is already known that a polyphenylene ether-based reinforced resin composition having improved impact resistance, durability and the like can be obtained by improving the adhesion between the surface of the inorganic filler and the resin component (see, for example, Patent Document 1). .
一方、これら部品の多くは駆動部品あるいは駆動部と接触する部品として使用されている。近年、処理速度の大幅な増加に伴う駆動部の高速化により、樹脂部品に摩擦による静電気が帯電しやすく、その結果、埃などが付着して汚れが生じたり、記録媒体の読み取りエラー等の誤作動を起こすなどの好ましくない静電気障害を招く欠点を有している。
従来、静電気が帯電しやすい樹脂の帯電を防止する方法として、一般的な帯電防止剤としての界面活性剤を樹脂に押出機等で溶融混練する方法が広く知られている。しかし多くの樹脂においてこれら界面活性剤の添加は、成形体の帯電防止性能を改良する反面、耐熱性や剛性、難燃性、成形体の表面外観等を低下させることも知られている。
On the other hand, many of these parts are used as drive parts or parts that come into contact with the drive unit. In recent years, due to the increase in the speed of the drive unit accompanying a significant increase in processing speed, static electricity due to friction tends to be easily charged on resin parts. It has the disadvantage of causing undesired electrostatic disturbances such as activation.
Conventionally, as a method for preventing charging of a resin that is easily charged with static electricity, a method in which a surfactant as a general antistatic agent is melt-kneaded with a resin by an extruder or the like is widely known. However, in many resins, the addition of these surfactants is known to improve the antistatic performance of the molded product, but lowers the heat resistance, rigidity, flame retardancy, surface appearance of the molded product, and the like.
ポリフェニレンエーテル系樹脂組成物においても同様な傾向が見られるが、特に無機質充填剤強化系においてはこれら界面活性剤の多くは無機質充填剤と樹脂成分との密着性を悪化させるため機械的物性、耐久性等の低下が著しいばかりか、更にこのような方法で帯電防止性能を付与すること自体が非強化の樹脂に比べて極めて困難なことであった。
そのため、無機質充填剤強化系材料よりなる成形品に帯電防止性を付与するためには、成形品表面に界面活性剤を溶媒に溶かして溶液化したものを塗布する方法が従来行われてきた。このような方法なら材料の物性を低下させず確実に目標レベルの帯電防止性を付与できるが、その反面、作業工程を増やしてコスト的な負担もまた大きかった。
The same tendency can be seen in the polyphenylene ether resin composition, but especially in the inorganic filler reinforced system, many of these surfactants deteriorate the adhesion between the inorganic filler and the resin component, so that mechanical properties and durability are improved. In addition to the remarkable decrease in properties and the like, it was extremely difficult to impart antistatic performance by such a method as compared with non-reinforced resin.
Therefore, in order to impart antistatic properties to a molded article made of an inorganic filler-reinforced material, a method of applying a solution obtained by dissolving a surfactant in a solvent on the surface of the molded article has been conventionally performed. Such a method can reliably provide a target level of antistatic properties without deteriorating the physical properties of the material, but on the other hand, it has increased the number of work steps and has a high cost burden.
本発明で使用される帯電防止剤であるアルキルスルホン酸金属塩も一般的な界面活性剤、或いは帯電防止剤として広く知られた存在であり、既にこのような化合物とポリフェニレンエーテル系樹脂との組成物は公知である（例えば、特許文献２参照）が、該特許文献は非強化系のポリフェニレンエーテル系樹脂組成物である。
また、アルキルスルホン酸金属塩とポリフェニレンエーテル系樹脂の樹脂組成物はその他にも公知であるが（例えば、特許文献３、４参照）、これらの特許に記された技術も非強化系でのポリフェニレンエーテル系樹脂組成物に関するものであり、その上いずれも耐環境応力亀裂性改良や耐光性改良等に関するものである。帯電防止効果についての記載はない。
以上、説明したように、無機質充填剤を配合した強化樹脂組成物材料からなる成形品に機械的物性、耐久性等を低下させることなく、且つ作業工程を増やすことなく、帯電防止性能を付与する技術が望まれていた。
Alkyl sulfonic acid metal salts, which are antistatic agents used in the present invention, are also widely known as general surfactants or antistatic agents. The composition of such a compound and a polyphenylene ether resin is already present. Although the thing is well-known (for example, refer patent document 2), this patent document is a non-reinforced polyphenylene ether-type resin composition.
Other resin compositions of alkylsulfonic acid metal salts and polyphenylene ether resins are also known (see, for example, Patent Documents 3 and 4), but the technology described in these patents is also non-reinforced polyphenylene. The present invention relates to an ether-based resin composition, and all of them relate to improvement of environmental stress crack resistance and light resistance. There is no description about the antistatic effect.
As described above, an antistatic performance is imparted to a molded article made of a reinforced resin composition material containing an inorganic filler without deteriorating mechanical properties, durability, and the like, and without increasing work steps. Technology was desired.
本発明は事務機器分野や情報機器分野に有効に使用できる、帯電防止性に優れると共に、成形体の表面平滑性や組成物中の無機質充填剤の樹脂密着性に優れ、更に耐熱性、剛性、流動性、耐衝撃性、摺動性にも優れた強化ポリフェニレンエーテル系樹脂組成物およびその製造方法を提供することを目的とする。 The present invention can be effectively used in the field of office equipment and information equipment, is excellent in antistatic properties, is excellent in surface smoothness of molded articles and resin adhesion of inorganic fillers in the composition, and further has heat resistance, rigidity, An object of the present invention is to provide a reinforced polyphenylene ether resin composition excellent in fluidity, impact resistance, and slidability, and a method for producing the same.
本発明者らは、環境に悪影響を及ぼさず、耐熱性、剛性、流動性、耐衝撃性等をさほど低下させずに、無機質充填剤で強化したポリフェニレンエーテル系樹脂組成物の帯電防止性を改良することを目的として鋭意検討した結果、ポリフェニレンエーテル樹脂、またはポリフェニレンエーテル樹脂とスチレン系樹脂とからなる組成物中の少なくとも２重量％以上を不飽和カルボン酸或いはその官能的誘導体で変性した官能化ポリフェニレンエーテルで置き換え、シラン化合物で表面処理した無機質充填剤を用い、更に帯電防止剤としてアルキルスルホン酸金属塩を使用することによって、成形体の表面外観や組成物中の無機質充填剤の樹脂密着性を悪化させることなく、耐熱性や剛性の低下を抑えて流動性、耐衝撃性、摺動性等に優れると共に他の帯電防止剤では付与することのできない良好な帯電防止性能の付与が可能であることを見出し、また、燐酸エステル系難燃剤の配合によって難燃効果が飛躍的に向上することも見出し、本発明に至った。 The inventors have improved the antistatic property of a polyphenylene ether resin composition reinforced with an inorganic filler without adversely affecting the environment and without significantly reducing heat resistance, rigidity, fluidity, impact resistance, etc. As a result of intensive studies aimed at achieving the above, functionalized polyphenylene in which at least 2% by weight or more in a composition comprising a polyphenylene ether resin or a polyphenylene ether resin and a styrenic resin is modified with an unsaturated carboxylic acid or a functional derivative thereof. By using an inorganic filler that has been replaced with ether and surface-treated with a silane compound, and further using an alkylsulfonic acid metal salt as an antistatic agent, the surface appearance of the molded body and the resin adhesion of the inorganic filler in the composition can be improved. Without exacerbating the deterioration of heat resistance and rigidity, it has excellent fluidity, impact resistance, slidability, etc. The present inventors have found that it is possible to impart good antistatic performance that cannot be imparted by the antistatic agent of the present invention, and that the flame retardant effect is drastically improved by the incorporation of a phosphate ester flame retardant, the present invention It came to.
即ち本発明は、
［１］ポリフェニレンエーテル樹脂中の一部または全部が不飽和カルボン酸もしくはその官能的誘導体で変性された官能化ポリフェニレンエーテルで置き換えたポリフェニレンエーテル樹脂（Ａ）成分１００重量部に対し、アルキルスルホン酸金属塩（Ｂ）０．５〜１５重量部およびシラン化合物で表面処理した無機質充填剤（Ｃ）５〜１５０重量部、を含有する強化ポリフェニレンエーテル系樹脂組成物、
［２］ポリフェニレンエーテル樹脂が、ポリフェニレンエーテル樹脂とスチレン系樹脂とからなることを特徴とする上記１に記載の強化ポリフェニレンエーテル系樹脂組成物、
［３］（Ｂ）成分が、帯電防止剤であることを特徴とする上記１または２に記載の強化ポリフェニレンエーテル系樹脂組成物、
That is, the present invention
[1] Alkylsulfonic acid metal with respect to 100 parts by weight of polyphenylene ether resin (A) component in which part or all of polyphenylene ether resin is replaced with functionalized polyphenylene ether modified with unsaturated carboxylic acid or functional derivative thereof A reinforced polyphenylene ether-based resin composition containing 0.5 to 15 parts by weight of a salt (B) and 5 to 150 parts by weight of an inorganic filler (C) surface-treated with a silane compound,
[2] The reinforced polyphenylene ether resin composition as described in 1 above, wherein the polyphenylene ether resin comprises a polyphenylene ether resin and a styrene resin.
[3] The reinforced polyphenylene ether-based resin composition as described in 1 or 2 above, wherein the component (B) is an antistatic agent,
［４］（Ａ）成分が、不飽和カルボン酸もしくはその官能的誘導体で変性した官能化ポリフェニレンエーテル樹脂２〜１００重量％およびポリフェニレンエーテル樹脂９８〜０重量％からなることを特徴とする上記１〜３のいずれか記載の強化ポリフェニレンエーテル系樹脂組成物、
［５］（Ａ）成分が、不飽和カルボン酸もしくはその官能的誘導体で変性した官能化ポリフェニレンエーテル樹脂を２〜１０重量％およびポリフェニレンエーテル樹脂９８〜９０重量部からなることを特徴とする上記１〜４のいずれか１項に記載の強化ポリフェニレンエーテル系樹脂組成物、
［６］不飽和カルボン酸もしくはその官能的誘導体で変性された官能化ポリフェニレンエーテル樹脂の不飽和カルボン酸或いはその官能的誘導体の付加量が０．０５〜５重量％の範囲にあることを特徴とする上記１〜５のいずれか１項に記載の強化ポリフェニレンエーテル系樹脂組成物、
[4] The component (A) is composed of 2 to 100% by weight of a functionalized polyphenylene ether resin modified with an unsaturated carboxylic acid or a functional derivative thereof and 98 to 0% by weight of a polyphenylene ether resin. 3. The reinforced polyphenylene ether resin composition according to any one of 3,
[5] The component 1 above, wherein the component (A) comprises 2 to 10% by weight of a functionalized polyphenylene ether resin modified with an unsaturated carboxylic acid or a functional derivative thereof and 98 to 90 parts by weight of the polyphenylene ether resin. Reinforced polyphenylene ether resin composition according to any one of -4,
[6] The addition amount of the unsaturated carboxylic acid or functional derivative thereof in the functionalized polyphenylene ether resin modified with the unsaturated carboxylic acid or functional derivative thereof is in the range of 0.05 to 5% by weight. The reinforced polyphenylene ether-based resin composition according to any one of 1 to 5 above,
［７］更に、燐酸エステル系難燃剤（Ｄ）５〜４０重量部、を含有してなる上記１〜５のいずれか１項に記載の強化ポリフェニレンエーテル系樹脂組成物、
［８］強化ポリフェニレンエーテル系樹脂組成物の製造方法において、単軸或いは二軸押出機を用い、（Ｂ）成分の平均粒子径が２〜１０ｍｍの粒（ペレット）状であるものを使用して製造することを特徴とする上記１〜７のいずれか１項に記載の強化ポリフェニレンエーテル系樹脂組成物の製造方法、
［９］上記８に記載の強化ポリフェニレンエーテル系樹脂組成物の製造方法で得られた強化ポリフェニレンエーテル系樹脂組成物、
［１０］上記１〜７および９のいずれか１項に記載の強化ポリフェニレンエーテル系樹脂組成物を用い成形してなる成形体、
である。
[7] The reinforced polyphenylene ether-based resin composition according to any one of 1 to 5, further comprising 5 to 40 parts by weight of a phosphoric ester-based flame retardant (D),
[8] In the method for producing a reinforced polyphenylene ether-based resin composition, a single-screw or twin-screw extruder is used, and the component (B) is in the form of particles (pellets) having an average particle diameter of 2 to 10 mm. A method for producing a reinforced polyphenylene ether-based resin composition according to any one of the above 1 to 7, characterized in that it is produced,
[9] A reinforced polyphenylene ether resin composition obtained by the method for producing a reinforced polyphenylene ether resin composition as described in 8 above,
[10] A molded product formed by molding the reinforced polyphenylene ether-based resin composition according to any one of 1 to 7 and 9,
It is.
本発明の強化樹脂組成物は帯電防止性に優れると共に、成形品の表面平滑性や組成物中の無機質充填剤の樹脂密着性、更に耐熱性、剛性、流動性、耐衝撃性、摺動性に優れる。 The reinforced resin composition of the present invention is excellent in antistatic property, surface smoothness of a molded product, resin adhesion of an inorganic filler in the composition, heat resistance, rigidity, fluidity, impact resistance, slidability Excellent.
本発明を更に詳細に説明する。
本発明の（Ａ）成分を構成するポリフェニレンエーテル樹脂としては、下記に示す構成単位が一般式（１−ａ）または（１−ｂ）からなる単独重合体、あるいは共重合体が使用できる。
The present invention will be described in further detail.
As the polyphenylene ether resin constituting the component (A) of the present invention, a homopolymer or copolymer in which the structural units shown below are represented by the general formula (1-a) or (1-b) can be used.
（式中、Ｒ１，Ｒ２，Ｒ３，Ｒ４，Ｒ５，Ｒ６は炭素１〜４のアルキル基、アリール基、ハロゲン、水素等の一価の残基であり、Ｒ５，Ｒ６は同時に水素ではない。） (In the formula, R1, R2, R3, R4, R5, and R6 are monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, and hydrogen, and R5 and R6 are not hydrogen at the same time.)
ポリフェニレンエーテル系樹脂の単独重合体の代表例としては、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（２，６−ジエチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２，６−ジ−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ｎ−ブチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−イソプロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ヒドロキシエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル等のホモポリマーが挙げられる。 Typical examples of the homopolymer of polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl 1,4-phenylene) ether, poly (2 , 6-Diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ) Ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl) -1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenol) Include homopolymers of alkylene) ether.
ポリフェニレンエーテル共重合体としては、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、２，６−ジメチルフェノールとｏ−クレゾールとの共重合体あるいは２，３，６−トリメチルフェノールとｏ−クレゾールとの共重合体等、ポリフェニレンエーテル構造を主体とするポリフェニレンエーテル共重合体である。
また、本発明のポリフェニレンエーテル系樹脂中には、本発明の主旨に反しない限り、他の種々のフェニレンエーテルユニットを部分構造として含んでいても構わない。これらフェニレンエーテルユニットとしては、例えば、特開平１−２９７４２８号公報及び特開昭６３−３０１２２２号公報に記載されている、２−（ジアルキルアミノメチル）−６−メチルフェニレンエーテルユニットや、２−（Ｎ−アルキル−Ｎ−フェニルアミノメチル）−６−メチルフェニレンエーテルユニット等が挙げられる。
また、ポリフェニレンエーテル樹脂の主鎖中にジフェノキノン等が少量結合したものも含まれる。
Examples of the polyphenylene ether copolymer include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2,3,6. -Polyphenylene ether copolymers mainly composed of a polyphenylene ether structure, such as a copolymer of trimethylphenol and o-cresol.
In addition, the polyphenylene ether resin of the present invention may contain other various phenylene ether units as partial structures as long as it does not contradict the gist of the present invention. As these phenylene ether units, for example, 2- (dialkylaminomethyl) -6-methylphenylene ether units described in JP-A-1-297428 and JP-A-63-301222, 2- ( N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit and the like.
Also included are those in which a small amount of diphenoquinone or the like is bonded to the main chain of the polyphenylene ether resin.
本発明（Ａ）成分を構成するポリフェニレンエーテル樹脂において、その一部または全部を不飽和カルボン酸或いはその官能的誘導体で変性した官能化ポリフェニレンエーテルで置き換えることが必要である。この場合、変性は不飽和カルボン酸やその官能的誘導体の中の１種により行われても良いし、２種以上の組み合わせによって行われても良い。またその他の単量体、例えばスチレンとの組み合わせで行うこともできる。
本発明に用いられるポリフェニレンエーテル樹脂の固有粘度（クロロホルム溶媒で３０℃にて測定）は０．２〜０．９が好ましく、より好ましくは０．４〜０．６である。耐熱性や耐衝撃性等の機械物性や耐薬品性、耐久性の観点から０．２以上が好ましく、成形加工性の観点から０．９以下が好ましい。
In the polyphenylene ether resin constituting the component (A) of the present invention, it is necessary to replace part or all of it with a functionalized polyphenylene ether modified with an unsaturated carboxylic acid or a functional derivative thereof. In this case, the modification may be performed with one of unsaturated carboxylic acids or functional derivatives thereof, or may be performed with a combination of two or more. Moreover, it can also carry out in combination with another monomer, for example, styrene.
The intrinsic viscosity (measured with a chloroform solvent at 30 ° C.) of the polyphenylene ether resin used in the present invention is preferably 0.2 to 0.9, more preferably 0.4 to 0.6. From the viewpoint of mechanical properties such as heat resistance and impact resistance, chemical resistance, and durability, 0.2 or more is preferable, and from the viewpoint of molding processability, 0.9 or less is preferable.
不飽和カルボン酸或いはその官能的誘導体としては、例えば、マレイン酸、フマル酸、イタコン酸、ハロゲン化マレイン酸、シス−４シクロヘキセン−１，２−ジカルボン酸、エンド−シス−ビシクロ〔２，２，１〕−５−ヘプテン−２，３−ジカルボン酸などや、これらジカルボン酸の酸無水物、エステル、アミド、イミドなど、更にはアクリル酸、メタクリル酸などや、これらモノカルボン酸のエステル、アミドなどが挙げられる。これらは１種用いてもよいし、２種以上を組み合わせて用いてもよい。これらの中で特に、無水マレイン酸が好適である。 Examples of unsaturated carboxylic acids or functional derivatives thereof include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo [2,2, 1] -5-heptene-2,3-dicarboxylic acid, etc., acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, etc., esters of these monocarboxylic acids, amides, etc. Is mentioned. These may be used alone or in combination of two or more. Of these, maleic anhydride is particularly preferred.
本発明で使用される不飽和カルボン酸或いはその官能的誘導体で変性した官能化ポリフェニレンエーテルの製造は、例えば、ラジカル開始剤の存在下で、ポリフェニレンエーテル樹脂に不飽和カルボン酸やその官能的誘導体を溶融混練して反応させることによって製造される。また溶融させずに固相反応によっても製造される。また、スチレン系単量体を共存させてこれを構成単位中に含ませることもできるし、スチレン系樹脂を共存させて変性スチレン系樹脂を生成させ、これを含有したまま用いることもできる。 The production of a functionalized polyphenylene ether modified with an unsaturated carboxylic acid or a functional derivative thereof used in the present invention is performed, for example, by adding an unsaturated carboxylic acid or a functional derivative thereof to a polyphenylene ether resin in the presence of a radical initiator. Manufactured by melt-kneading and reacting. It is also produced by solid phase reaction without melting. Moreover, a styrene monomer can be coexisted and contained in the structural unit, or a styrene resin can be coexisted to produce a modified styrene resin, which can be used as it is contained.
本発明で使用される不飽和カルボン酸或いはその官能的誘導体で変性した官能化ポリフェニレンエーテルは、不飽和カルボン酸或いはその官能的誘導体の付加量は０．０５〜５重量％が好ましく、より好ましくは０．２〜３重量％である。機械物性や耐久性改良効果の観点から０．０５重量％以上５重量％以下が好ましい。５重量％を超えてもその改良効果はさほど顕著で無くなる。
本発明で使用されるスチレン系樹脂とは、スチレン系化合物またはスチレン系化合物と共重合可能な化合物を、ゴム質重合体存在下または非存在下に重合して得られる重合体である。
本発明においてスチレン系化合物とは、一般式（２）
In the functionalized polyphenylene ether modified with the unsaturated carboxylic acid or functional derivative thereof used in the present invention, the addition amount of the unsaturated carboxylic acid or functional derivative thereof is preferably 0.05 to 5% by weight, more preferably 0.2 to 3% by weight. From the viewpoint of mechanical properties and durability improving effect, it is preferably 0.05% by weight or more and 5% by weight or less. Even if it exceeds 5% by weight, the improvement effect is not so remarkable.
The styrene resin used in the present invention is a polymer obtained by polymerizing a styrene compound or a compound copolymerizable with a styrene compound in the presence or absence of a rubbery polymer.
In the present invention, the styrene compound is a compound represented by the general formula (2).
（式中、Ｒは水素、低級アルキルまたはハロゲンを示し、Ｚはビニル基、水素、ハロゲン及び低級アルキル基よりなる群から選択され、ｐは０〜５の整数である。） (In the formula, R represents hydrogen, lower alkyl, or halogen, Z is selected from the group consisting of vinyl group, hydrogen, halogen, and lower alkyl group, and p is an integer of 0-5.)
これらの具体例としては、スチレン、α−メチルスチレン、２，４−ジメチルスチレン、モノクロロスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、エチルスチレン等が挙げられる。また、スチレン系化合物と共重合可能な化合物としては、メチルメタクリレート、エチルメタクリレート等のメタクリル酸エステル類；アクリロニトリル、メタクリロニトリル等の不飽和ニトリル化合物類；無水マレイン酸等の酸無水物等が挙げられ、スチレン系化合物と共に使用される。また、ゴム質重合体としては共役ジエン系ゴムおよび共役ジエンと芳香族ビニル化合物のコポリマーまたはこれらの水添物あるいはエチレン−プロピレン共重合体系ゴム等が挙げられる。本発明のために特に好適なポリスチレン系樹脂はポリスチレンおよびゴム強化ポリスチレンである。 Specific examples thereof include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Examples of the compound copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used with styrenic compounds. Examples of rubbery polymers include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, hydrogenated products thereof, or ethylene-propylene copolymer rubbers. Particularly preferred polystyrene resins for the present invention are polystyrene and rubber reinforced polystyrene.
本発明の（Ｂ）成分であるアルキルスルホン酸金属塩とは、化学式Ｒ−ＳＯ３Ｘ（Ｒ：アルキル基、Ｘ：アルカリ金属またはアルカリ土類金属）で示される化合物を示す。このようなアルキルスルホン酸金属塩の中でも炭素数８〜２４のアルキルスルホン酸金属塩が好ましく、より好ましい炭素数の範囲は１２〜２０であり、特に好ましくは１２〜１６である。耐熱性、耐衝撃性等の機械物性の観点から８以上が好ましく、帯電防止性、成形加工性の観点から２４以下が好ましい。
その中でもアルキルスルホン酸ナトリウムが特に好ましい。具体例を挙げれば、ドデカンスルホン酸ナトリウム、テトラデカンスルホン酸ナトリウム、ヘキサデカンスルホン酸ナトリウム、オクタデカンスルホン酸ナトリウム、デシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、テトラデシルベンゼンスルホン酸ナトリウム等が挙げられる。これらは単独で用いても良いし、これら２種以上の混合物として用いても良い。
The alkylsulfonic acid metal salt which is the component (B) of the present invention refers to a compound represented by the chemical formula R—SO 3 X (R: alkyl group, X: alkali metal or alkaline earth metal). Among such alkylsulfonic acid metal salts, alkylsulfonic acid metal salts having 8 to 24 carbon atoms are preferable, and a more preferable range of the carbon number is 12 to 20, particularly preferably 12 to 16. From the viewpoint of mechanical properties such as heat resistance and impact resistance, 8 or more is preferable, and from the viewpoint of antistatic properties and molding processability, 24 or less is preferable.
Of these, sodium alkylsulfonate is particularly preferred. Specific examples include sodium dodecane sulfonate, sodium tetradecane sulfonate, sodium hexadecane sulfonate, sodium octadecane sulfonate, sodium decyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodium tetradecyl benzene sulfonate, and the like. These may be used alone or as a mixture of two or more thereof.
アルキルスルホン酸金属塩を本発明に用いる際のその性状は粉体状、顆粒状、鱗片（フレーク）状、粒（ペレット）状等用いることが可能である。しかし本発明樹脂組成物の、押出機による大量生産時にアルキルスルホン酸金属塩の吸湿によって配合原料中に塊が生じる等、原料ホッパーから押出機スクリューまでのフィードライン間で原料のライン詰りを起こして、生産を阻害される場合が少なくないことに本発明者らは気づいた。そのため、粒子が小さく吸湿しやすい粉体状よりはむしろ粒子が比較的大きく吸湿し難い粒（ペレット）状であることが望ましい。特に加工作業場での作業環境に及ぼす影響やハンドリング性、本発明樹脂組成物の生産安定性等を総合的に考慮した場合、平均粒子径が２〜１０ｍｍの粒（ペレット）状であることが望ましく、更には平均粒子径３〜７ｍｍの粒（ペレット）状であることがよりいっそう望ましい。尚、ここで言う平均粒子径とは粒（ペレット）５０個を無作為に抽出してその最長径と最短径を測定し、各々の粒（ペレット）の最長径と最短径の和を２で割った値を合計した数値を５０で割って求めた値のことを示している。 When the alkylsulfonic acid metal salt is used in the present invention, it can be used in the form of powder, granules, scales (flakes), grains (pellets) or the like. However, when the resin composition of the present invention is mass-produced by an extruder, lumps are formed in the blended raw material due to moisture absorption of the alkyl sulfonic acid metal salt. The present inventors have found that production is often inhibited. Therefore, it is desirable that the particles are relatively large and difficult to absorb moisture, rather than a powder that is small and easy to absorb moisture. In particular, when considering the influence on the working environment in the processing workplace, handling properties, production stability of the resin composition of the present invention, etc., it is desirable that the particles have a mean particle size of 2 to 10 mm (pellet). Furthermore, it is even more desirable that it is in the form of particles (pellets) having an average particle diameter of 3 to 7 mm. The average particle size referred to here means that 50 grains (pellets) are randomly extracted and the longest diameter and shortest diameter are measured, and the sum of the longest diameter and shortest diameter of each grain (pellet) is 2. It shows a value obtained by dividing the sum of the divided values by 50.
本発明の（Ｃ）成分であるシラン化合物で表面処理した無機質充填剤において、本発明に使用される無機質充填剤は熱可塑性樹脂を強化するために一般的に用いられるものである。その具体例としては、ガラス繊維、ガラスフレーク等のガラスフィラー、シリカ、ワラストナイト、アルミナ、タルク、マイカ、クレー類、酸化チタン、亜鉛華、酸化鉄、炭酸カルシウム、硫酸バリウム等が挙げられる。無機質充填剤の形状は特に限定されるものではなく、繊維状、鱗片状、針状、粒状のいずれであっても良いし、二種以上を併用することもできる。 In the inorganic filler surface-treated with the silane compound which is the component (C) of the present invention, the inorganic filler used in the present invention is generally used to reinforce the thermoplastic resin. Specific examples thereof include glass fillers such as glass fibers and glass flakes, silica, wollastonite, alumina, talc, mica, clays, titanium oxide, zinc white, iron oxide, calcium carbonate, barium sulfate and the like. The shape of the inorganic filler is not particularly limited, and may be any of a fibrous shape, a scale shape, a needle shape, and a granular shape, and two or more types may be used in combination.
本発明の（Ｃ）成分において無機質充填剤を表面処理するに用いられるシラン化合物は通常ガラスフィラーやミネラルフィラー等を表面処理するに用いられるものである。その具体例としては、ビニルトリクロルシラン、ビニルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン等のビニルシラン化合物、γ−グリシドキシプロピルトリメトキシシラン等のエポキシシラン化合物、ビスー（３−トリエトキシシリルプロピル）テトラサルファイド等の硫黄系シラン化合物、γ−メルカプトプロピルトリメトキシシラン等のメルカプトシラン化合物、γ−アミノプロピルトリエトキシシラン、γ−ユレイドプロピルトリエトキシシラン等のアミノシラン化合物等が挙げられる。本発明の目的のために特に好適なのはメルカプトシラン化合物及び、アミノシラン化合物である。シラン化合物は単独で用いても二種類以上を併用しても良い。異なるシラン化合物で表面処理した無機質充填剤を混合して用いることもできる。また、これらシラン化合物で表面処理した無機質充填剤と共にシラン化合物以外の表面処理剤で表面処理した無機質充填剤や表面処理していない無機質充填剤を併用しても良い。 The silane compound used for the surface treatment of the inorganic filler in the component (C) of the present invention is usually used for the surface treatment of a glass filler, a mineral filler or the like. Specific examples thereof include vinyl silane compounds such as vinyltrichlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, epoxy silane compounds such as γ-glycidoxypropyltrimethoxysilane, and bis (3-triethoxysilyl). Sulfur-based silane compounds such as propyl) tetrasulfide, mercaptosilane compounds such as γ-mercaptopropyltrimethoxysilane, and aminosilane compounds such as γ-aminopropyltriethoxysilane and γ-ureidopropyltriethoxysilane. Particularly suitable for the purposes of the present invention are mercaptosilane compounds and aminosilane compounds. Silane compounds may be used alone or in combination of two or more. An inorganic filler surface-treated with different silane compounds can also be mixed and used. Moreover, you may use together the inorganic filler surface-treated with surface treating agents other than a silane compound, and the inorganic filler which is not surface-treated with the inorganic filler surface-treated with these silane compounds.
本発明の（Ｄ）成分である燐酸エステル系難燃剤は難燃性付与が必要な場合に用いられるが、本発明（Ｂ）成分であるアルキルスルホン酸金属塩と併用して添加されることによって、特に優れた難燃性が発現される。燐酸エステル系難燃剤の中でも芳香族燐酸エステル系難燃剤が特に好適に用いられ、例えばトリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート、ジキシレニルフェニルホスフェート、ヒドロキシノンビスフェノール、レゾルシノールビスホスフェート、ビスフェノールＡビスホスフェート等のトリフェニル置換タイプの芳香族リン酸エステル類が特に好適に用いられる。これらは単独でも二種以上組み合わせて用いても良い。 The phosphoric ester-based flame retardant as component (D) of the present invention is used when it is necessary to impart flame retardancy, but is added in combination with the alkyl sulfonate metal salt as component (B) of the present invention. In particular, excellent flame retardancy is exhibited. Among the phosphate ester flame retardants, aromatic phosphate ester flame retardants are particularly preferably used. For example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, dixylenyl Triphenyl-substituted aromatic phosphates such as phenyl phosphate, hydroxynon bisphenol, resorcinol bisphosphate, bisphenol A bisphosphate are particularly preferably used. These may be used alone or in combination of two or more.
本発明の（Ａ）成分は、（Ａ）成分の合計量１００重量部に対して、不飽和カルボン酸もしくはその官能的誘導体で変性した官能化ポリフェニレンエーテル樹脂を２〜１０重量部と、ポリフェニレンエーテル樹脂またはポリフェニレンエーテル樹脂およびスチレン系樹脂とからなる組成物９８〜９０重量部とを配合することが好ましく、より好ましくは不飽和カルボン酸もしくはその官能的誘導体で変性した官能化ポリフェニレンエーテル樹脂を３〜７重量部と、ポリフェニレンエーテル樹脂またはポリフェニレンエーテル樹脂およびスチレン系樹脂とからなる組成物９７〜９３重量部とを配合することである。（Ｂ）成分を添加した場合の無機質充填剤との樹脂密着性および剛性、耐衝撃性等の物性の観点から２重量部以上が好ましく、密着性改良効果、溶融流動性および成形体の表面外観の観点から１０重量部以下が好ましい。１０重量部を超えて含有しても無機質充填剤との樹脂密着性改良効果はさほど向上しない。 The component (A) of the present invention comprises 2 to 10 parts by weight of a functionalized polyphenylene ether resin modified with an unsaturated carboxylic acid or a functional derivative thereof with respect to 100 parts by weight of the total amount of the component (A), and a polyphenylene ether It is preferable to blend 98 to 90 parts by weight of a resin or a composition comprising a polyphenylene ether resin and a styrenic resin, more preferably 3 to 3 functionalized polyphenylene ether resin modified with an unsaturated carboxylic acid or a functional derivative thereof. 7 parts by weight and 97 to 93 parts by weight of a composition comprising a polyphenylene ether resin or a polyphenylene ether resin and a styrene resin are blended. (B) 2 parts by weight or more is preferable from the viewpoint of physical properties such as resin adhesion to the inorganic filler and rigidity, impact resistance, etc. when the component is added. Adhesion improving effect, melt flowability and surface appearance of molded article In view of the above, 10 parts by weight or less is preferable. Even if it contains exceeding 10 weight part, the resin adhesive improvement effect with an inorganic filler does not improve so much.
本発明の（Ｂ）成分であるアルキルスルホン酸金属塩の添加量は、（Ａ）成分１００重量部に対して、０．５〜１５重量部の範囲より選ばれる。好ましい範囲は２〜１２重量部であり、より好ましい範囲は４〜９重量部である。十分な帯電防止性付与の観点から０．５重量部以上が好ましく、無機質充填剤との樹脂密着性や成形品表面外観、機械物性の観点から１５重量部以下の添加が好ましい。
本発明の（Ｃ）成分であるシラン化合物で表面処理した無機質充填剤の添加量は、（Ａ）成分１００重量部に対して、５〜１５０重量部の範囲より選ばれる。好ましい範囲は１０〜１２０重量部であり、より好ましい範囲は２０〜１００重量部である。剛性、耐久性付与の観点から５重量部以上の添加が望ましく、成形加工性の観点から１５０重量部以下の添加が望ましい。
The addition amount of the alkylsulfonic acid metal salt which is the component (B) of the present invention is selected from the range of 0.5 to 15 parts by weight with respect to 100 parts by weight of the component (A). A preferable range is 2 to 12 parts by weight, and a more preferable range is 4 to 9 parts by weight. 0.5 parts by weight or more is preferable from the viewpoint of imparting sufficient antistatic properties, and addition of 15 parts by weight or less is preferable from the viewpoints of resin adhesion with an inorganic filler, surface appearance of a molded product, and mechanical properties.
The amount of the inorganic filler surface-treated with the silane compound which is the component (C) of the present invention is selected from the range of 5 to 150 parts by weight with respect to 100 parts by weight of the component (A). A preferred range is 10 to 120 parts by weight, and a more preferred range is 20 to 100 parts by weight. Addition of 5 parts by weight or more is desirable from the viewpoint of imparting rigidity and durability, and addition of 150 parts by weight or less is desirable from the viewpoint of molding processability.
本発明の（Ｄ）成分である燐酸エステル系難燃剤の添加量は（Ａ）成分１００重量部に対して、５〜４０重量部の範囲より選ばれる。好ましい範囲は１０〜３５重量部であり、より好ましい範囲は１５〜３０重量部である。難燃性付与の観点から５重量部以上の添加が望ましく、十分な耐熱性を保持するためには４０重量部以下の添加が望ましい。
本発明の強化樹脂組成物には必要に応じて酸化防止剤、紫外線吸収剤、熱安定剤等の安定剤類や着色剤、離型剤等も添加することができる。
本発明の組成物の調製方法は特に限定されるものではないが、樹脂組成物を大量に安定して製造するには単軸または二軸の押出機が好適に用いられる。
本発明の強化樹脂組成物を用いて成形体を成形する場合、特に成形法に制限は無いが、射出成形、押出成形、真空成形、圧空成形など既に広く知られた成形法が好適に用いられる。
The addition amount of the phosphate ester flame retardant which is the component (D) of the present invention is selected from the range of 5 to 40 parts by weight with respect to 100 parts by weight of the component (A). A preferred range is 10 to 35 parts by weight, and a more preferred range is 15 to 30 parts by weight. The addition of 5 parts by weight or more is desirable from the viewpoint of imparting flame retardancy, and the addition of 40 parts by weight or less is desirable to maintain sufficient heat resistance.
If necessary, stabilizers such as antioxidants, ultraviolet absorbers, heat stabilizers, coloring agents, release agents and the like can be added to the reinforced resin composition of the present invention.
The method for preparing the composition of the present invention is not particularly limited, but a single-screw or twin-screw extruder is preferably used for stably producing a large amount of the resin composition.
When a molded body is molded using the reinforced resin composition of the present invention, there is no particular limitation on the molding method, but already known molding methods such as injection molding, extrusion molding, vacuum molding, and pressure molding are preferably used. .
本発明について、実施例に基づき以下具体的に説明する。本発明がこれらの例によって何ら限定されるものではない。尚、以下の用いる部は重量部である。
実施例および比較例中の各測定値は以下の方法によって求めた。
（１）荷重たわみ温度（ＨＤＴ）
ＡＳＴＭ Ｄ６４８に従い、厚み０．６３５ｃｍの試験片を用いて荷重１８．６ｋｇ／ｃｍ２で測定した。
（２）流動性（ＭＩ）
（株）東洋精機製作所製のメルトインデクサーＰ−１１１を用いて、２５０℃、１０ｋｇ荷重にてメルトインデックスを測定した。
（３）ノッチ付きアイゾッド衝撃値（耐衝撃性）
ＡＳＴＭのＤ２５６に基づき２３℃にて測定した。
The present invention will be specifically described below based on examples. The present invention is not limited to these examples. The parts used below are parts by weight.
Each measured value in Examples and Comparative Examples was determined by the following method.
(1) Deflection temperature under load (HDT)
According to ASTM D648, measurement was performed at a load of 18.6 kg / cm 2 using a test piece having a thickness of 0.635 cm.
(2) Fluidity (MI)
Using a melt indexer P-111 manufactured by Toyo Seiki Seisakusho, the melt index was measured at 250 ° C. and a load of 10 kg.
(3) Notched Izod impact value (impact resistance)
Measurements were made at 23 ° C. based on ASTM D256.
（４）曲げ強度、曲げ弾性率
ＡＳＴＭのＤ７９０による曲げ試験法に基づいて三点曲げ試験を２３゜Ｃで測定した。
（５）難燃性
１．６ｍｍ厚みの試験片を用いてＵＬ−９４試験法に基づいて測定した。
（６）無機質充填剤の樹脂密着性
ノッチ付きアイゾッド試験片の破断面をイオンスパッタリング装置で金蒸着を行った後、走査型電子顕微鏡（ＳＥＭ）を用いて３５０倍の倍率で破断面上の無機質充填剤表面の観察を行い、樹脂の密着状態を目視によって評価した。
(4) Bending strength and flexural modulus A three-point bending test was measured at 23 ° C based on the bending test method according to ASTM D790.
(5) Flame retardance It measured based on the UL-94 test method using the 1.6 mm-thick test piece.
(6) Resin Adhesiveness of Inorganic Filler After fracturing the fracture surface of the notched Izod test piece with an ion sputtering apparatus, the inorganic material on the fracture surface at a magnification of 350 times using a scanning electron microscope (SEM) The surface of the filler was observed, and the adhesion state of the resin was visually evaluated.
（７）動摩擦係数、摩耗深さ（摺動性）
（株）オリエンテック社製の往復摺動試験機ＡＦＴ−１５Ｍを用いて、５０ｍｍ×９０ｍｍ×厚み２．５ｍｍの平板成形片表面を次の条件でピン／ディスク摩擦係数を測定した。ピン：ＳＵＳ３０４製５ｍｍ径のステンレス球、荷重：０．５ｋｇ、移動速度：３０ｍｍ／ｓｅｃ、片道距離：２０ｍｍ、往復回数５，０００回、測定温度：２３℃。動摩擦係数は往復回数５，０００回後の測定値である。摩耗深さも往復回数５，０００回後の平板成形片表面の摩耗部分を、（株）東京精密社製の表面粗さ計サーフコムＥ−ＭＵ−Ｓ０３Ａを用いて測定した値である。
（８）帯電防止性（表面抵抗率）
５０ｍｍ×９０ｍｍ×厚み２．５ｍｍの平板成形片を用い、三菱化学（株）製の抵抗率計（ハイレスターＩＰ）により、温度２１〜２５℃、湿度４０〜６０％の条件下で２４時間以上放置した後測定した。
(7) Dynamic friction coefficient, wear depth (slidability)
Using a reciprocating sliding tester AFT-15M manufactured by Orientec Co., Ltd., the pin / disk friction coefficient was measured on the surface of a flat molded piece of 50 mm × 90 mm × 2.5 mm thickness under the following conditions. Pin: SUS304 5 mm diameter stainless steel sphere, load: 0.5 kg, moving speed: 30 mm / sec, one-way distance: 20 mm, number of reciprocations 5,000 times, measurement temperature: 23 ° C. The dynamic friction coefficient is a measured value after 5,000 reciprocations. The wear depth is also a value obtained by measuring the worn portion of the surface of the flat plate molded piece after 5,000 reciprocations using a surface roughness meter Surfcom E-MU-S03A manufactured by Tokyo Seimitsu Co., Ltd.
(8) Antistatic property (surface resistivity)
Using a flat-plate molded piece of 50 mm x 90 mm x thickness 2.5 mm, using a resistivity meter (Hiresta IP) manufactured by Mitsubishi Chemical Corporation under conditions of a temperature of 21 to 25 ° C and a humidity of 40 to 60% for 24 hours or more. Measured after standing.
［実施例１］
固有粘度（クロロホルム溶媒で３０℃にて測定）が０．４６ｄｌ／ｇのポリ（２，６−ジメチル−１，４−フェニレン）エーテル３４重量部、無水マレイン酸により変性したポリ（２，６−ジメチル−１，４−フェニレン）エーテル〔ナトリウムメチラートの滴定により求めた無水マレイン酸変性ポリ（２，６−ジメチル−１，４−フェニレン）エーテル１００重量％中における無水マレイン酸付加量０．４８重量％〕２．５重量部、ＰＳジャパン（株）社製ポリスチレンＨ９４０５を８．５重量部、平均粒子径が約５ｍｍの粒（ペレット）状である日本油脂（株）製のアルキルスルホン酸ナトリウム（商品名：エレガンＡ−２０００ＳＧ）２重量部、大八化学工業（株）製の芳香族縮合リン酸エステル系難燃剤（商品名：ＣＲ−７４１）１３重量部および、日本硝子繊維（株）製のシラン化合物で表面処理したガラス繊維（商品名：ＲＥＳ０３−ＴＰ３０）２０重量部、クラレ（株）製スゾライトマイカ２００ＨＫを２０重量部とを池貝鉄工所（株）製のＰＣＭ３０二軸押出機を使用し、ニーディングディスクＬ：２個、ニーディングディスクＲ：３個、シーリング：１個を有するスクリューパターンで、シリンダー温度３００℃、スクリュー回転数１００ｒｐｍで溶融混練して樹脂組成物を得た。該樹脂組成物の物性試験結果を表１に示す。
[Example 1]
34 parts by weight of poly (2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity (measured at 30 ° C. in a chloroform solvent) of 0.46 dl / g, poly (2,6-modified) with maleic anhydride Dimethyl-1,4-phenylene) ether [maleic anhydride addition in 0.4% maleic anhydride-modified poly (2,6-dimethyl-1,4-phenylene) ether determined by titration of sodium methylate 0.48 % By weight] 2.5 parts by weight, 8.5 parts by weight of polystyrene H9405 made by PS Japan Co., Ltd., sodium alkyl sulfonate made by Nippon Oil & Fats Co., Ltd. in the form of particles (pellets) with an average particle diameter of about 5 mm (Product name: Elegan A-2000SG) 2 parts by weight, an aromatic condensed phosphate ester flame retardant (trade name: CR-741) manufactured by Daihachi Chemical Industry Co., Ltd. Ikekai Iron Works, 20 parts by weight of glass fiber (trade name: RES03-TP30) surface-treated with a silane compound manufactured by Nippon Glass Fiber Co., Ltd., and 20 parts by weight of Kuraray Co., Ltd. Szolite Mica 200HK Using a PCM30 twin screw extruder manufactured by Co., Ltd., a screw pattern having 2 kneading discs L, 3 kneading discs R, and 1 sealing, with a cylinder temperature of 300 ° C. and a screw rotation speed of 100 rpm The resin composition was obtained by melt-kneading. Table 1 shows the physical property test results of the resin composition.
［実施例２］
固有粘度（クロロホルム溶媒で３０℃にて測定）が０．５１ｄｌ／ｇのポリ（２，６−ジメチル−１，４−フェニレン）エーテル１８重量部、実施例１で使用したものと同じ無水マレイン酸変性ポリ（２，６−ジメチル−１，４−フェニレン）エーテル３重量部、ＰＳジャパン（株）製ポリスチレンＨ９４０５を２０重量部、ＰＳジャパン（株）製ポリスチレン６８５を１５重量部、実施例１で使用したものと同じアルキルスルホン酸ナトリウム５部、実施例１で使用したものと同じ芳香族縮合リン酸エステル系難燃剤９重量部および日本硝子繊維（株）製のシラン化合物で表面処理したガラスフレーク（商品名：ＲＥＦＧ−３０２）３０重量部を実施例１と同じ方法で溶融混練して樹脂組成物を得た。該樹脂組成物の物性試験結果を表３に示す。
[Example 2]
18 parts by weight of poly (2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity (measured in chloroform solvent at 30 ° C.) of 0.51 dl / g, the same maleic anhydride as used in Example 1 In Example 1, 3 parts by weight of modified poly (2,6-dimethyl-1,4-phenylene) ether, 20 parts by weight of polystyrene H9405 from PS Japan, 15 parts by weight of polystyrene 685 from PS Japan, Glass flakes surface-treated with 5 parts of the same alkyl sulfonate sodium used, 9 parts by weight of the same aromatic condensed phosphate ester flame retardant used in Example 1, and a silane compound manufactured by Nippon Glass Fiber Co., Ltd. (Product name: REFG-302) 30 parts by weight was melt-kneaded in the same manner as in Example 1 to obtain a resin composition. Table 3 shows the physical property test results of the resin composition.
［実施例３］
固有粘度（クロロホルム溶媒で３０℃にて測定）が０．５１ｄｌ／ｇのポリ（２，６−ジメチル−１，４−フェニレン）エーテル１８重量部を、実施例１で使用したものと同じ無水マレイン酸変性ポリ（２，６−ジメチル−１，４−フェニレン）エーテルに置き換えて実施例２を繰り返して樹脂組成物を得た。該組成物の物性試験結果を表３に示す。
[Example 3]
The same anhydrous maleate as used in Example 1 with 18 parts by weight of poly (2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity (measured with chloroform solvent at 30 ° C.) of 0.51 dl / g The resin composition was obtained by repeating Example 2 by replacing with acid-modified poly (2,6-dimethyl-1,4-phenylene) ether. Table 3 shows the physical property test results of the composition.
［比較例１］
アルキルスルホン酸ナトリウムをＰＳジャパン（株）製ポリスチレンＨ９４０５に置き換えて実施例１を繰り返して樹脂組成物を得た。該組成物の物性試験結果を表１に示す。
[Comparative Example 1]
The resin composition was obtained by repeating Example 1 by replacing sodium alkylsulfonate with polystyrene H9405 manufactured by PS Japan Corporation. The physical property test results of the composition are shown in Table 1.
［比較例２］
アルキルスルホン酸ナトリウムを三洋化成工業（株）製のジオクチルスルホコハク酸ナトリウム（商品名：サンセパラー１００）に置き換えて実施例１を繰り返して樹脂組成物を得た。該組成物の物性試験結果を表１に示す。
[Comparative Example 2]
Example 1 was repeated by replacing sodium alkylsulfonate with sodium dioctylsulfosuccinate (trade name: Sansepara 100) manufactured by Sanyo Chemical Industries, Ltd. to obtain a resin composition. The physical property test results of the composition are shown in Table 1.
［比較例３］
アルキルスルホン酸ナトリウムを日本油脂（株）製のアシル〔牛脂〕メチルタウリン酸ナトリウム（商品名：ダイヤポンＴ）に置き換えて実施例１を繰り返して樹脂組成物を得た。該組成物の物性試験結果を表１に示す。
[Comparative Example 3]
Example 1 was repeated by replacing sodium alkyl sulfonate with acyl [beef tallow] sodium methyl taurate (trade name: Diapon T) manufactured by Nippon Oil & Fats Co., Ltd. to obtain a resin composition. The physical property test results of the composition are shown in Table 1.
［比較例４］
アルキルスルホン酸ナトリウムを日本油脂（株）製のアニオン型界面活性剤（商品名：フィレットＬ）に置き換えて実施例１を繰り返して樹脂組成物を得た。該組成物の物性試験結果を表２に示す。
[Comparative Example 4]
Example 1 was repeated by replacing sodium alkyl sulfonate with an anionic surfactant (trade name: Fillet L) manufactured by NOF Corporation to obtain a resin composition. The physical property test results of the composition are shown in Table 2.
［比較例５］
アルキルスルホン酸ナトリウムを日本油脂（株）製の含窒素非イオン型界面活性剤（商品名：スタホームＤＬ）に置き換えて実施例１を繰り返して樹脂組成物を得た。該組成物の物性試験結果を表２に示す。
[Comparative Example 5]
Example 1 was repeated by replacing the sodium alkylsulfonate with a nitrogen-containing nonionic surfactant (trade name: Stahome DL) manufactured by NOF Corporation to obtain a resin composition. The physical property test results of the composition are shown in Table 2.
［比較例６］
アルキルスルホン酸ナトリウムをミヨシ油脂（株）製のカチオン型界面活性剤（商品名：ダスパー１４００Ｂ）に置き換えて実施例１を繰り返して樹脂組成物を得た。該組成物の物性試験結果を表２に示す。
[Comparative Example 6]
Example 1 was repeated by replacing sodium alkyl sulfonate with a cationic surfactant (trade name: Dasper 1400B) manufactured by Miyoshi Oil & Fats Co., Ltd., to obtain a resin composition. The physical property test results of the composition are shown in Table 2.
［比較例７］
アルキルスルホン酸ナトリウムをＰＳジャパン（株）製のポリスチレン６８５に置き換えて実施例２を繰り返して樹脂組成物を得た。該組成物の物性試験結果を表３に示す。
[Comparative Example 7]
The resin composition was obtained by repeating Example 2 by replacing sodium alkylsulfonate with polystyrene 685 manufactured by PS Japan Corporation. Table 3 shows the physical property test results of the composition.
［比較例８］
無水マレイン酸変性ポリ（２，６−ジメチル−１，４−フェニレン）エーテル３重量部を、固有粘度（クロロホルム溶媒で３０℃にて測定）０．５１ｄｌ／ｇのポリ（２，６−ジメチル−１，４−フェニレン）エーテルに置き換えて実施例２を繰り返して樹脂組成物を得た。該組成物の物性試験結果を表３に示す。
[Comparative Example 8]
3 parts by weight of maleic anhydride-modified poly (2,6-dimethyl-1,4-phenylene) ether was added to poly (2,6-dimethyl-) having an intrinsic viscosity (measured at 30 ° C. with a chloroform solvent) of 0.51 dl / g. The resin composition was obtained by repeating Example 2 substituting for 1,4-phenylene) ether. Table 3 shows the physical property test results of the composition.
本発明の強化ポリフェニレンエーテル系樹脂組成物は帯電防止性、摺動性、無機質充填剤の樹脂密着性等に優れ、なおかつ良好な機械物性を保持ししており、家電ＯＡ機器、事務機、情報・通信機器、電気電子部品、建材、日用品、玩具、自動車部品等に広く用いることができる。特に家電・ＯＡ事務機分野においては好適に用いられ、例えば、テレビハウジング、テレビシャーシ、デフレクションヨーク等のテレビ部品、エアコン部品、オーディオ部品、ＴＶゲーム機部品、モニターハウジング、モニターシャーシ、ノート型ＰＣハウジング、ＭＤシャーシ類、ＤＶＤシャーシ類、ＤＶＤスリムトレー、車載用ＣＤチェンジャートレー、車載用ＤＶＤデッキフレーム、モーターカバー、ギアボックス、液晶プロジェクターハウジング、ＰＤＡハウジング、アンテナカバー、プリンターハウジング、プリンターシャーシ、プリンター光学箱、トナーカートリッジ、給紙用トレー、スキャナーハウジング、スキャナーフレーム、携帯電話ハウジング、デジタルカメラ周辺部品、空気清浄機部品等の用途が挙げられる。 The reinforced polyphenylene ether-based resin composition of the present invention is excellent in antistatic properties, sliding properties, resin adhesion of inorganic fillers, etc., and has good mechanical properties. -Can be widely used for communication equipment, electrical and electronic parts, building materials, daily necessities, toys, automobile parts, etc. Particularly, it is suitably used in the field of home appliances / OA office machines, for example, TV parts such as TV housings, TV chassis, deflection yokes, air conditioner parts, audio parts, TV game machine parts, monitor housings, monitor chassis, notebook PCs. Housing, MD chassis, DVD chassis, DVD slim tray, in-vehicle CD changer tray, in-vehicle DVD deck frame, motor cover, gear box, LCD projector housing, PDA housing, antenna cover, printer housing, printer chassis, printer optics Applications include boxes, toner cartridges, paper feed trays, scanner housings, scanner frames, mobile phone housings, digital camera peripheral parts, air purifier parts, and the like.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014181318A (en) * | 2013-03-21 | 2014-09-29 | Asahi Kasei Chemicals Corp | Method of producing resin composition |
| CN104292801A (en) * | 2014-09-26 | 2015-01-21 | 苏州博利迈新材料科技有限公司 | Head cover of automobile and preparation method thereof |
| WO2019127939A1 (en) * | 2017-12-26 | 2019-07-04 | 深圳光启尖端技术有限责任公司 | Radome substrate and preparation method therefor |
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2004
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014181318A (en) * | 2013-03-21 | 2014-09-29 | Asahi Kasei Chemicals Corp | Method of producing resin composition |
| CN104292801A (en) * | 2014-09-26 | 2015-01-21 | 苏州博利迈新材料科技有限公司 | Head cover of automobile and preparation method thereof |
| WO2019127939A1 (en) * | 2017-12-26 | 2019-07-04 | 深圳光启尖端技术有限责任公司 | Radome substrate and preparation method therefor |
| US11512172B2 (en) | 2017-12-26 | 2022-11-29 | Kuang-Chi Cutting Edge Technology Ltd. | Radome substrate and preparation method thereof |
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