JP4920210B2 - Resin composition, molded product and IC tray - Google Patents
Resin composition, molded product and IC tray Download PDFInfo
- Publication number
- JP4920210B2 JP4920210B2 JP2005215057A JP2005215057A JP4920210B2 JP 4920210 B2 JP4920210 B2 JP 4920210B2 JP 2005215057 A JP2005215057 A JP 2005215057A JP 2005215057 A JP2005215057 A JP 2005215057A JP 4920210 B2 JP4920210 B2 JP 4920210B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- weight
- resin composition
- polyphenylene ether
- styrene
- 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.)
- Active
Links
- 239000011342 resin composition Substances 0.000 title claims description 59
- 229920005989 resin Polymers 0.000 claims description 80
- 239000011347 resin Substances 0.000 claims description 80
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 66
- 229920001955 polyphenylene ether Polymers 0.000 claims description 66
- 239000006229 carbon black Substances 0.000 claims description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 238000000465 moulding Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 9
- 239000000806 elastomer Substances 0.000 claims description 9
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- 229920006132 styrene block copolymer Polymers 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 24
- -1 polyphenylene Polymers 0.000 description 23
- 238000000034 method Methods 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000428 dust Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 8
- 229920000388 Polyphosphate Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000001205 polyphosphate Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 235000011176 polyphosphates Nutrition 0.000 description 4
- 229920005990 polystyrene resin Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920001890 Novodur Polymers 0.000 description 3
- 229920000265 Polyparaphenylene Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
- VJVQIXWLBAKWDJ-UHFFFAOYSA-N 1-phenoxy-2,5-diphenyl-4,6-di(propan-2-yl)-3-propan-2-yloxybenzene Chemical compound C1(=CC=CC=C1)OC=1C(=C(OC(C)C)C(=C(C1C(C)C)C1=CC=CC=C1)C(C)C)C1=CC=CC=C1 VJVQIXWLBAKWDJ-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RZYPTVQMXHHFAK-UHFFFAOYSA-N C1(=CC=CC=C1)C=1C(=C(C(=C(O)C1)C1=CC=CC=C1)O)C(C)C Chemical compound C1(=CC=CC=C1)C=1C(=C(C(=C(O)C1)C1=CC=CC=C1)O)C(C)C RZYPTVQMXHHFAK-UHFFFAOYSA-N 0.000 description 1
- DSJDDPQZEHCNRB-UHFFFAOYSA-N CC(O)=O.[N-2]CC[N-2].[Na+].[Na+].[Na+].[Na+] Chemical compound CC(O)=O.[N-2]CC[N-2].[Na+].[Na+].[Na+].[Na+] DSJDDPQZEHCNRB-UHFFFAOYSA-N 0.000 description 1
- AWBPYAPGLOPEJJ-UHFFFAOYSA-N CC1(C(C(=CC=C1)C)(C)O)C Chemical compound CC1(C(C(=CC=C1)C)(C)O)C AWBPYAPGLOPEJJ-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 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
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- HPUPGAFDTWIMBR-UHFFFAOYSA-N [methyl(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(C)OC1=CC=CC=C1 HPUPGAFDTWIMBR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920001923 acrylonitrile-ethylene-styrene Polymers 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 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
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- PNWJXICONNROSM-UHFFFAOYSA-N ethene;prop-2-enenitrile;styrene Chemical compound C=C.C=CC#N.C=CC1=CC=CC=C1 PNWJXICONNROSM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- KGHYGBGIWLNFAV-UHFFFAOYSA-N n,n'-ditert-butylethane-1,2-diamine Chemical compound CC(C)(C)NCCNC(C)(C)C KGHYGBGIWLNFAV-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229910001174 tin-lead alloy Inorganic materials 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-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
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Landscapes
- Wrappers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
Description
本発明は、樹脂組成物等に関する。さらに詳しくは、スチレン系樹脂を含むポリフェニレンエーテル樹脂とカーボンブラックからなる、機械的強度、耐熱性に優れ、かつ、接触・摩擦時の摩耗によるカーボンブラックの脱離の小さい樹脂組成物、及び該樹脂組成物を用いた成形品、特に、ＩＣトレーに関する。 The present invention relates to a resin composition and the like. More specifically, a resin composition comprising a polyphenylene ether resin containing styrene-based resin and carbon black, excellent in mechanical strength and heat resistance, and having a small carbon black detachment due to wear during contact and friction, and the resin The present invention relates to a molded article using the composition, particularly to an IC tray.
近年、ＯＡ機器や電子機器の小型軽量化や高集積化、高精度化が進み、それに伴い、電気電子部品への塵やほこりの付着を極力低減させたいという要求が増えてきている。これら電気電子部品は、塵やほこりが付着すると接点不良や読みとりエラー等の問題を起こすため、元来、塵やほこりの付着を嫌うものである。特に、近年の小型軽量化、高集積化および高精度化により、その要求が一層厳しくなっている。例えば、半導体に使われるＩＣチップや、ウエハー、コンピューターに使われるハードディスクの内部部品等はその最たる例である。通常これらの部品の製造や組立ては、塵やほこりの極めて少ない、いわゆるクリーンルームで行われており、ここでの塵、ほこりの付着は起こらない。しかしながら、これらの部品は、搬送時には外気にさらされるため、ここでの塵やほこりの付着が問題となる。 In recent years, OA devices and electronic devices have been reduced in size, weight, integration, and accuracy, and accordingly, there has been an increasing demand for reducing dust and dust adhesion to electrical and electronic parts as much as possible. Since these electric and electronic parts cause problems such as contact failure and reading error when dust or dust adheres, they naturally dislike the adhesion of dust and dust. In particular, due to the recent reduction in size and weight, higher integration, and higher accuracy, the requirements have become more severe. For example, IC chips used for semiconductors, internal parts of hard disks used for wafers and computers are the best examples. Usually, these parts are manufactured and assembled in a so-called clean room with very little dust and dust, and no dust or dust adheres here. However, since these parts are exposed to the outside air during transportation, adhesion of dust and dust here becomes a problem.
ところで、上記のような電気電子部品の搬送用の部品（ＩＣトレーやケース、ハウジング等）には、意匠性、軽量化の意味から合成樹脂を用いられることが多く、中でもスチレン系樹脂を含むポリフェニレンエーテル樹脂は、機械的強度、耐熱性、寸法安定性に優れるため、該用途に適した樹脂であるとされている。
しかしながら、スチレン系樹脂を含むポリフェニレンエーテル樹脂は、本来電気を通さない絶縁性であるため、帯電しやすく、塵やほこりが付着しやすい。このため搬送中に、搬送用部品に付着した塵やほこりが、その後電気電子部品本体に付着してしまうという問題がある。これを防ぐため、搬送用部品に使われる樹脂には、電気抵抗を下げ、導電性を持たせるために、各種の添加剤を入れることが行われている。
代表的な添加剤としては、導電性のカーボンブラックが挙げられる。これは少量の添加で電気抵抗を下げることができる有用な添加剤である。しかしながら、カーボンブラックを添加した場合には、いわゆる「カーボンブラックの脱離」と言われる現象が問題となってくる。この現象はカーボンブラックを含む樹脂成形品を他の物品とこすり合わせた時に、成形品表面のカーボンブラックが削り取られて、粉として出てくる現象で、脱離したカーボンブラックがＩＣチップや、ウエハー、コンピューターに使われるハードディスクの内部部品等を汚染してしまう。
By the way, synthetic resins are often used for the components (IC trays, cases, housings, etc.) for transporting electrical and electronic components as described above from the viewpoint of design and weight reduction, and in particular, polyphenylene containing a styrene resin. An ether resin is considered to be a resin suitable for the application because it is excellent in mechanical strength, heat resistance and dimensional stability.
However, a polyphenylene ether resin containing a styrene resin is inherently non-conductive and therefore easily charged and dust and dust are likely to adhere to it. For this reason, there is a problem that dust and dust adhering to the parts for conveyance will adhere to the electric / electronic parts main body after the conveyance. In order to prevent this, various additives are added to the resin used for the conveying parts in order to lower the electrical resistance and make it conductive.
A typical additive is conductive carbon black. This is a useful additive that can lower the electrical resistance with a small amount of addition. However, when carbon black is added, a phenomenon called “carbon black desorption” becomes a problem. This phenomenon is a phenomenon in which when the resin molded product containing carbon black is rubbed with another product, the carbon black on the surface of the molded product is scraped off and comes out as a powder. The detached carbon black is removed from the IC chip, wafer, It will contaminate the internal components of hard disks used in computers.
このようなカーボンブラックの脱離による問題を解決するため、特許文献１ではポリフェニレンエーテル系樹脂に、数平均繊維長が０．０５〜１．５ｍｍの範囲にある炭素繊維、アスペクト比が２０以上である板状無機充填剤を混練した熱可塑性樹脂組成物から成形され、その表面固有抵抗が１０1 〜１０12Ωの範囲であるＩＣ用トレーが開示されている。また、特許文献２には、ポリフェニレンエーテル樹脂および、ポリスチレン系樹脂を主成分とする樹脂組成物と、炭素繊維と、無機充填材とを含む耐熱樹脂組成物が開示されている。しかしながら、特許文献１及び特許文献２に開示されているような炭素繊維が添加された組成物では、得られる成形品の組成が均一ではなく、成形品の部位（箇所）によって電気抵抗にばらつきが生じるといった問題がある。加えて、電気抵抗が下がりすぎて、通電してショートを起こしやすいといった問題もあった。 In order to solve such a problem caused by carbon black detachment, Patent Document 1 discloses that a polyphenylene ether-based resin includes a carbon fiber having a number average fiber length of 0.05 to 1.5 mm and an aspect ratio of 20 or more. An IC tray is disclosed which is molded from a thermoplastic resin composition kneaded with a certain plate-like inorganic filler and whose surface specific resistance is in the range of 10 1 to 10 12 Ω. Patent Document 2 discloses a heat resistant resin composition containing a resin composition containing polyphenylene ether resin and polystyrene resin as main components, carbon fiber, and an inorganic filler. However, in the composition added with carbon fibers as disclosed in Patent Document 1 and Patent Document 2, the composition of the obtained molded product is not uniform, and the electric resistance varies depending on the part (location) of the molded product. There is a problem that occurs. In addition, the electrical resistance is too low, and there is a problem that it is easy to cause a short circuit when energized.
また、特許文献３には、ポリフェニレンエーテル系樹脂、ポリスチレン系樹脂又はＡＢＳ系樹脂の少なくとも１種類から選ばれた熱可塑性樹脂、カーボンブラック及び主骨格又は側鎖にシロキサン結合を有する重合体又は共重合体を特定割合含有し、その組成物の表面固有抵抗値が１０2 〜１０10Ωであり、かつ、ＪＩＳ−Ｋ−７１２５に準ずる測定法による、錫−鉛合金（錫５０ｗｔ％）との動摩擦係数が０．６以下であるＩＣ包装用樹脂組成物が開示されている。しかしながら、かかる樹脂組成物も、カーボンブラックの脱離の抑制は不十分であった。 In Patent Document 3, a thermoplastic resin selected from at least one of a polyphenylene ether resin, a polystyrene resin, or an ABS resin, carbon black, and a polymer or copolymer having a siloxane bond in the main skeleton or side chain. Dynamic friction with a tin-lead alloy (tin 50 wt%) by a measuring method according to JIS-K-7125, containing a specific proportion of coalesc, the surface resistivity of the composition being 10 2 to 10 10 Ω A resin composition for IC packaging having a coefficient of 0.6 or less is disclosed. However, such a resin composition also has insufficient suppression of carbon black detachment.
さらに、特許文献４には、ポリフェニレンエーテル系樹脂、カーボンブラック、ＪＩＳ−Ｋ−７２１５によるデユロメータＡ型表面硬度が９０以下のエチレン−α−オレフィン共重合体樹脂からなり、表面固有抵抗値が１０2〜１０10ΩであるＩＣ包装用樹脂組成物、該樹脂組成物からなるＩＣ包装用の成形品およびシートが開示されている。しかしながら、特許文献４に記載の成形品もカーボンブラックの脱離の抑制は不十分であった。
加えて、特許文献５には、ポリフェニレンエーテル系樹脂、ポリスチレン系樹脂またはアクリロニトリルブタジエンスチレン系樹脂（ＡＢＳ系樹脂）から選ばれた少なくとも１種類の熱可塑性樹脂、カーボンブラック、オレフィン系樹脂およびスチレン／ブタジエン／ブチレン／スチレンブロック共重合体を含有し、その表面固有抵抗値が１０2〜１０10Ωである樹脂組成物が開示されている。しかしながら、特許文献５に記載の樹脂組成物もカーボンブラックの脱離の抑制は不十分であった。
Further, Patent Document 4 includes polyphenylene ether resin, carbon black, and ethylene-α-olefin copolymer resin having a durometer A type surface hardness of 90 or less according to JIS-K-7215, and has a surface resistivity of 10 2. The resin composition for IC packaging which is 10 < 10 > (omega | ohm), the molded article and sheet | seat for IC packaging which consist of this resin composition are disclosed. However, the molded product described in Patent Document 4 is also insufficient in suppressing the desorption of carbon black.
In addition, Patent Document 5 discloses at least one thermoplastic resin selected from polyphenylene ether resin, polystyrene resin, or acrylonitrile butadiene styrene resin (ABS resin), carbon black, olefin resin, and styrene / butadiene. A resin composition containing a / butylene / styrene block copolymer and having a surface resistivity of 10 2 to 10 10 Ω is disclosed. However, the resin composition described in Patent Document 5 also has insufficient suppression of carbon black detachment.
本発明が解決しようとする課題は、スチレン系樹脂を含むポリフェニレンエーテル樹脂と、カーボンブラックとを含む樹脂組成物であって、機械的強度、耐熱性および寸法安定性に優れ、かつ、接触・摩擦時の摩耗によるカーボンブラックの脱離の少ない樹脂組成物、及び該樹脂組成物を用いてなる成形品（特に、ＩＣトレー）を提供することにある。 The problem to be solved by the present invention is a resin composition comprising a polyphenylene ether resin containing a styrenic resin and carbon black, having excellent mechanical strength, heat resistance and dimensional stability, and contact / friction. Another object is to provide a resin composition with less carbon black detachment due to wear and a molded article (particularly, an IC tray) using the resin composition.
本発明者は、前記課題を解決するため鋭意研究を重ねた結果、特定の末端基を特定の比率で有し、銅含有量が少ないポリフェニレンエーテル樹脂を用いると、樹脂成分とカーボンブラックとの密着性を著しく向上させることができ、その結果、上記課題を全て解決できる樹脂組成物、及び該樹脂組成物からなる成形品（例えば、ＩＣトレー）を見出し、本発明を完成させた。
すなわち、本発明の要旨は、ポリフェニレンエーテル樹脂（Ａ）２０〜９０重量％とスチレン系樹脂（Ｂ）８０〜１０重量％からなる樹脂混合物１００重量部に対し、カーボンブラック（Ｃ）を１〜３０重量部配合してなり、前記ポリフェニレンエーテル樹脂（Ａ）が、下記一般式（２）で示されるフェニレンエーテルユニット１００個に対し、下記一般式（１）で示される末端基を０．３個以上有し、極限粘度が０．３〜０．６ｄｌ／ｇであり、且つ銅含有率が０．２ｐｐｍ以下である樹脂組成物（特に、導電性樹脂組成物）、及び該樹脂組成物を用いてなる成形品（例えば、ＩＣトレー）にある。
As a result of intensive studies to solve the above problems, the present inventor has found that when a polyphenylene ether resin having a specific end group at a specific ratio and a low copper content is used, the resin component and the carbon black are adhered to each other. As a result, the present inventors have found a resin composition that can solve all of the above problems, and a molded product (for example, an IC tray) comprising the resin composition, thereby completing the present invention.
That is, the gist of the present invention is that carbon black (C) is added in an amount of 1 to 30 with respect to 100 parts by weight of a resin mixture composed of 20 to 90% by weight of polyphenylene ether resin (A) and 80 to 10% by weight of styrene resin (B). The polyphenylene ether resin (A) is blended in parts by weight, and the end group represented by the following general formula (1) is 0.3 or more per 100 phenylene ether units represented by the following general formula (2). A resin composition (particularly a conductive resin composition) having an intrinsic viscosity of 0.3 to 0.6 dl / g and a copper content of 0.2 ppm or less, and the resin composition In a molded product (for example, an IC tray).
一般式（１）
一般式（２）
General formula (2)
本発明により、機械的強度、耐熱性、寸法安定性に優れ、かつ、接触・摩擦時の摩耗によるカーボンブラックの脱離の少ない樹脂組成物を提供することが可能になった。さらに、該樹脂組成物から成形された反りの小さい成形品（特に、導電性を有する成形品、導電性材料等）も提供できるようになった。特に、ＩＣトレーを製造するのに好ましい樹脂組成物が得られた。 According to the present invention, it has become possible to provide a resin composition that is excellent in mechanical strength, heat resistance, and dimensional stability, and has little carbon black detachment due to wear during contact and friction. Furthermore, it is also possible to provide a molded product having a small warpage (particularly, a molded product having conductivity, a conductive material, etc.) molded from the resin composition. In particular, a resin composition preferable for producing an IC tray was obtained.
以下において、本発明の内容について詳細に説明する。尚、本願明細書において「〜」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。
また、本発明における導電性とは、例えば、表面固有抵抗値が１０2Ω以上、好ましくは１０4〜１０18Ωのものをいう。
Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
Moreover, the electroconductivity in this invention means that whose surface specific resistance value is 10 < 2 > (omega | ohm) or more, Preferably it is 10 < 4 > -10 < 18 > (ohm).
本発明の樹脂組成物に用いられるポリフェニレンエーテル樹脂（Ａ）は、前記一般式（２）で示されるフェニレンエーテルユニットを主鎖に持つ重合体であって、ホモポリマーであってもコポリマーであってもよい。 The polyphenylene ether resin (A) used in the resin composition of the present invention is a polymer having a phenylene ether unit represented by the general formula (2) in the main chain, and is a homopolymer or a copolymer. Also good.
一般式（２）中、２つのＲ3は、それぞれ独立して、炭素原子数１〜３のアルキル基、特にメチル基が好ましく、２つのＲ4は、それぞれ独立して、水素原子が好ましい。 In general formula (2), two R 3 s are each independently preferably an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, and two R 4 s are each independently preferably a hydrogen atom.
ホモポリマーとしては、具体的には、例えば、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、ポリ（２，６−ジエチル−１，４−フェニレン）エーテル、ポリ（２，６−ジプロピル−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−プロピル−１，４−フェニレン）エーテル等の２，６−ジアルキルフェニレンエーテルの重合体が挙げられ、コポリマーとしては、各種２，６−ジアルキルフェノール／２，３，６−トリアルキルフェノール共重合体が挙げられる。本発明に使用されるポリフェニレンエーテル（Ａ）としては、特に、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／２，３，６−トリメチルフェノール共重合体が好ましい。 Specific examples of the homopolymer include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, and poly (2,6-phenylene). 2,6 such as dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether -Dialkyl phenylene ether polymers are mentioned, and examples of the copolymer include various 2,6-dialkylphenol / 2,3,6-trialkylphenol copolymers. Examples of the polyphenylene ether (A) used in the present invention include poly (2,6-dimethyl-1,4-phenylene) ether and 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer. Is preferred.
また、本発明の樹脂組成物に用いられるポリフェニレンエーテル樹脂（Ａ）が有する、前記一般式（１）で示される末端基は、一般式（１）中の２つのＲ1およびＲ2は、Ｒ1およびＲ2の少なくとも１個が水素原子がよく、Ｒ1は炭素原子数１〜３のアルキル基がであることが好ましい。具体的には、前記一般式（１）で示される末端基は、３，５−ジメチル−４−ヒドロキシフェニル基、３，５−ジエチル−４−ヒドロキシフェニル基、３，５−ジプロピル−４−ヒドロキシフェニル基、３−メチル−５−エチル−４−ヒドロキシフェニル基、３−メチル−５−プロピル−４−ヒドロキシフェニル基、２，３，５−トリメチル−４−ヒドロキシフェニル基等が挙げられる。 Moreover, the terminal group shown by the said General formula (1) which the polyphenylene ether resin (A) used for the resin composition of this invention has is two R < 1 > and R < 2 > in General formula (1) are R At least one of 1 and R 2 is preferably a hydrogen atom, and R 1 is preferably an alkyl group having 1 to 3 carbon atoms. Specifically, the terminal group represented by the general formula (1) is 3,5-dimethyl-4-hydroxyphenyl group, 3,5-diethyl-4-hydroxyphenyl group, 3,5-dipropyl-4- Examples thereof include a hydroxyphenyl group, a 3-methyl-5-ethyl-4-hydroxyphenyl group, a 3-methyl-5-propyl-4-hydroxyphenyl group, and a 2,3,5-trimethyl-4-hydroxyphenyl group.
本発明の樹脂組成物に用いられるポリフェニレンエーテル樹脂（Ａ）の製法は、特に限定されるものではないが、第一銅塩とアミンの化合物からなる触媒の存在下、２，６−キシレノール等のモノマーを酸化重合させることにより容易に製造できる。 The production method of the polyphenylene ether resin (A) used in the resin composition of the present invention is not particularly limited, but 2,6-xylenol or the like can be used in the presence of a catalyst composed of a cuprous salt and an amine compound. It can be easily produced by oxidative polymerization of the monomer.
本発明で使用されるポリフェニレンエーテル樹脂（Ａ）は、前記一般式（１）で示される末端基を前記一般式（２）で示されるフェニレンエーテルユニット１００個に対し、０．３個以上有することが必要である。前記一般式（１）で示される末端基が０．３個未満のポリフェニレンエーテル樹脂を用いると、カーボンブラックとの密着性が低下するので、例えば、本発明の樹脂組成物からなるＩＣトレーとＩＣチップ等との接触・摩擦時に、摩耗によるカーボンブラックの脱離が多く、ＩＣトレー表面から脱離したカーボンブラックがＩＣチップや、ウエハー、コンピューターに使われるハードディスクの内部部品等を汚染するという問題が発生する。また、前記一般式（１）で示される末端基の数が０．３個未満のポリフェニレンエーテルを用いると、スチレン系樹脂（Ｂ）との相溶性が低下するので、成形品の外観不良や層状剥離が発生することがあり、さらには破断伸びや面衝撃強度が低下する。
前記一般式（１）で示される末端基の数が０．３個以上である本発明のポリフェニレンエーテルを得る方法は、特に限定されるものではないが、例えば特公昭６１−２０５７６号公報にも記載されている様にモノマー（例えば、２，６−ジメチルキシレノール）を、第一銅塩とアミンの化合物を触媒として、トルエン等の溶媒中で、酸素存在下に酸化重合反応させ、得られたポリフェニレンエーテル溶液に、銅とキレート化合物を形成する化合物を添加する等の方法で、触媒を失活させた後、酸素の混入を避けた雰囲気下で該ポリフェニレンエーテル溶液を攪拌することにより得ることができる。なお、攪拌中の溶液の温度は、好ましくは５０℃以上、より好ましくは７０℃程度に維持するのがよい。前記一般式（１）で示される末端基の数は、前記一般式（２）で示されるフェニレンエーテルユニット１００個に対し、好ましくは０．４〜２個、より好ましくは０．５〜１．５個である。末端基の数を２個以下とすることにより、強度や熱安定性がより向上する傾向にあり好ましい。
The polyphenylene ether resin (A) used in the present invention has 0.3 or more terminal groups represented by the general formula (1) with respect to 100 phenylene ether units represented by the general formula (2). is required. When a polyphenylene ether resin having less than 0.3 terminal groups represented by the general formula (1) is used, adhesion with carbon black is lowered. For example, an IC tray and an IC made of the resin composition of the present invention are used. There is a problem that carbon black is detached due to wear during contact and friction with chips, and the carbon black detached from the surface of the IC tray contaminates IC chips, wafers and internal components of hard disks used in computers. appear. Moreover, since the compatibility with the styrenic resin (B) is lowered when polyphenylene ether having a number of end groups represented by the general formula (1) of less than 0.3 is used, the appearance of the molded product is poor and the layered shape is reduced. Peeling may occur, and further, elongation at break and surface impact strength are reduced.
The method for obtaining the polyphenylene ether of the present invention in which the number of terminal groups represented by the general formula (1) is 0.3 or more is not particularly limited, but for example, also in JP-B 61-20576 As described, it was obtained by subjecting a monomer (for example, 2,6-dimethylxylenol) to an oxidative polymerization reaction in the presence of oxygen in a solvent such as toluene using a cuprous salt and amine compound as a catalyst. It can be obtained by deactivating the catalyst by a method such as adding a compound that forms a chelate compound with copper into the polyphenylene ether solution, and then stirring the polyphenylene ether solution in an atmosphere that avoids oxygen contamination. it can. The temperature of the solution during stirring is preferably maintained at 50 ° C. or higher, more preferably about 70 ° C. The number of terminal groups represented by the general formula (1) is preferably 0.4 to 2, more preferably 0.5 to 1. with respect to 100 phenylene ether units represented by the general formula (2). Five. It is preferable that the number of end groups is 2 or less because strength and thermal stability tend to be further improved.
また、本発明で使用されるポリフェニレンエーテル樹脂（Ａ）は、クロロホルム中で測定した３０℃の極限粘度が０．３〜０．６dl/gのものであり、好ましくは０．３５〜０．５dl/gである。極限粘度が０．３dl/g未満では樹脂組成物の機械的強度が不足し、０．６dl/gを越えると流動性が不足し、さらには成形品表面にカーボンブラックが多く露出し、カーボンブラックの離脱が激しくなり、外観不良も発生する。かかる極限粘度のポリフェニレンエーテルは、酸化重合の反応条件、例えば、反応温度、反応時間、触媒量などを調整することにより製造できる。 The polyphenylene ether resin (A) used in the present invention has an intrinsic viscosity at 30 ° C. measured in chloroform of 0.3 to 0.6 dl / g, preferably 0.35 to 0.5 dl. / g. If the intrinsic viscosity is less than 0.3 dl / g, the mechanical strength of the resin composition is insufficient. If it exceeds 0.6 dl / g, the fluidity is insufficient, and more carbon black is exposed on the surface of the molded product. Detachment becomes severe and appearance defects also occur. Such intrinsic viscosity polyphenylene ether can be produced by adjusting reaction conditions for oxidative polymerization, for example, reaction temperature, reaction time, catalyst amount and the like.
本発明で使用されるポリフェニレンエーテル樹脂（Ａ）は、銅含有率が、ポリフェニレンエーテルの重量基準で０．２ｐｐｍ以下のものである。銅含有率は残存触媒に起因する。
ポリフェニレンエーテル樹脂（Ａ）の銅含有率が０．２ｐｐｍを超えると、本発明の樹脂組成物を製造及び成形する際の熱安定性や、成形品を高温雰囲気で使用する際の熱安定性が低下し、成形品の外観不良や機械的強度の低下を引き起こすことがある。ここで、ポリフェニレンエーテル樹脂（Ａ）の銅含有率を０．２ｐｐｍ以下とするには、酸化重合反応の触媒に使用された銅塩を溶液から有効に除去することが重要である。除去方法は特に限定されるものではないが、例えば、酸化重合反応により得られたポリフェニレンエーテル溶液に、エチレンジアミン４酢酸ナトリウムのような銅とキレート化合物を形成する水溶液を添加し、充分攪拌した後に、水層を分離することにより、効率よく銅を分離することができる。一般的には、更に、この操作を繰り返すことにより、ポリフェニレンエーテルの銅含有率を効果的に低減させることができる。また、反応溶液からポリフェニレンエーテルを分離する際、ポリマー含有相と銅塩含有相の分離が良好となるような物質を添加する方法やこれらを組み合わせた方法が採用できる。
酸化反応終了後、銅イオンの低減操作が不十分のまま、ポリフェニレンエーテル溶液にメタノールなどの非溶媒を添加した後では、固体として分離されたポリフェニレンエーテルをメタノール、水等で十分に洗浄してもポリフェニレンエーテルの銅含有率を低減させることが困難となる場合が多い。
ポリフェニレンエーテルの銅含有率は、好ましくは０．１５ｐｐｍ以下である。
The polyphenylene ether resin (A) used in the present invention has a copper content of 0.2 ppm or less based on the weight of the polyphenylene ether. The copper content is attributed to the residual catalyst.
When the copper content of the polyphenylene ether resin (A) exceeds 0.2 ppm, the thermal stability when producing and molding the resin composition of the present invention and the thermal stability when using the molded product in a high temperature atmosphere It may cause deterioration of appearance and mechanical strength of the molded product. Here, in order to make the copper content of the polyphenylene ether resin (A) 0.2 ppm or less, it is important to effectively remove the copper salt used as a catalyst for the oxidative polymerization reaction from the solution. Although the removal method is not particularly limited, for example, an aqueous solution that forms a chelate compound with copper such as sodium ethylenediaminetetraacetate is added to a polyphenylene ether solution obtained by an oxidative polymerization reaction, and after sufficient stirring, By separating the aqueous layer, copper can be separated efficiently. Generally, the copper content of polyphenylene ether can be effectively reduced by repeating this operation. In addition, when polyphenylene ether is separated from the reaction solution, a method of adding a substance that improves the separation of the polymer-containing phase and the copper salt-containing phase, or a method combining these can be employed.
After completion of the oxidation reaction, after adding a non-solvent such as methanol to the polyphenylene ether solution while the copper ion reduction operation is insufficient, the polyphenylene ether separated as a solid may be sufficiently washed with methanol, water, etc. In many cases, it is difficult to reduce the copper content of polyphenylene ether.
The copper content of the polyphenylene ether is preferably 0.15 ppm or less.
本発明で使用されるスチレン系樹脂（Ｂ）は、スチレン系単量体の重合体、スチレン系単量体と他の共重合可能な単量体との共重合体及びスチレン系グラフト共重合体等が挙げられる。スチレン系単量体と他の共重合可能な単量体との共重合体としては、例えば、ＡＳ樹脂等が挙げられ、スチレン系グラフト共重合体としては、例えば、耐衝撃性ポリスチレン樹脂（ＨＩＰＳ樹脂）、アクリロニトリルブタジエンスチレン樹脂（ＡＢＳ樹脂）、アクリロニトリルエチレンスチレン樹脂（ＡＥＳ樹脂）、アクリロニトリルアセチレートスチレン樹脂（ＡＡＳ樹脂）等が挙げられる。スチレン系共重合体の製造方法としては、乳化重合法、溶液重合法、懸濁重合法および塊状重合法等の公知の方法が挙げられる。 The styrene resin (B) used in the present invention is a polymer of a styrene monomer, a copolymer of a styrene monomer and another copolymerizable monomer, and a styrene graft copolymer. Etc. Examples of the copolymer of the styrene monomer and other copolymerizable monomer include AS resin, and examples of the styrene graft copolymer include impact resistant polystyrene resin (HIPS). Resin), acrylonitrile butadiene styrene resin (ABS resin), acrylonitrile ethylene styrene resin (AES resin), acrylonitrile acetylate styrene resin (AAS resin), and the like. Examples of the method for producing the styrene copolymer include known methods such as an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method.
スチレン系単量体としては、好ましくは、スチレン、α−メチルスチレン、ｐ−メチルスチレン等が挙げられ、より好ましくはスチレンが挙げられる。スチレン系単量体と共重合可能な単量体としては、好ましくは、アクリロニトリル、メタクリロニトリル等のシアン化ビニル単量体、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、メタクリル酸メチル、メタクリル酸エチル等の（メタ）アクリル酸アルキルエステル、マレイミド、Ｎ−フェニルマレイミド等が挙げられ、より好ましくは、シアン化ビニル単量体、（メタ）アクリル酸アルキルエステルが挙げられる。 Preferred examples of the styrenic monomer include styrene, α-methylstyrene, p-methylstyrene, and more preferred is styrene. The monomer copolymerizable with the styrenic monomer is preferably a vinyl cyanide monomer such as acrylonitrile or methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate or methacrylic acid. Examples include (meth) acrylic acid alkyl esters such as ethyl acid, maleimide, N-phenylmaleimide, and the like, and more preferable examples include vinyl cyanide monomers and (meth) acrylic acid alkyl esters.
本発明の樹脂組成物の樹脂成分は、ポリフェニレンエーテル樹脂（Ａ）２０〜９０重量％と、スチレン系樹脂（Ｂ）８０〜１０重量％からなり、ポリフェニレンエーテル樹脂が２０重量％より少ないと、荷重撓み温度や機械的強度が低下する。また、ポリフェニレンエーテル樹脂が９０重量％を越えると樹脂組成物の流動性が著しく低下し、成形工程において実用に堪えないものとなる。さらに、本発明の樹脂組成物の樹脂成分は、ポリフェニレンエーテル樹脂（Ａ）５０〜８０重量％と、スチレン系樹脂（Ｂ）５０〜２０重量％からなることが好ましい。 The resin component of the resin composition of the present invention comprises 20 to 90% by weight of the polyphenylene ether resin (A) and 80 to 10% by weight of the styrene resin (B). When the polyphenylene ether resin is less than 20% by weight, Deflection temperature and mechanical strength decrease. On the other hand, if the polyphenylene ether resin exceeds 90% by weight, the fluidity of the resin composition is remarkably lowered, and it becomes unpractical in the molding process. Furthermore, it is preferable that the resin component of the resin composition of this invention consists of 50-80 weight% of polyphenylene ether resins (A) and 50-20 weight% of styrene resin (B).
本発明で使用するカーボンブラック（Ｃ）は、天然黒鉛、人造黒鉛、カーボンブラックが好ましく、アセチレンブラック、チャンネルブラックおよびファネスブラックなどの人造黒鉛で、粉末状や顆粒状のもので、比表面積が大きく、樹脂への添加量が少量で高度の導電性が得られるものがより好ましい。ファネスブラックとしては、具体的には、ライオン・アクゾ社製・商品名ケッチェンブラックＥＣおよびケッチェンブラックＥＣ−６００Ｊ、旭カーボン（株）製・商品名旭ＨＳ−５００などが例示される。 Carbon black (C) used in the present invention is preferably natural graphite, artificial graphite, or carbon black, and is artificial graphite such as acetylene black, channel black, and funnes black, and is in the form of powder or granules and has a specific surface area. Larger ones that can obtain high conductivity with a small amount added to the resin are more preferable. Specific examples of the funes black include Lion Kakuzo Co., Ltd., trade name Ketjen Black EC and Ketjen Black EC-600J, Asahi Carbon Co., Ltd., trade name Asahi HS-500, and the like.
カーボンブラック（Ｃ）の配合量は、ポリフェニレンエーテル樹脂（Ａ）２０〜９０重量％と、スチレン系樹脂（Ｂ）８０〜１０重量％からなる樹脂成分１００重量部に対し１〜３０重量部、好ましくは３〜２５重量部、さらに好ましくは５〜２０重量部である。カーボンブラック（Ｃ）の配合量が１重量部より少ないと導電性が不足し、３０重量部を越えると樹脂成分中での分散性が低下し、機械的強度や流動性も低下し、成形品の外観も悪化するので好ましくない。 The amount of carbon black (C) is 1 to 30 parts by weight, preferably 20 to 90% by weight of the polyphenylene ether resin (A) and 100 parts by weight of the resin component consisting of 80 to 10% by weight of the styrene resin (B). Is 3 to 25 parts by weight, more preferably 5 to 20 parts by weight. If the blending amount of carbon black (C) is less than 1 part by weight, the conductivity is insufficient, and if it exceeds 30 parts by weight, the dispersibility in the resin component is lowered, the mechanical strength and the fluidity are also lowered, and the molded product. This is not preferable because the appearance of the material deteriorates.
本発明では、樹脂組成物の衝撃強度を改良するために、さらにスチレン系エラストマー（Ｄ）を配合することが好ましい。本発明で好ましく配合されるスチレン系エラストマー（Ｄ）は、ハードセグメントがスチレン重合体で構成され、ソフトセグメントがポリブタジエン、ポリイソプレン及びそれらの水添物よりなる群から選択された少なくとも１種類の重合体で構成されたブロック共重合体、具体的には、ＳＢＳ（スチレン／ブタジエン／スチレンブロックコポリマー）、ＳＩＳ（スチレン／イソプレン／スチレンブロックコポリマー）、ＳＥＢＳ（スチレン／エチレン／ブチレン／スチレンブロックコポリマー：ＳＢＳの水添物）、ＳＥＰＳ（スチレン／エチレン／プロピレン／スチレンブロックコポリマー：ＳＩＳの水添物）等を例示することができ、特に好ましくはＳＥＢＳである。
スチレン系エラストマーのハードセグメントとソフトセグメントの構成比率は好ましくは１０：９０〜９０：１０、より好ましくは１０：９０〜５０：５０の範囲内で適宜選択することができ、該ハードセグメントブロックと該ソフトセグメントブロックの結合形態はジブロックタイプであってもトリブロックタイプであってもよい。
In this invention, in order to improve the impact strength of a resin composition, it is preferable to mix | blend a styrene-type elastomer (D) further. In the styrene elastomer (D) preferably blended in the present invention, the hard segment is composed of a styrene polymer, and the soft segment is at least one type selected from the group consisting of polybutadiene, polyisoprene and hydrogenated products thereof. Block copolymer composed of a polymer, specifically, SBS (styrene / butadiene / styrene block copolymer), SIS (styrene / isoprene / styrene block copolymer), SEBS (styrene / ethylene / butylene / styrene block copolymer: SBS) ), SEPS (styrene / ethylene / propylene / styrene block copolymer: hydrogenated SIS), and the like, and SEBS is particularly preferable.
The composition ratio of the hard segment and the soft segment of the styrene-based elastomer can be suitably selected within the range of preferably 10:90 to 90:10, more preferably 10:90 to 50:50. The combination form of the soft segment blocks may be a diblock type or a triblock type.
スチレン系エラストマー（Ｄ）の配合率は、ポリフェニレンエーテル樹脂（Ａ）２０〜９０重量％と、スチレン系樹脂（Ｂ）８０〜１０重量％からなる樹脂成分１００重量部に対し、好ましくは１〜２５重量部、より好ましくは３〜１５重量部、さらに好ましくは５〜１５重量部である。スチレン系エラストマー（Ｄ）の配合量を１重量部以上とすることにより、衝撃強度がより向上する傾向にあり好ましい。また、スチレン系エラストマー（Ｄ）の配合量を２５重量部以下とすることにより、樹脂組成物の剛性や荷重撓み温度が低くなりすぎるのを抑え、例えば、ＩＣ製造時のベーキング工程で樹脂組成物からなるＩＣトレーの変形をより抑止でき好ましい。 The blending ratio of the styrene elastomer (D) is preferably 1 to 25 with respect to 100 parts by weight of the resin component comprising 20 to 90% by weight of the polyphenylene ether resin (A) and 80 to 10% by weight of the styrene resin (B). Parts by weight, more preferably 3 to 15 parts by weight, still more preferably 5 to 15 parts by weight. By making the blending amount of the styrene elastomer (D) 1 part by weight or more, the impact strength tends to be further improved, which is preferable. Moreover, by setting the blending amount of the styrene-based elastomer (D) to 25 parts by weight or less, it is possible to suppress the rigidity and load deflection temperature of the resin composition from becoming too low. For example, the resin composition can be used in a baking process during IC manufacturing. It is preferable because the deformation of the IC tray can be further suppressed.
本発明では、樹脂組成物の寸法安定性と剛性等の機械的強度をより改良するために、ガラスフレーク、シリカ、アルミナ、カオリン、タルク、マイカなどの無機充填材（Ｅ）を配合することが好ましく、特にマイカ（ｅ−１）及び／またはタルク（ｅ−２）からなる無機充填材（Ｅ）を配合することがより好ましい。無機充填材（Ｅ）の配合量は、ポリフェニレンエーテル樹脂（Ａ）２０〜９０重量％と、スチレン系樹脂（Ｂ）８０〜１０重量％からなる樹脂成分１００重量部に対し、好ましくは１〜２０重量部、より好ましくは３〜１５重量部である。無機充填材（Ｅ）の配合量を１重量部以上とすることにより、寸法安定性と機械的強度のいずれについてもより好ましい傾向になり、２０重量部以下とすることにより流動性や外観がより好ましい傾向になる。 In the present invention, an inorganic filler (E) such as glass flake, silica, alumina, kaolin, talc, or mica may be blended in order to further improve the mechanical strength such as dimensional stability and rigidity of the resin composition. In particular, it is more preferable to blend an inorganic filler (E) made of mica (e-1) and / or talc (e-2). The blending amount of the inorganic filler (E) is preferably 1 to 20 with respect to 100 parts by weight of the resin component composed of 20 to 90% by weight of the polyphenylene ether resin (A) and 80 to 10% by weight of the styrene resin (B). Part by weight, more preferably 3 to 15 parts by weight. By making the blending amount of the inorganic filler (E) 1 part by weight or more, both dimensional stability and mechanical strength tend to be more preferable, and by making it 20 parts by weight or less, fluidity and appearance are more improved. It becomes a favorable tendency.
本発明の樹脂組成物の製造及び成形工程における溶融混練時や、ＩＣ製造時に高温雰囲気で実施されるベーキング工程でのＩＣトレーの熱安定性を向上させる目的で、ヒンダードフェノール系化合物、ホスファイト系化合物、酸化亜鉛から選ばれた１種以上の安定剤を配合することが好ましい。安定剤の配合率は、ポリフェニレンエーテル樹脂とスチレン系樹脂からなる樹脂成分１００重量部に対し、好ましくは０．０１〜５重量部、より好ましくは０．０３〜３重量部である。安定剤の配合率を０．０１重量部以上とすることにより、安定剤の効果がより得られやすく、５重量部以下とすることにより、モールドデボジットの発生が少なくなる傾向にあり好ましい。 For the purpose of improving the thermal stability of the IC tray in the baking process carried out in a high temperature atmosphere during the manufacture and molding process of the resin composition of the present invention and in the IC manufacturing process, a hindered phenol compound, a phosphite It is preferable to blend one or more stabilizers selected from a system compound and zinc oxide. The blending ratio of the stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight with respect to 100 parts by weight of the resin component composed of the polyphenylene ether resin and the styrene resin. When the blending ratio of the stabilizer is 0.01 parts by weight or more, the effect of the stabilizer is more easily obtained, and by 5 parts by weight or less, the occurrence of mold deposit tends to be reduced, which is preferable.
本発明の樹脂組成物に難燃性を賦与する目的で、難燃剤、例えば、リン酸エステル系難燃剤を配合することができる。リン酸エステル系難燃剤の具体例としては、フェニル・レゾルシン・ポリホスフェート、クレジル・レゾルシン・ポリホスフェート、フェニル・クレジル・レゾルシン・ポリホスフェート、キシリル・レゾルシン・ポリホスフェート、フェニル−ｐ−ｔｅｒｔ−ブチルフェニル・レゾルシン・ポリホスフェート、フェニル・イソプロピルフェニル・レゾルシン・ポリホスフェート、クレジル・キシレル・レゾルシン・ポリホスフェート、フェニル・イソプロピルフェニル・ジイソプロピルフェニル・レゾルシン・ポリホスフェート、ビスフェノールＡビス（ジフェニルホスフェート）等の縮合リン酸エステル化合物が挙げられる。さらに、リン酸トリフェニル、リン酸トリクレジル、リン酸ジフェニル２エチルクレジル、リン酸トリ(イソプロピルフェニル)、メチルホスホン酸ジフェニルエステル、フェニルホスホン酸ジエチルエステル、リン酸ジフェニルクレジル、リン酸トリブチル等が挙げられる。 For the purpose of imparting flame retardancy to the resin composition of the present invention, a flame retardant such as a phosphate ester flame retardant can be blended. Specific examples of phosphate ester flame retardants include phenyl-resorcin-polyphosphate, cresyl-resorcin-polyphosphate, phenyl-cresyl-resorcin-polyphosphate, xylyl-resorcin-polyphosphate, phenyl-p-tert-butylphenyl・ Condensed phosphoric acid such as resorcinol polyphosphate, phenyl isopropylphenyl resorcinol polyphosphate, cresyl xyler resorcinol polyphosphate, phenyl isopropylphenyl diisopropylphenyl resorcinol polyphosphate, bisphenol A bis (diphenyl phosphate), etc. An ester compound is mentioned. Further, triphenyl phosphate, tricresyl phosphate, diphenyl 2-ethyl cresyl phosphate, tri (isopropylphenyl) phosphate, methylphosphonic acid diphenyl ester, phenylphosphonic acid diethyl ester, diphenyl cresyl phosphate, tributyl phosphate and the like can be mentioned.
リン酸エステル系難燃剤の配合率は、ポリフェニレンエーテル樹脂及びスチレン系樹脂の合計１００重量部に対して好ましくは１〜３０重量部、より好ましくは５〜２５重量部である。リン酸エステル系難燃剤の配合割合を１重量部以上とすることにより、難燃効果がより得られやすい傾向にあり、３０重量部以下とすることにより、荷重撓み温度が上昇または機械的強度が向上する傾向にあり好ましい。 The blending ratio of the phosphate ester flame retardant is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the total of the polyphenylene ether resin and the styrene resin. By making the blending ratio of the phosphate ester flame retardant 1 part by weight or more, the flame retardant effect tends to be more easily obtained, and by making it 30 parts by weight or less, the load deflection temperature is increased or the mechanical strength is increased. It tends to improve, which is preferable.
本発明の樹脂組成物には、上記成分のほか、他の成分を添加できる。他の成分としては、例えば、ガラス繊維、炭素繊維、チタン酸カリウム、ホウ酸アルミニウム等のウィスカー、離型剤、滑剤、流動性改良剤、分散剤等が挙げられる。 In addition to the above components, other components can be added to the resin composition of the present invention. Examples of other components include glass fibers, carbon fibers, potassium titanate, aluminum borate and other whiskers, mold release agents, lubricants, fluidity improvers, and dispersants.
本発明の樹脂組成物は、一般に熱可塑性樹脂組成物の製造に用いられる設備と方法により製造することができる。例えば、本発明の組成物を構成する成分を一括してタンブラーなどの混合機で混合し、一軸や二軸の押出機を使用して溶融・混練し、押出して成形用ペレットを製造することも可能である。また、カーボンブラックの含有率の高いペレットと低いペレットをドライブレンドしたものを成形し、表面固有抵抗を調整することもできる。 The resin composition of the present invention can be produced by facilities and methods generally used for producing a thermoplastic resin composition. For example, the components constituting the composition of the present invention may be mixed together in a mixer such as a tumbler, melted and kneaded using a single or twin screw extruder, and extruded to produce a pellet for molding. Is possible. In addition, it is possible to adjust the surface resistivity by molding a dry blend of pellets having a high carbon black content and low pellets.
混練温度と混練時間は、樹脂組成物や混練機の種類等の条件により、任意に選ぶことができるが、混練温度は、好ましくは２００〜３５０℃、より好ましくは２２０〜３２０℃、混練時間は２０分以下が好ましい。このような温度範囲とすることにより、ポリフェニレンエーテル樹脂やスチレン系樹脂の熱劣化をより効果的に抑止でき、成形品の物性や外観を向上させる傾向にあり、好ましい。 The kneading temperature and kneading time can be arbitrarily selected according to conditions such as the type of the resin composition and the kneader, but the kneading temperature is preferably 200 to 350 ° C., more preferably 220 to 320 ° C., and the kneading time is 20 minutes or less is preferable. By setting it as such a temperature range, the thermal deterioration of a polyphenylene ether resin or a styrene resin can be more effectively suppressed, and the physical properties and appearance of a molded product tend to be improved, which is preferable.
本発明の樹脂組成物を用いて成形品を得る方法は、特に限定されるものでなく、熱可塑性樹脂組成物について一般に用いられている成形法、例えば、射出成形、中空成形、押出成形、シート成形、熱成形、回転成形、積層成形等の成形方法が適用できる。本発明の樹脂組成物から得られる成形品は、特に電気電子部品搬送用成形品が好適である。例えば、ウエハーのトレー、回路基盤収納ボックス、ハードディスク、ＣＤ、ＤＶＤ、ＭＯ等の光や磁気記録装置の基盤、ハウジング、ＩＣ部品ボックス、ＩＣトレー等があり、特にＩＣトレーとして好適に使用される。ＩＣトレーをはじめとした搬送用部品は、塵やほこりの付着を嫌うことから、表面抵抗が低いことが要求されるが、低すぎるとショートの危険性があり好ましくない。具体的には、表面抵抗は１０2〜１０10Ωが好ましく、１０3〜１０9Ωがさらに好ましく、１０4〜１０8Ωが最も好ましい。 The method for obtaining a molded article using the resin composition of the present invention is not particularly limited, and is a molding method generally used for thermoplastic resin compositions, such as injection molding, hollow molding, extrusion molding, and sheet. A molding method such as molding, thermoforming, rotational molding, and lamination molding can be applied. The molded product obtained from the resin composition of the present invention is particularly preferably a molded product for transporting electrical and electronic parts. For example, there are wafer trays, circuit board storage boxes, optical disks such as hard disks, CDs, DVDs, and MOs, and magnetic recording device boards, housings, IC component boxes, IC trays, and the like. Since parts for conveyance such as an IC tray do not like adhesion of dust and dust, it is required to have a low surface resistance. However, if it is too low, there is a risk of short circuit, which is not preferable. Specifically, the surface resistance is preferably 10 2 to 10 10 Ω, more preferably 10 3 to 10 9 Ω, and most preferably 10 4 to 10 8 Ω.
以下、本発明を実施例によりさらに詳細に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.
また、ポリフェニレンエーテル樹脂の製造例、樹脂組成物の実施例と比較例に使用した原材料、樹脂組成物の製法、試験片の成形条件と評価法は次の通りである。
＜ポリフェニレンエーテルの物性＞
（１）極限粘度：ポリフェニレンエーテルをクロロホルムに溶解し、濃度０．５ｇ／ｄｌ以下の異なる濃度の溶液を調製し、３０℃においてウベローデ型の粘度計を用いて、該異なる濃度における比粘度を測定し、比粘度と濃度との比を計算し、濃度を０に外挿した時の比を算出し、極限粘度とした。
（２）末端基の種類及び数：日本電子（株）製のＪＮＭ−Ａ４００を用い、ＣＤＣｌ3を溶媒、テトラメチルシランを基準として、測定モードは13Ｃ−ＮＭＲ完全デカップリングモードとして、ポリフェニレンエーテル樹脂の13Ｃ−核磁気共鳴吸収スペクトルを測定した。得られたスペクトラムから、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ、１９９０，２３，１３１８〜１３２９に記載の方法により、水酸基末端の種類及び数を求めた。
（３）銅含有率：ポリフェニレンエーテルを硝酸で分解した後に残渣中の銅を原子吸光分析により定量し、ポリフェニレンエーテル中の銅含有率を算出した。
Moreover, the raw material used for the manufacture example of a polyphenylene ether resin, the Example and comparative example of a resin composition, the manufacturing method of a resin composition, the molding conditions and evaluation method of a test piece are as follows.
<Physical properties of polyphenylene ether>
(1) Intrinsic viscosity: Polyphenylene ether is dissolved in chloroform, solutions having different concentrations of 0.5 g / dl or less are prepared, and the specific viscosity at the different concentrations is measured at 30 ° C. using an Ubbelohde viscometer. Then, the ratio between the specific viscosity and the concentration was calculated, and the ratio when the concentration was extrapolated to 0 was calculated as the intrinsic viscosity.
(2) Types and number of end groups: JNM-A400 manufactured by JEOL Ltd., CDCl 3 as a solvent, tetramethylsilane as a reference, measurement mode as 13 C-NMR complete decoupling mode, polyphenylene ether The 13 C-nuclear magnetic resonance absorption spectrum of the resin was measured. From the obtained spectrum, the type and number of hydroxyl terminals were determined by the method described in Macromolecules, 1990, 23, 1318-1329.
(3) Copper content: After decomposing polyphenylene ether with nitric acid, the copper in the residue was quantified by atomic absorption analysis, and the copper content in the polyphenylene ether was calculated.
〔ポリフェニレンエーテル樹脂−Ｉ（ＰＰＥ−Ｉ）の製造例〕
反応器底部に酸素含有ガス導入のためのスパージャー、攪拌タービン翼及びバッフル、反応器上部のベントガスラインに凝縮液分離のためのデカンターを底部に付属させた還流冷却器を備えた１０Ｌのジャケット付きオートクレーブ反応器に、１．４１７２ｇの酸化第一銅、８．５２４３ｇの４７％臭化水素水溶液、１６．５２７７ｇのＮ，Ｎ−ジ−ｎ−ブチルアミン、４１．９１９６ｇのＮ，Ｎ−ジメチル−ｎ−ブチルアミン、３．４１３９ｇのＮ，Ｎ’−ジ−ｔ−ブチルエチレンジアミン、トリオクチルメチルアンモニウムクロライド１．００ｇ及び２７７０．３ｇのトルエンを入れ、初期仕込み液を作製した。次いで、反応器気相部に窒素を導入し、反応器気相部の絶対圧力を０．１０８ＭＰａに制御した。
[Production Example of Polyphenylene Ether Resin-I (PPE-I)]
With a 10-liter jacket equipped with a sparger for introducing oxygen-containing gas at the bottom of the reactor, a stirring turbine blade and baffle, and a reflux condenser with a decanter for separation of condensate at the bottom of the vent gas line at the top of the reactor The autoclave reactor was charged with 1.4172 g cuprous oxide, 8.5243 g 47% aqueous hydrogen bromide solution, 16.5277 g N, N-di-n-butylamine, 41.9196 g N, N-dimethyl-n. -Butylamine, 3.4139 g of N, N'-di-t-butylethylenediamine, 1.00 g of trioctylmethylammonium chloride and 2770.3 g of toluene were added to prepare an initial charging solution. Next, nitrogen was introduced into the reactor gas phase, and the absolute pressure in the reactor gas phase was controlled to 0.108 MPa.
続いて、酸素を窒素で希釈して作った、絶対圧力が０．１０８ＭＰａでその酸素濃度が７０％のガスを、スパージャーより導入し、以後重合中も含めて反応器気相部に窒素を導入しながら、窒素と上記ガスとにより、反応器気相部の絶対圧力が０．１０８ＭＰａに維持される様に、コントロールバルブを制御した。上記ガスの導入速度は３．４５ＮＬ／ｍｉｎとした。上記ガスの導入を開始してから直ちに、１１００ｇの２，６−ジメチルフェノールを１０５６．９ｇのトルエンに溶かした溶液を、プランジャーポンプを用いて３０分で全量を投入し終わる速度で、添加を開始した。重合温度は４０℃を保つようにジャケットに熱媒体を通して調節した。ガス導入開始後約１４０分で、酸素含有ガスに替えて窒素を導入すると共に、反応器にエチレンジアミン４酢酸ナトリウム（ＥＤＴＡ４ナトリウム）５％の水溶液５００ｇを添加し攪拌した。 Subsequently, a gas made by diluting oxygen with nitrogen and having an absolute pressure of 0.108 MPa and an oxygen concentration of 70% was introduced from a sparger, and thereafter nitrogen was introduced into the reactor gas phase part including during polymerization. During the introduction, the control valve was controlled so that the absolute pressure in the gas phase of the reactor was maintained at 0.108 MPa with nitrogen and the above gas. The gas introduction rate was 3.45 NL / min. Immediately after starting the introduction of the gas, a solution in which 1100 g of 2,6-dimethylphenol was dissolved in 1056.9 g of toluene was added at a speed at which the whole amount was charged in 30 minutes using a plunger pump. Started. The polymerization temperature was adjusted by passing a heating medium through the jacket so as to maintain 40 ° C. About 140 minutes after the start of gas introduction, nitrogen was introduced instead of the oxygen-containing gas, and 500 g of an aqueous solution of 5% ethylenediaminetetrasodium acetate (4 sodium EDTA) was added to the reactor and stirred.
その後反応溶液の温度が７０℃になる様に熱媒体でコントロールしながら、攪拌を２時間継続した。攪拌を停止した後、静置分離した水溶液を系外に排出し、更に純水２５０ｇを反応液に添加して１０分間攪拌し、１０分間静置した後に分離した水層を系外に排出した。水層を分離した反応液にほぼ等容のメタノールを添加してポリフェニレンエーテルを沈殿させた。沈殿をろ取し、更に適量のメタノールで洗浄した後に１４０℃程度で１時間強乾燥させ、粉末状ポリフェニレンエーテルを得た。 Thereafter, stirring was continued for 2 hours while controlling with a heat medium so that the temperature of the reaction solution became 70 ° C. After the stirring was stopped, the aqueous solution separated by standing was discharged out of the system, and 250 g of pure water was further added to the reaction solution, stirred for 10 minutes, and allowed to stand for 10 minutes, and then the separated aqueous layer was discharged out of the system. . An approximately equal volume of methanol was added to the reaction solution from which the aqueous layer was separated to precipitate polyphenylene ether. The precipitate was collected by filtration, further washed with an appropriate amount of methanol, and then strongly dried at about 140 ° C. for 1 hour to obtain powdered polyphenylene ether.
得られたポリフェニレンエーテル樹脂−Ｉ（以下、ＰＰＥ−Ｉと略記することがある。）の評価結果を次に示す。
極限粘度：０．４８ｄｌ／ｇ
末端基の数：フェニレンエーテルユニット１００個に対し、０．６４個
銅含有率：０.１ｐｐｍ
The evaluation results of the obtained polyphenylene ether resin-I (hereinafter sometimes abbreviated as PPE-I) are shown below.
Intrinsic viscosity: 0.48 dl / g
Number of end groups: 0.64 per 100 phenylene ether units Copper content: 0.1 ppm
〔ポリフェニレンエーテル樹脂−II（ＰＰＥ−II）の製造例〕
上記ポリフェニレンエーテル−Ｉの製造方法と同様に製造したが、トリオクチルメチルアンモニウムクロライド(ＴＯＭ)の添加量を０.３ｇに、ガス導入開始後の窒素導入開始を約１４０分から約１５５分に変更し、他は同様に行って、粉末状のポリフェニレンエーテルを得た。
[Production Example of Polyphenylene Ether Resin-II (PPE-II)]
The polyphenylene ether-I was produced in the same manner as described above, but the amount of trioctylmethylammonium chloride (TOM) added was changed to 0.3 g, and the nitrogen introduction start after gas introduction was changed from about 140 minutes to about 155 minutes. The others were carried out in the same manner to obtain a powdered polyphenylene ether.
得られたポリフェニレンエーテル樹脂−II（以下、ＰＰＥ−IIと略記することがある。）の評価結果を次に示す。
極限粘度：０．４８ｄｌ／ｇ
末端基の数：フェニレンエーテルユニット１００個に対し、０．６０個
銅含有率：０.５ｐｐｍ
The evaluation results of the obtained polyphenylene ether resin-II (hereinafter sometimes abbreviated as PPE-II) are shown below.
Intrinsic viscosity: 0.48 dl / g
Number of terminal groups: 0.60 per 100 phenylene ether units Copper content: 0.5 ppm
〔ポリフェニレンエーテル樹脂―III（ＰＰＥ−III）の製造例〕
空気吹き込み管の付いた重合反応器に、コンデンサーを２段直列に繋いだ。コンデンサーの温度が約０℃になる様に冷媒を流し温度調節をし、缶出液のトルエン相は連続的に重合器内に戻す様にした。臭化第二銅２２ｇ、ジブチルアミン４００ｇ、トルエン９８００ｇの触媒溶液中に空気をモノマー１ｋｇあたり、１０ＮＬ／分で供給しながら、２，６−ジメチルフェノール（モノマー）２３５０ｇをトルエン５４００ｇに溶かした溶液を６０分かけて滴下し、４０℃で重合を行った。モノマー滴下１２０分後、ＥＤＴＡ４ナトリウムを触媒銅に対し１．５倍モル量溶解した水溶液（水溶液量は重合反応液全量に対し０．２重量倍）を攪拌しながら反応液に加え反応を停止した。
[Production Example of Polyphenylene Ether Resin-III (PPE-III)]
Two stages of condensers were connected in series to a polymerization reactor equipped with an air blowing tube. The temperature of the condenser was adjusted so that the condenser temperature was about 0 ° C., and the temperature was adjusted so that the toluene phase of the bottoms was continuously returned to the polymerization reactor. A solution prepared by dissolving 2,350 g of 2,6-dimethylphenol (monomer) in 5400 g of toluene while supplying air at a rate of 10 NL / min per kg of monomer into a catalyst solution of 22 g of cupric bromide, 400 g of dibutylamine and 9800 g of toluene. The solution was added dropwise over 60 minutes and polymerized at 40 ° C. 120 minutes after dropping the monomer, an aqueous solution in which EDTA4 sodium was dissolved in a 1.5-fold molar amount with respect to the catalyst copper (the amount of the aqueous solution was 0.2 weight times the total amount of the polymerization reaction solution) was added to the reaction solution while stirring to stop the reaction .
反応を停止した後、静置分離して水層を系外に排出し、純水５５０ｇを反応液に添加して１０分間攪拌し、１０分間静置し、分離した水層を系外に排出した。更に同様の操作を繰り返した。すなわち、２回目はＥＤＴＡ４ナトリウムを使用触媒銅の０．５倍モル量溶解した水溶液（水溶液量は重合反応液全量に対し０．２重量倍）を攪拌しながら反応液に加え静置分離した。その後上記と同様に水層を系外に排出し、純水６００ｇを反応液に添加して１０分間攪拌し、１０分間静置し、分離した水層を系外に排出した。
得られた反応液にほぼ等容のメタノールを添加してポリフェニレンエーテルを沈殿させた。沈殿をろ取し、更に適量のメタノールでポリフェニレンエーテルを洗浄し、１４０℃程度で１時間強乾燥させ、粉末状ポリフェニレンエーテルを得た。
After stopping the reaction, the mixture was left standing and separated, the aqueous layer was discharged out of the system, 550 g of pure water was added to the reaction solution, stirred for 10 minutes, allowed to stand for 10 minutes, and the separated aqueous layer was discharged out of the system. did. Further, the same operation was repeated. That is, in the second time, an aqueous solution in which EDTA tetrasodium was dissolved in a molar amount of 0.5 times the amount of catalyst copper (the amount of the aqueous solution was 0.2 times by weight with respect to the total amount of the polymerization reaction solution) was added to the reaction solution while stirring and left to stand. Thereafter, in the same manner as described above, the aqueous layer was discharged out of the system, 600 g of pure water was added to the reaction solution, stirred for 10 minutes, allowed to stand for 10 minutes, and the separated aqueous layer was discharged out of the system.
An approximately equal volume of methanol was added to the resulting reaction solution to precipitate polyphenylene ether. The precipitate was collected by filtration, further washed with an appropriate amount of methanol and washed with polyphenylene ether at about 140 ° C. for 1 hour to obtain powdery polyphenylene ether.
得られたポリフェニレンエーテル−III（以下、ＰＰＥ−IIIと略記することがある）の評価結果を次に示す。
極限粘度：０．４８ｄｌ／ｇ
末端基の数：フェニレンエーテルユニット１００個に対し、０．２３個
銅含有率：０.１ｐｐｍ
The evaluation results of the obtained polyphenylene ether-III (hereinafter sometimes abbreviated as PPE-III) are shown below.
Intrinsic viscosity: 0.48 dl / g
Number of end groups: 0.23 per 100 phenylene ether units Copper content: 0.1 ppm
ポリフェニレンエーテル樹脂（ＰＰＥ−Ａ）以外の原材料は、次のとおりである。
（１）スチレン系樹脂：ハイインパクトポリスチレン、エー・アンド・エム社製（品番：ＨＴ４７８）、分子量（Ｍｗ）２００，０００、ＭＦＲ３．２ｇ／１０分（以下、ＨＩＰＳと略記）
（２）カーボンブラック：ケッチェンブラックＥＣ、ライオン・アクゾ製（以下、カーボンブラックＥＣと略記）
（３）スチレン系エラストマー：シェル化学製ＳＥＢＳ（商品名：クレイトンＧ１６５２）（以下、ＳＥＢＳと略記）
（４）マイカ：（株）レプコ社から発売（商品名：フロゴパイトマイカＳ２００）（以下、マイカと略記）
（５）タルク：シランカップリング剤（γ-メタクリロキシプロピルトリメトキシシラン）で処理されたタルクＫ−５、松村産業（株）製（以下、タルクと略記）
（６）安定剤：試薬１級の酸化亜鉛（以下、酸化亜鉛と略記）
Raw materials other than the polyphenylene ether resin (PPE-A) are as follows.
(1) Styrenic resin: high impact polystyrene, manufactured by A & M Co. (product number: HT478), molecular weight (Mw) 200,000, MFR 3.2 g / 10 min (hereinafter abbreviated as HIPS)
(2) Carbon Black: Ketjen Black EC, manufactured by Lion Akzo (hereinafter abbreviated as Carbon Black EC)
(3) Styrenic elastomer: SEBS manufactured by Shell Chemical (trade name: Kraton G1652) (hereinafter abbreviated as SEBS)
(4) Mica: Released from Repco, Inc. (Product name: Phlogopite Mica S200) (hereinafter abbreviated as Mica)
(5) Talc: Talc K-5 treated with a silane coupling agent (γ-methacryloxypropyltrimethoxysilane), manufactured by Matsumura Sangyo Co., Ltd. (hereinafter abbreviated as talc)
(6) Stabilizer: Reagent primary zinc oxide (hereinafter abbreviated as zinc oxide)
〔樹脂組成物の製造〕
所定の重量比で配合した組成物を、田辺機械（株）製スクリュー径４０ｍｍの単軸押出機を使用し、シリンダー設定温度２７０〜３２０℃、スクリュー回転速度５０ｒｐｍの条件で溶融・混練し、押出し、ペレット状の樹脂組成物を製造した。
[Production of resin composition]
A composition blended at a predetermined weight ratio is melted and kneaded using a single screw extruder with a screw diameter of 40 mm manufactured by Tanabe Machine Co., Ltd. under conditions of a cylinder set temperature of 270 to 320 ° C. and a screw rotation speed of 50 rpm, and extruded. A pellet-shaped resin composition was produced.
〔試験片の成形条件〕
ペレット状の樹脂組成物を１１０℃で５時間乾燥後、射出成形機（東芝機械製、ＩＳ１５０型）により金型温度１２０℃、シリンダー設定温度２９０〜３３０℃、射出速度１５％で、５０ｍｍ×９０ｍｍ×３．２ｍｍの角板成形品を射出成形した。角板成形品と同一条件で、６３．５ｍｍ×１２．７ｍｍ×３．２ｍｍのアイゾット衝撃試験片、１２７ｍｍ×１２．７ｍｍ×６．３５ｍｍの荷重撓み温度試験片を成形した。
[Test specimen molding conditions]
After drying the pellet-shaped resin composition at 110 ° C. for 5 hours, the injection molding machine (manufactured by Toshiba Machine, IS150 type) has a mold temperature of 120 ° C., a cylinder set temperature of 290 to 330 ° C., an injection speed of 15%, and 50 mm × 90 mm. A 3.2 mm square plate molded product was injection molded. A 63.5 mm × 12.7 mm × 3.2 mm Izod impact test piece and a 127 mm × 12.7 mm × 6.35 mm load deflection temperature test piece were molded under the same conditions as the square plate molded product.
〔試験片の物性評価〕
（１）アイゾット衝撃強度：ＡＳＴＭ−Ｄ２５６に準じ、ノッチなしで、２３℃で５本づつ測定し、５本の平均値でアイゾット衝撃強度（以下、ＩＺと略記）を示した。
（２）熱処理後のアイゾット衝撃強度：ＩＣ製造時の高温ベーキング工程での熱劣化の度合いを試験するため、アイゾット衝撃試験片を荷重撓み温度より１５℃低い温度で５０時間熱処理後、２３℃で２４時間放置し、前記（１）に準じてアイゾット衝撃強度（以下、熱処理ＩＺと略記）を求めた。
（３）荷重たわみ温度：ＡＳＴＭ Ｄ６４８に従い、１．８２ＭＰａの条件で、荷重たわみ温度（以下、ＤＴＵＬと略記）を測定した。
（４）表面抵抗率：５０ｍｍ×９０ｍｍ×３．２ｍｍの角板成形品を用い、ロレスタ又はハイレスタ（いずれも、三菱化学（株）製）にて任意の３ヶ所について測定を行った。（１０4Ω以上の値のものについてはハイレスタを用い、それ以下になるものについてはロレスタを用いた。）
[Evaluation of physical properties of test piece]
(1) Izod impact strength: According to ASTM-D256, five Izod impact strengths were measured at 23 ° C. without notches, and the average value of the five Izod impact strengths (hereinafter abbreviated as IZ) was shown.
(2) Izod impact strength after heat treatment: In order to test the degree of thermal degradation in the high-temperature baking process at the time of IC manufacture, the Izod impact test piece was heat-treated at a temperature 15 ° C. lower than the load deflection temperature for 50 hours and then at 23 ° C. After standing for 24 hours, the Izod impact strength (hereinafter abbreviated as heat treatment IZ) was determined according to the above (1).
(3) Deflection temperature under load: The deflection temperature under load (hereinafter abbreviated as DTUL) was measured in accordance with ASTM D648 under the condition of 1.82 MPa.
(4) Surface resistivity: A square plate molded product of 50 mm × 90 mm × 3.2 mm was used, and measurement was performed at any three locations using Loresta or Hiresta (both manufactured by Mitsubishi Chemical Corporation). (Hiresta was used for those with a value of 10 4 Ω or more, and Loresta was used for those with a value lower than 10 4 Ω.)
（５）ＩＣトレー反り量：上記の５０ｍｍ×９０ｍｍ×３．２ｍｍ角板成形品と同一条件で、図１に示すＩＣ用トレーを成形し、２３℃、相対湿度５５±３％の室内で４８時間状態調節した。その後、トレーを１枚ずつ定盤上に置き、図１に示すａ〜ｉの８箇所を三次元寸法測定器で測定した。同様にして、荷重撓み温度より１０℃低い温度で３時間熱処理し、室温で４８時間冷却後、未処理反り量の測定と同一方法で熱処理後の反り量を測定した。
（６）カーボンブラックの脱離性：５０ｍｍ×９０ｍｍ×３．２ｍｍの角板状成形品にセロテープ（登録商標）（ニチバン（株）製、ＣＴ４０５Ａ−１８）を貼り付け、それをはがした時の剥離状態を目視にて下記基準に基づき判断した。
○：力を入れてこすってもほとんど剥離しない。
△：力を入れてこすれば剥離する。
×：軽くこすっただけでも剥離する。
(5) IC tray warpage amount: The IC tray shown in FIG. 1 was molded under the same conditions as the above-mentioned 50 mm × 90 mm × 3.2 mm square plate molded product, and it was 48 in a room at 23 ° C. and relative humidity 55 ± 3%. Time condition was adjusted. Thereafter, the trays were placed one by one on the surface plate, and eight points a to i shown in FIG. 1 were measured with a three-dimensional dimension measuring instrument. Similarly, heat treatment was performed at a temperature 10 ° C. lower than the load deflection temperature for 3 hours, and after cooling at room temperature for 48 hours, the warpage amount after the heat treatment was measured by the same method as the measurement of the untreated warpage amount.
(6) Carbon black detachability: When cellotape (registered trademark) (manufactured by Nichiban Co., Ltd., CT405A-18) is attached to a square plate-shaped molded product of 50 mm × 90 mm × 3.2 mm, and peeled off The peeled state was visually determined based on the following criteria.
○: Almost no peeling even when rubbed with force.
Δ: Detach if force is applied.
X: It peels only by rubbing lightly.
〔実施例１〜５、比較例１〜５〕
各原材料を表１及び表２に示した比率で配合し、上記条件でペレット状樹脂組成物を製造し、試験片を成形し、物性評価を行い、評価結果を表１及び表２に示した。表１及び表２より、本発明の樹脂組成物は、カーボンブラックの脱離が少なく、該樹脂組成物から成形されたＩＣ用トレーは熱処理前後の反り量も小さいことが明らかになった。
[Examples 1-5, Comparative Examples 1-5]
Each raw material is blended in the ratios shown in Table 1 and Table 2, a pellet-shaped resin composition is produced under the above conditions, a test piece is molded, physical properties are evaluated, and the evaluation results are shown in Table 1 and Table 2. . From Tables 1 and 2, it was found that the resin composition of the present invention has little carbon black detachment, and the IC tray molded from the resin composition has a small amount of warpage before and after heat treatment.
Claims (6)
一般式（１）
一般式（２）
General formula (1)
General formula (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005215057A JP4920210B2 (en) | 2005-07-25 | 2005-07-25 | Resin composition, molded product and IC tray |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005215057A JP4920210B2 (en) | 2005-07-25 | 2005-07-25 | Resin composition, molded product and IC tray |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007031519A JP2007031519A (en) | 2007-02-08 |
| JP4920210B2 true JP4920210B2 (en) | 2012-04-18 |
Family
ID=37791151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005215057A Active JP4920210B2 (en) | 2005-07-25 | 2005-07-25 | Resin composition, molded product and IC tray |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4920210B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5004595B2 (en) * | 2007-01-16 | 2012-08-22 | 旭化成ケミカルズ株式会社 | Polyphenylene ether resin tray and method for producing the same |
| US20080306205A1 (en) * | 2007-06-06 | 2008-12-11 | Brett David Ermi | Black-colored thermoplastic compositions, articles, and methods |
| JP5393411B2 (en) * | 2009-11-13 | 2014-01-22 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing molded product of polyphenylene ether resin composition |
| JP5715484B2 (en) * | 2011-05-12 | 2015-05-07 | 三菱エンジニアリングプラスチックス株式会社 | Process for producing conductive polyphenylene ether resin composition |
| CN111372372B (en) * | 2020-03-30 | 2023-12-22 | 广东生益科技股份有限公司 | Circuit material and circuit board comprising same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07116353B2 (en) * | 1984-02-17 | 1995-12-13 | 三菱瓦斯化学株式会社 | Polyphenylene ether resin composition having excellent thermal stability |
| JPH11256025A (en) * | 1998-03-10 | 1999-09-21 | Asahi Chem Ind Co Ltd | Conductive resin composition |
| JPH11322921A (en) * | 1998-05-19 | 1999-11-26 | Asahi Chem Ind Co Ltd | Aromatic (co)polymer solution and insulation film made therefrom |
| JPH11335549A (en) * | 1998-05-26 | 1999-12-07 | Mitsui Chem Inc | Electrically conductive resin composition, semiconductor-packaging container, and ic tray |
| US6472499B1 (en) * | 2000-08-04 | 2002-10-29 | General Electric Company | Preparation of high intrinsic viscosity poly(arylene ether) resins |
| KR100381972B1 (en) * | 2000-10-02 | 2003-05-01 | 한국지이플라스틱스 유한회사 | Polyphenyleneoxide-based composite resin composition for ic tray |
| US6860966B2 (en) * | 2001-11-12 | 2005-03-01 | General Electric | Method for isolating polyphenylene ether polymer resins from solution |
| JP2004083733A (en) * | 2002-08-27 | 2004-03-18 | Asahi Kasei Chemicals Corp | Crystalline polyphenylene oxide resin |
-
2005
- 2005-07-25 JP JP2005215057A patent/JP4920210B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007031519A (en) | 2007-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8367755B2 (en) | Thermoplastic resin composition, and molded product and sheet comprising the composition | |
| EP0048154B1 (en) | Resin composition for injection molding, method for producing the composition, and articles molded therefrom | |
| CN1192053C (en) | Method for improving adhesion of metal films to polyphenylene ether resins | |
| JP5032032B2 (en) | Low odor resin composition | |
| EP1678255B1 (en) | Composition comprising functionalized poly(arylene ether) and ethylene-alkyl (meth)acrylate copolymer, method for the preparation thereof, and articles prepared therefrom | |
| AU3759400A (en) | Polyphenylene ether resin concentrates containing organic phosphates | |
| JP2004176071A (en) | Additive for thermoplastic resin and flame-retardant resin composition | |
| EP3327086A1 (en) | Resin composition and molded article | |
| JP4920210B2 (en) | Resin composition, molded product and IC tray | |
| CN108117738B (en) | Resin composition | |
| JP2008101200A (en) | Thermoplastic resin composition | |
| JP4804165B2 (en) | Manufacturing method of resin sheet | |
| JP2007254620A (en) | Thermoplastic resin composition | |
| KR20150038968A (en) | Thermoplastic resin composition and article comprising the same | |
| JP6343516B2 (en) | Automotive interior parts made of reinforced polyphenylene ether resin composition | |
| JP7142636B2 (en) | Resin composition, molded product and electric wire | |
| JP2009067928A (en) | Thermoplastic resin composition | |
| JP6899258B2 (en) | Resin composition and molded product | |
| JP3745121B2 (en) | Polyphenylene ether resin composition | |
| JP4291012B2 (en) | Conductive resin composition | |
| JP5188073B2 (en) | Thermoplastic resin composition | |
| JP2020037663A (en) | Flame-retardant resin composition | |
| JP2009249515A (en) | Polyphenylene ether resin film | |
| JP2007246893A (en) | Thermoplastic resin composition | |
| JP4749205B2 (en) | Polyphenylene ether resin sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080115 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110322 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110329 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120117 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120201 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4920210 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150210 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |