JP6413424B2 - Thermoplastic resin composition, method for producing the same, and molded article - Google Patents
Thermoplastic resin composition, method for producing the same, and molded article Download PDFInfo
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- JP6413424B2 JP6413424B2 JP2014148732A JP2014148732A JP6413424B2 JP 6413424 B2 JP6413424 B2 JP 6413424B2 JP 2014148732 A JP2014148732 A JP 2014148732A JP 2014148732 A JP2014148732 A JP 2014148732A JP 6413424 B2 JP6413424 B2 JP 6413424B2
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- Prior art keywords
- thermoplastic resin
- range
- resin composition
- electrically conductive
- conductive filler
- 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.)
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- 229920005992 thermoplastic resin Polymers 0.000 title claims description 71
- 239000011342 resin composition Substances 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000011246 composite particle Substances 0.000 claims description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000011231 conductive filler Substances 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 23
- 238000000465 moulding Methods 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 238000004898 kneading Methods 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011164 primary particle Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- -1 polyethylene Polymers 0.000 description 23
- 229920000412 polyarylene Polymers 0.000 description 21
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 17
- 239000000945 filler Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000006229 carbon black Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 125000005372 silanol group Chemical group 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000019000 fluorine Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- FKOKUHFZNIUSLW-UHFFFAOYSA-N 2-Hydroxypropyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(C)O FKOKUHFZNIUSLW-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- JAUFWPNLLLUYNV-UHFFFAOYSA-N 3-(16-methylheptadecoxy)propane-1,2-diol Chemical compound CC(C)CCCCCCCCCCCCCCCOCC(O)CO JAUFWPNLLLUYNV-UHFFFAOYSA-N 0.000 description 1
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
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- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 206010047289 Ventricular extrasystoles Diseases 0.000 description 1
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- 238000005299 abrasion Methods 0.000 description 1
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
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- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CRNJBCMSTRNIOX-UHFFFAOYSA-N methanolate silicon(4+) Chemical compound [Si+4].[O-]C.[O-]C.[O-]C.[O-]C CRNJBCMSTRNIOX-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Landscapes
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
Description
本発明は、電気伝導性を安定して付与できる熱可塑性樹脂組成物と該組成物から成形される樹脂成形体、フィルムまたはシートに関する。 The present invention relates to a thermoplastic resin composition capable of stably imparting electrical conductivity and a resin molded body, film or sheet molded from the composition.
熱可塑性樹脂にカーボンブラックのような電気伝導性フィラーを溶融混練して製造される導電性熱可塑性樹脂を薄肉成形した導電性熱可塑性樹脂成形体、特にフィルム又はシートは、一般的に、半導体や電子部品の輸送や保管などに、また、電子写真等に用いられる転写ベルトなどに使用されている。導電性熱可塑性樹脂フィルム又はシートには、優れた導電性と表面平滑性が求められている。 A conductive thermoplastic resin molded product, particularly a film or sheet, formed by thinly molding a conductive thermoplastic resin produced by melting and kneading an electrically conductive filler such as carbon black in a thermoplastic resin, is generally a semiconductor or It is used for transportation and storage of electronic parts and for transfer belts used for electrophotography. The conductive thermoplastic resin film or sheet is required to have excellent conductivity and surface smoothness.
熱可塑性樹脂に電気伝導性を付与する方法としては、カーボンブラックや炭素繊維等の電気伝導性フィラーを２軸押出機やバンバリーミキサーなどで溶融混練する方法が一般的に行われている（特許文献１参照）。 As a method of imparting electrical conductivity to a thermoplastic resin, a method of melt-kneading an electrically conductive filler such as carbon black or carbon fiber with a twin screw extruder or a Banbury mixer is generally performed (Patent Literature). 1).
しかし、このような熱可塑性樹脂にカーボンブラックを溶融混練する方法で製造された熱可塑性樹脂フィルム又はシートを薄肉成形した場合、その表面にカーボンブラックの凝集物が発生するという問題がある。特に、ポリカーボネート、ポリエチレン、ポリプロピレン、ポリフェニレンエーテル、ポリエチレンテレフタレート、ポリフェニレンスルファイド等の熱可塑性樹脂を用いたシート又はフィルムにおいては、前記カーボンブラックの分散性が悪く、シート又はフィルム中でカーボンブラックの凝集体が形成される。その結果、成形体表面の外観を損ねたり、成形体表面の電気伝導性にばらつきが起こるなどの様々な問題が生じることがある。 However, when a thermoplastic resin film or sheet produced by melt-kneading carbon black in such a thermoplastic resin is formed into a thin wall, there is a problem that aggregates of carbon black are generated on the surface. In particular, in a sheet or film using a thermoplastic resin such as polycarbonate, polyethylene, polypropylene, polyphenylene ether, polyethylene terephthalate, or polyphenylene sulfide, the dispersibility of the carbon black is poor, and the aggregate of carbon black in the sheet or film. Is formed. As a result, various problems may occur, such as the appearance of the surface of the molded body being impaired or the electrical conductivity of the surface of the molded body being varied.
特に、半導体や電子部品との接触用途や、転写ベルトなどの用途では、非常に高精度の電気伝導性制御が求められており、上記のような電気伝導性フィラーの再凝集抑制による電気伝導性制御の精度向上や凝集物低減による表面外観の向上が求められていた。 In particular, in applications such as contact with semiconductors and electronic parts and in applications such as transfer belts, very high-precision electrical conductivity control is required. There has been a demand for improvement in surface appearance by improving control accuracy and reducing aggregates.
そこで本発明が解決しようとする課題は、電気伝導性フィラーの凝集を抑制し、成形体表面の外観性向上と電気伝導性のばらつきを抑え、電気伝導性を安定して付与できる熱可塑性樹脂成形体およびその製造方法を提供すること、そのような成形体を成形可能な熱可塑性樹脂組成物およびその製造方法を提供することにある。 Therefore, the problem to be solved by the present invention is to suppress the aggregation of the electrically conductive filler, to improve the appearance of the molded body surface, to suppress the variation in the electrical conductivity, and to stably provide the electrical conductivity. It is providing the body and its manufacturing method, providing the thermoplastic resin composition which can shape | mold such a molded object, and its manufacturing method.
本願発明者らは種々の検討を行った結果、用いる電気伝導性フィラーをシリカで被覆した複合粒子としたものを用いることで、前記課題を解決できることを見出し、本発明を完成するに至った。 As a result of various studies, the inventors of the present application have found that the above problems can be solved by using composite particles in which the electrically conductive filler used is coated with silica, and the present invention has been completed.
すなわち、本発明は、熱可塑性樹脂（Ａ）と、電気伝導性フィラーをシリカで被覆した複合粒子（Ｂ）を必須成分とする熱可塑性樹脂組成物であって、
熱可塑性樹脂（Ａ）が５０〜９９質量％の範囲であり、前記複合粒子（Ｂ）が１〜５０質量％の範囲であること、かつ、
前記複合粒子（Ｂ）の平均粒子径が０．１〜２０の範囲であること、かつ、前記複合粒子が、シリカをマトリックスとして、当該マトリックス中に前記電気伝導性フィラーの２粒子以上が分散した分散体であることを特徴とする熱可塑性樹脂組成物に関する。
That is, the present invention is a thermoplastic resin composition comprising, as essential components, a thermoplastic resin (A) and composite particles (B) in which an electrically conductive filler is coated with silica,
The thermoplastic resin (A) is in the range of 50 to 99% by mass, the composite particles (B) are in the range of 1 to 50% by mass, and
The composite particles (B) have an average particle size in the range of 0.1 to 20, and the composite particles have silica as a matrix and two or more particles of the electrically conductive filler are dispersed in the matrix. The present invention relates to a thermoplastic resin composition characterized by being a dispersion.
また、本発明は、前記記載の熱可塑性樹脂組成物を溶融成形してなる成形体に関する。 Moreover, this invention relates to the molded object formed by melt-molding the said thermoplastic resin composition.
また、本発明は、熱可塑性樹脂（Ａ）と、複合粒子（Ｂ）とを、溶融混錬押出機に投入し、溶融混練する熱可塑性樹脂組成物の製造方法であって、
前記複合粒子（Ｂ）の平均粒子径が０．１〜２０μｍの範囲であること、かつ、
前記複合粒子が、シリカをマトリックスとして、当該マトリックス中に前記電気伝導性フィラーの２粒子以上が分散した分散体であることを特徴とする熱可塑性樹脂組成物の製造方法に関する。
Further, the present invention is a method for producing a thermoplastic resin composition in which a thermoplastic resin (A) and composite particles (B) are charged into a melt kneading extruder and melt kneaded,
The average particle size of the composite particles (B) is in the range of 0.1 to 20 μm, and
The present invention relates to a method for producing a thermoplastic resin composition, wherein the composite particles are a dispersion in which two or more particles of the electrically conductive filler are dispersed in a matrix of silica.
本発明によれば、電気伝導性フィラーの凝集を抑制し、成形体表面の外観性向上と電気伝導性のばらつきを抑え、電気伝導性を安定して付与できる熱可塑性樹脂成形体およびその製造方法を提供すること、そのような成形体を成形可能な熱可塑性樹脂組成物およびその製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin molding which suppresses aggregation of an electroconductive filler, suppresses the external appearance improvement of a molded object surface, the dispersion | variation in electrical conductivity, and can provide electric conductivity stably, and its manufacturing method It is possible to provide a thermoplastic resin composition capable of molding such a molded body and a method for producing the same.
本発明の熱可塑性樹脂組成物は、熱可塑性樹脂（Ａ）と、電気伝導性フィラーをシリカで被覆した複合粒子（Ｂ）を必須成分とする熱可塑性樹脂組成物であって、
熱可塑性樹脂（Ａ）が５０〜９９質量％の範囲であり、前記複合粒子（Ｂ）が１〜５０質量％の範囲であること、かつ、
前記複合粒子（Ｂ）の平均粒子径が０．１〜２０μｍの範囲であること、かつ、
前記複合粒子が、シリカをマトリックスとして、当該マトリックス中に前記電気伝導性フィラーの２粒子以上が分散した分散体であることを特徴とする。
The thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising, as essential components, a thermoplastic resin (A) and composite particles (B) in which an electrically conductive filler is coated with silica,
The thermoplastic resin (A) is in the range of 50 to 99% by mass, the composite particles (B) are in the range of 1 to 50% by mass, and
The average particle size of the composite particles (B) is in the range of 0.1 to 20 μm, and
The composite particle is a dispersion in which silica is used as a matrix and two or more particles of the electrically conductive filler are dispersed in the matrix.
本発明に用いる熱可塑性樹脂（Ａ）としては、ポリオレフィン、ポリスチレン、ポリアミド、ハロゲン化ビニル樹脂、ポリアセタール、飽和ポリエステル、ポリカーボネート、ポリアリールスルホン、ポリアリールケトン、ポリアリーレンエーテル、ポリアリーレンスルフィド、ポリアリールエーテルケトン、ポリエーテルスルホン、ポリアリーレンサルファイドスルフォン、ポリアリレート、液晶ポリエステル、フッ素樹脂等の熱可塑性樹脂が挙げられるが、かかる群から選ばれる熱可塑性樹脂を単独で用いることもでき、または二種以上の熱可塑性樹脂を組み合わせてポリマーアロイとして用いることもできる。 As the thermoplastic resin (A) used in the present invention, polyolefin, polystyrene, polyamide, vinyl halide resin, polyacetal, saturated polyester, polycarbonate, polyarylsulfone, polyarylketone, polyarylene ether, polyarylene sulfide, polyarylether Thermoplastic resins such as ketone, polyethersulfone, polyarylene sulfide sulfone, polyarylate, liquid crystal polyester, fluororesin and the like can be mentioned, but a thermoplastic resin selected from such a group can be used alone, or two or more A thermoplastic resin can also be used in combination as a polymer alloy.
これらのうち、近年の電気出力向上に伴う発熱量の増加に対して充分に対応可能な耐熱性を有する点から、好ましくは融点が１７０℃以上、より好ましくは１７０〜３９０℃の範囲の熱可塑性樹脂、または、好ましくは軟化点が５０℃以上、より好ましくは７０〜２００℃のエラストマ、ゴムが、好ましい樹脂群として挙げられ、具体的にはポリアミド６（６−ナイロン）、ポリアミド６６（６，６−ナイロン）またはポリアミド１２（１２−ナイロン）などの脂肪族骨格を有するポリアミドや、ポリアミド６T（６T−ナイロン）、ポリアミド９T（９T−ナイロン）などの芳香族骨格を有するポリアミドなど融点が１７０℃以上、好ましくは１７０〜３１０℃の範囲であるポリアミドや、ポリブチレンテレフタレート、ポリイソブチレンテレフタレート、ポリエチレンテレフタレートまたはポリシクロヘキセンテレフタレートなどの融点が２２０℃以上、好ましくは２２０〜２８０℃の範囲であるポリエステル樹脂や、融点が２６５℃以上、好ましくは２６５〜３５０℃の範囲、さらに好ましくは２８０〜３００℃の範囲であるポリフェニレンスルフィドに代表されるポリアリーレンスルフィドや、融点が３００〜３９０℃の範囲であるポリエーテルエーテルケトンや、パラヒドロキシ安息香酸を骨格中に有する融点が３００℃以上、好ましくは３００℃〜熱分解温度（３８０℃）未満である液晶ポリマーや、融点が２２０℃以上、好ましくは２２０〜２８０℃の範囲であるシンジオタクチックポリスチレン等の融点が１７０〜３９０℃の範囲の熱可塑性樹脂といった、いわゆる汎用エンジニアリングプラスチックないしスーパーエンジニアリングプラスチックや、オレフィン系、スチレン系、ウレタン系、ポリエステル系、ポリアミド系、塩ビ系、フッ素系などのエラストマやゴムが挙げられ、このうち、優れた難燃性や寸法安定性を有するポリアリーレンスルフィドが好ましい。 Among these, the thermoplastic resin preferably has a melting point of 170 ° C. or higher, more preferably in the range of 170 to 390 ° C., from the viewpoint that it has sufficient heat resistance to cope with the increase in calorific value accompanying recent improvements in electrical output. Resin, or preferably an elastomer or rubber having a softening point of 50 ° C. or higher, more preferably 70 to 200 ° C. is mentioned as a preferable resin group. Specifically, polyamide 6 (6-nylon), polyamide 66 (6, Polyamide having an aliphatic skeleton such as 6-nylon) or polyamide 12 (12-nylon), or a polyamide having an aromatic skeleton such as polyamide 6T (6T-nylon) or polyamide 9T (9T-nylon). As described above, polyamide, polybutylene terephthalate, polyisobutylene terephthalate, preferably in the range of 170 to 310 ° C. A polyester resin having a melting point of 220 ° C. or higher, preferably 220 to 280 ° C., a melting point of 265 ° C. or higher, preferably 265 to 350 ° C., more preferably 280 to 350 ° C., such as tarate, polyethylene terephthalate or polycyclohexene terephthalate. A polyarylene sulfide typified by polyphenylene sulfide in the range of 300 ° C., a polyether ether ketone having a melting point in the range of 300 to 390 ° C., a melting point having parahydroxybenzoic acid in the skeleton of 300 ° C. or more, preferably Thermoplastic having a melting point in the range of 170 to 390 ° C., such as a liquid crystal polymer having a melting point of 300 ° C. to less than the thermal decomposition temperature (380 ° C.) or a syndiotactic polystyrene having a melting point of 220 ° C. or higher, preferably in the range of 220 to 280 ° C. So-called general-purpose resin Examples include engineering plastics and super engineering plastics, olefins, styrenes, urethanes, polyesters, polyamides, PVCs, fluorines, and other elastomers and rubbers. Of these, excellent flame retardancy and dimensional stability. Polyarylene sulfides having the following are preferred.
本発明に好ましく使用されるポリアリーレンスルフィド樹脂（Ａ１）は、芳香族環と硫黄原子とが結合した構造を繰り返し単位とする樹脂構造を有するものであり、具体的には、下記式（１） The polyarylene sulfide resin (A1) preferably used in the present invention has a resin structure having a repeating unit of a structure in which an aromatic ring and a sulfur atom are bonded. Specifically, the polyarylene sulfide resin (A1) is represented by the following formula (1):
ここで、前記式（１）で表される構造部位は、特に該式中のＲ１及びＲ２は、前記ポリアリーレンスルフィド樹脂（Ａ１）の機械的強度の点から水素原子であることが好ましく、その場合、下記式（２）で表されるパラ位で結合するもの、及び下記式（３）で表されるメタ位で結合するものが挙げられる。
Here, in the structural part represented by the formula (1), it is particularly preferable that R 1 and R 2 in the formula are hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin (A1). In this case, those bonded at the para position represented by the following formula (2) and those bonded at the meta position represented by the following formula (3) are exemplified.
また、前記ポリアリーレンスルフィド樹脂（Ａ１）は、前記式（１）で表される構造部位のみならず、下記の構造式（４）〜（７） In addition, the polyarylene sulfide resin (A1) includes not only the structural portion represented by the formula (1) but also the following structural formulas (4) to (7).
また、前記ポリアリーレンスルフィド樹脂（Ａ１）は、その分子構造中に、下記式（８）
The polyarylene sulfide resin (A1) has the following formula (8) in its molecular structure.
また、ポリアリーレンスルフィド樹脂（Ａ１）は３００℃で測定した溶融粘度（Ｖ６）が２〜１，０００〔Ｐａ・ｓ〕の範囲であることが好ましく、さらに流動性および機械的強度のバランスが良好となることから５〜１００〔Ｐａ・ｓ〕の範囲が好ましい。ただし、３００℃で測定した溶融粘度（Ｖ６）とは、フローテスターを用いて、温度３００℃、荷重１．９６ＭＰａ、オリフィス長とオリフィス径との、前者／後者の比が１０／１であるオリフィスを使用して６分間保持した後の溶融粘度を表す。また、ＰＡＳ樹脂（Ａ１）は、その非ニュートン指数が０．９０〜２．００の範囲であることが好ましい。リニア型ポリアリーレンスルフィド樹脂を用いる場合には、非ニュートン指数が０．９０〜１．２０の範囲、さらに０．９５〜１．１５の範囲であることが好ましく、特に０．９５〜１．１０であることが好ましい。このようなポリアリーレンスルフィド樹脂は機械的物性、流動性、耐磨耗性に優れる。ただし、非ニュートン指数（Ｎ値）は、キャピログラフを用いて３００℃、オリフィス長（Ｌ）とオリフィス径（Ｄ）の比、Ｌ／Ｄ＝４０の条件下で、剪断速度及び剪断応力を測定し、下記式を用いて算出した値である。 The polyarylene sulfide resin (A1) preferably has a melt viscosity (V6) measured at 300 ° C. in the range of 2 to 1,000 [Pa · s], and further has a good balance between fluidity and mechanical strength. Therefore, the range of 5 to 100 [Pa · s] is preferable. However, melt viscosity (V6) measured at 300 ° C. is an orifice having a temperature / 300 ° C., a load of 1.96 MPa, an orifice length and an orifice diameter of 10/1 using a flow tester. Represents the melt viscosity after holding for 6 minutes. The PAS resin (A1) preferably has a non-Newtonian index in the range of 0.90 to 2.00. When the linear polyarylene sulfide resin is used, the non-Newtonian index is preferably in the range of 0.90 to 1.20, more preferably in the range of 0.95 to 1.15, particularly 0.95 to 1.10. It is preferable that Such a polyarylene sulfide resin is excellent in mechanical properties, fluidity, and abrasion resistance. However, the non-Newtonian index (N value) is measured by measuring the shear rate and shear stress using a capillograph at 300 ° C, the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40. These are values calculated using the following formula.
ポリアリーレンスルフィド樹脂（Ａ１）の製造方法としては、特に限定されないが、例えば１）ジハロゲノ芳香族化合物と、更に必要ならばその他の共重合成分とを、硫黄と炭酸ソーダの存在下で重合させる方法、２）ｐ−クロルチオフェノールと、更に必要ならばその他の共重合成分とを自己縮合させる方法、３）有機極性溶媒中で、スルフィド化剤とジハロゲノ芳香族化合物と、更に必要ならばその他の共重合成分とを反応させる方法、４）ジヨード芳香族化合物と単体硫黄と必要に応じて重合禁止剤とを重合触媒の存在下で溶融重合する方法等が挙げられる。これらの方法のなかでも、３）の方法が汎用的であり好ましい。反応の際に、重合度を調節するためにカルボン酸やスルホン酸のアルカリ金属塩を添加したり、水酸化アルカリを添加しても良い。上記３）方法のなかでも、加熱した有機極性溶媒とジハロゲノ芳香族化合物を含む混合物に含水スルフィド化剤を水が反応混合物から除去され得る速度で導入し、有機極性溶媒中でジハロゲノ芳香族化合物とスルフィド化剤とを反応させること、及び反応系内の水分量を該有機極性溶媒１モルに対して０．０２〜０．５モルの範囲にコントロールすることによりポリアリーレンスルフィド樹脂を製造する方法（特開平０７−２２８６９９号公報参照。）や、固形のアルカリ金属硫化物及び非プロトン性極性有機溶媒の存在下でポリハロ芳香族化合物、アルカリ金属水硫化物及び有機酸アルカリ金属塩を、硫黄源１モルに対して０．０１〜０．９モルの有機酸アルカリ金属塩および反応系内の水分量を非プロトン性極性有機溶媒１モルに対して０．０２モルの範囲にコントロールしながら反応させる方法（ＷＯ２０１０／０５８７１３号パンフレット参照。）で得られるものが特に好ましい。 The production method of the polyarylene sulfide resin (A1) is not particularly limited. For example, 1) a method of polymerizing a dihalogenoaromatic compound and, if necessary, other copolymerization components in the presence of sulfur and sodium carbonate. 2) Self-condensation of p-chlorothiophenol with other copolymerization components if necessary, 3) In an organic polar solvent, sulfidizing agent and dihalogenoaromatic compound, and further if necessary Examples thereof include a method of reacting a copolymerization component, and 4) a method of melt polymerization of a diiodo aromatic compound, elemental sulfur and, if necessary, a polymerization inhibitor in the presence of a polymerization catalyst. Among these methods, the method 3) is versatile and preferable. In the reaction, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above methods 3), a hydrous sulfiding agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogenoaromatic compound and A method for producing a polyarylene sulfide resin by reacting with a sulfidizing agent and controlling the amount of water in the reaction system in the range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent ( Japanese Patent Application Laid-Open No. 07-228699), a polyhaloaromatic compound, an alkali metal hydrosulfide and an organic acid alkali metal salt in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent. 0.01-0.9 mol of organic acid alkali metal salt and 1 mol of water in the reaction system with respect to 1 mol of aprotic polar organic solvent A method of reacting while controlling the .02 mols (WO2010 / 058 713 pamphlet reference.) Is what is particularly preferably obtained by.
本発明で用いる電気伝導性フィラーとしては、公知の物が使用できる。例えば、ニッケル、銅、金、銀、アルミニウム、亜鉛、ニッケル、スズ、鉛、クロム、プラチナ、パラジウム、タングステン、モリブデンなどの金属材料およびこれら２種以上の合金、混合体、あるいはこれら金属の化合物で良好な電気伝導性を有するものや、人造黒鉛、天然黒鉛、ガラス状カーボン、カーボンブラック、アセチレンブラック、ケッチェンブラック、炭素繊維、カーボンナノファイバーなどの炭素材料およびこれら２種以上の混合体が挙げられる。特に、銀粉、カーボンブラックは、安定した導電性を実現し易いため好ましい。 A well-known thing can be used as an electrically conductive filler used by this invention. For example, a metal material such as nickel, copper, gold, silver, aluminum, zinc, nickel, tin, lead, chromium, platinum, palladium, tungsten, molybdenum, and an alloy or mixture of these two or more, or a compound of these metals Examples include those having good electrical conductivity, carbon materials such as artificial graphite, natural graphite, glassy carbon, carbon black, acetylene black, ketjen black, carbon fiber, carbon nanofiber, and mixtures of two or more of these. It is done. In particular, silver powder and carbon black are preferable because stable conductivity is easily realized.
電気伝導性フィラーの形状は、発明の効果を損ねなければ特に限定されることはなく、板状、球状、繊維状、無定形等いずれであってよい。 The shape of the electrically conductive filler is not particularly limited as long as the effects of the invention are not impaired, and may be any of a plate shape, a spherical shape, a fiber shape, an amorphous shape, and the like.
本発明の電気伝導性フィラーの一次粒子の平均粒子径が０．０１〜１０μｍの範囲のものを用いることが好ましく、０．０１〜５μｍの範囲のものを用いることがより好ましい。この範囲の電気伝導性フィラーは、シラノール基を含有する化合物を用いて被覆してなることが、成形時の流動性の改善効果がより大きく、流動性をより良好とすることができ、安定的に良好な電気伝導性を奏することができる。 The average particle diameter of the primary particles of the electrically conductive filler of the present invention is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.01 to 5 μm. The electrically conductive filler in this range is formed by coating with a compound containing a silanol group, has a greater effect of improving fluidity during molding, can improve fluidity, and is stable. In addition, good electrical conductivity can be achieved.
このような銀粉としては、例えば、ＡＧ２−１Ｃ（ＤＯＷＡエレクトロニクス株式会社製、平均粒径Ｄ５０：０．８μｍ）、ＳＰＱ０３Ｓ（三井金属鉱山株式会社製、平均粒径Ｄ５０：０．５μｍ）、ＥＨＤ（三井金属鉱山株式会社製、平均粒径Ｄ５０：０．５μｍ）、シルベストＣ−３４（株式会社徳力化学研究所製、平均粒径Ｄ５０：０．３５μｍ）、ＡＧ２−１（ＤＯＷＡエレクトロニクス株式会社製、平均粒径Ｄ５０：１．３μｍ）、シルベストＡｇＳ−０５０（株式会社徳力化学研究所製、平均粒径Ｄ５０：１．４μｍ）などが挙げられる。 Examples of such silver powder include AG2-1C (manufactured by DOWA Electronics Co., Ltd., average particle size D50: 0.8 μm), SPQ03S (manufactured by Mitsui Metal Mining Co., Ltd., average particle size D50: 0.5 μm), EHD ( Mitsui Metal Mining Co., Ltd., average particle size D50: 0.5 μm), Sylbest C-34 (Tokuriku Chemical Laboratory Co., Ltd., average particle size D50: 0.35 μm), AG2-1 (DOWA Electronics Co., Ltd.) Average particle diameter D50: 1.3 μm), Sylbest AgS-050 (manufactured by Tokuru Chemical Laboratory Co., Ltd., average particle diameter D50: 1.4 μm) and the like.
また、カーボンブラックとしては、例えば、カーボン（電気化学工業株式会社製「デンカブラック粒状品」平均一次粒子径：３５ｎｍ）、カーボン（電気化学工業株式会社製「デンカブラックＨＳ−１００」平均一次粒子径：４８ｎｍ）、カーボン（ライオン株式会社製 ライオナイトＥＣ２００Ｌ 平均一次粒子径：４０ｎｍ）、人造黒鉛（昭和電工株式会社製「ＵＦ−Ｇ５」平均粒径Ｄ５０ ３μｍ）などが挙げられる。 Examples of the carbon black include carbon (“DENKA BLACK granular product” average primary particle size: 35 nm manufactured by Denki Kagaku Kogyo Co., Ltd.), carbon (“DENKA BLACK HS-100” average primary particle size manufactured by Denki Kagaku Kogyo Co., Ltd.). : 48 nm), carbon (Lionite EC200L average primary particle size: 40 nm) manufactured by Lion Corporation, artificial graphite (“UF-G5” average particle diameter D50 3 μm manufactured by Showa Denko KK) and the like.
前記電気伝導性フィラーをシリカで被覆した複合粒子（Ｂ）の製法は、特に制限は無く例えば、以下の方法が挙げられる。 There is no restriction | limiting in particular in the manufacturing method of the composite particle (B) which coat | covered the said electroconductive filler with the silica, For example, the following method is mentioned.
複合粒子は、（１）電気伝導性フィラーと、シラノール基を有する化合物を加水分解させることによって得られるゾル溶液とを含む混合ゾル溶液を調製する工程と、（２）その混合ゾル溶液から複合粒子を形成する工程と、を経て製造することができる。 The composite particles include (1) a step of preparing a mixed sol solution containing an electrically conductive filler and a sol solution obtained by hydrolyzing a compound having a silanol group, and (2) a composite particle from the mixed sol solution. Can be manufactured through the process of forming.
例えば、電気伝導性フィラー及びシラノール基を有する化合物を含む混合ゾル溶液として、シリカコロイドの溶液に前記電気伝導性フィラーを混合して調製することができる。また、シリコンテトラメトキシド、シリコンテトラエトキシド等のシリコンアルコキシドの加水分解脱水縮合液に電気伝導性フィラーを混合して調製してもよい。さらに、シリカ源として水ガラス（珪酸ナトリウム）を混合ゾル溶液に加えてもよい。 For example, a mixed sol solution containing an electrically conductive filler and a compound having a silanol group can be prepared by mixing the electrically conductive filler in a silica colloid solution. Alternatively, it may be prepared by mixing an electrically conductive filler with a hydrolytic dehydration condensation liquid of silicon alkoxide such as silicon tetramethoxide or silicon tetraethoxide. Furthermore, water glass (sodium silicate) may be added to the mixed sol solution as a silica source.
混合ゾル溶液中の電気伝導性フィラーの含有率は、全固形分に対して、例えば０．１〜９５質量％の範囲であることが好ましく、さらに２０〜８０質量％の範囲にあることがより好ましく、さらに５０〜７８質量％の範囲にあることが最も好ましい。 The content of the electrically conductive filler in the mixed sol solution is preferably, for example, in the range of 0.1 to 95% by mass and more preferably in the range of 20 to 80% by mass with respect to the total solid content. More preferably, it is most preferably in the range of 50 to 78% by mass.
混合ゾル溶液は、電気伝導性フィラーの分散性を向上させるために、分散剤を含んでいてもよい。分散剤としては、モノステアリン酸ソルビタン、モノオレイン酸ソルビタン、トリオレイン酸ソルビタン、モノラウリン酸ポリオキシエチレンソルビタン、モノオレイン酸ポリオキシエチレンソルビタン、モノステアリン酸ポリオキシエチレンソルビタン、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、モノステアリン酸グリセリン、モノステアリン酸プロピレングリコール、イソステアリルグリセリルエーテル、モノステアリン酸ポリエチレングリコール、ジステアリン酸ポリエチレングリコール、ポリオキシエチレン硬化ヒマシ油等が挙げられる。 The mixed sol solution may contain a dispersant in order to improve the dispersibility of the electrically conductive filler. Dispersants include sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene lauryl ether, polyoxyethylene Examples include oxyethylene oleyl ether, sodium polyoxyethylene lauryl ether sulfate, glyceryl monostearate, propylene glycol monostearate, isostearyl glyceryl ether, polyethylene glycol monostearate, polyethylene glycol distearate, polyoxyethylene hydrogenated castor oil, and the like. .
次に、混合ゾル溶液から複合粒子を形成する。例えば、混合ゾル溶液を噴霧乾燥することによって、複合粒子を得ることができる。噴霧乾燥は、高温雰囲気下に液体を微粒化して散布することによって直接乾燥して粒子を得る技術である。噴霧乾燥は、例えば、スプレードライヤーを用いて、混合ゾル溶液の溶媒（水、アルコール等）が蒸発するのに十分な温度の雰囲気下に、混合ゾル溶液を噴霧することによって行うことができる。噴霧乾燥することによって、電気伝導性フィラーがシラノール基を有する化合物のコロイド粒子に囲まれて当該化合物のマトリックス中に強固に内包及び／又は分散された略球状の複合粒子が形成される。 Next, composite particles are formed from the mixed sol solution. For example, the composite particles can be obtained by spray drying the mixed sol solution. Spray drying is a technique in which particles are obtained by direct drying by atomizing and spraying a liquid in a high-temperature atmosphere. Spray drying can be performed, for example, by spraying the mixed sol solution using a spray dryer in an atmosphere at a temperature sufficient to evaporate the solvent (water, alcohol, etc.) of the mixed sol solution. By spray drying, substantially spherical composite particles are formed in which the electrically conductive filler is surrounded by colloidal particles of a compound having a silanol group and is firmly encapsulated and / or dispersed in the matrix of the compound.
噴霧乾燥工程の後に、得られた複合粒子を熱処理する工程をさらに行ってもよい。当該熱処理によって、複合粒子をさらに乾燥することができる。また、シリコンアルコキシド等の加水分解脱水縮合液を用いた場合には、脱水縮合をさらに進行させることもできる。 You may further perform the process of heat-processing the obtained composite particle after a spray-drying process. The composite particles can be further dried by the heat treatment. Further, when a hydrolytic dehydration condensate such as silicon alkoxide is used, dehydration condensation can be further advanced.
熱処理の温度及び時間については、目的に応じて適宜決定すればよい。この他、例えば、窒素、アルゴン等の不活性気体雰囲気中、シラノール基を有する化合物の粘性流動が起こる温度、例えば８００〜１０００℃で２〜５時間熱処理することができる。 What is necessary is just to determine suitably the temperature and time of heat processing according to the objective. In addition, for example, heat treatment can be performed at a temperature at which viscous flow of the compound having a silanol group occurs, for example, at 800 to 1000 ° C. for 2 to 5 hours in an inert gas atmosphere such as nitrogen or argon.
このようにして得られた複合粒子（Ｂ）は、シリカをマトリックスとして、当該マトリックス中に前記電気伝導性フィラーの２以上が分散した分散体として得ることができる。得られた複合粒子の平均粒子径は、０．１〜２０μｍの範囲であり、好ましくは０．１〜１０μｍの範囲であり、さらに好ましくは０．１〜５μｍの範囲である。当該範囲で、成形体表面における電気伝導性のばらつきを抑え、電気伝導性を安定して付与できる熱可塑性樹脂成形体を提供することができる。一方、０．１μｍ未満の場合には、複合粒子自身が凝集しやすくなり、成形体表面における電気伝導性のばらつきが大きくなる傾向となる。一方、２０μｍを超えると、成形体表面の外観性が低下する傾向となる。 The composite particles (B) thus obtained can be obtained as a dispersion in which silica is used as a matrix and two or more of the electrically conductive fillers are dispersed in the matrix. The average particle diameter of the obtained composite particles is in the range of 0.1 to 20 μm, preferably in the range of 0.1 to 10 μm, and more preferably in the range of 0.1 to 5 μm. Within this range, it is possible to provide a thermoplastic resin molded body that can suppress variation in electrical conductivity on the surface of the molded body and can stably impart electrical conductivity. On the other hand, when the particle size is less than 0.1 μm, the composite particles themselves tend to aggregate, and the variation in electrical conductivity on the surface of the molded body tends to increase. On the other hand, when it exceeds 20 μm, the appearance of the surface of the molded product tends to be lowered.
熱可塑性樹脂組成物中における前記熱可塑性樹脂（Ａ）と前記複合粒子（Ｂ）の含有量は、本発明の効果を損なう範囲でなければ特に限定されるものではないが、優れた機械的強度や導電性、電気伝導性を安定して良好に付与できる観点から、熱可塑性樹脂（Ａ）１００質量部に対して、１質量部以上の範囲であることが好ましく、さらに３質量部以上の範囲であることがより好ましく、さらに５質量部以上の範囲であることが最も好ましい。一方、成形物の外観の悪化を抑制することができる点から、熱可塑性樹脂（Ａ）１００質量部に対して、５０質量部以下の範囲であることが好ましく、さらに４０質量部以下の範囲がより好ましく、さらに３０質量部以下の範囲であることが最も好ましい。 The contents of the thermoplastic resin (A) and the composite particles (B) in the thermoplastic resin composition are not particularly limited as long as they do not impair the effects of the present invention, but have excellent mechanical strength. From the viewpoint of stably and satisfactorily imparting electrical conductivity and electrical conductivity, it is preferably in the range of 1 part by mass or more, more preferably in the range of 3 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin (A) More preferably, it is most preferably in the range of 5 parts by mass or more. On the other hand, from the viewpoint of suppressing deterioration of the appearance of the molded product, the range is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (A). More preferably, it is most preferably in the range of 30 parts by mass or less.
本発明の熱可塑性樹脂（Ａ）には、本発明の効果を損なわない範囲で、強度、耐熱性、寸法安定性等の性能を改善するため、上記成分に加え、さらに充填材やその他添加剤が含まれていてもよい。 In the thermoplastic resin (A) of the present invention, in addition to the above components, in addition to the above components, fillers and other additives are added in order to improve the performance such as strength, heat resistance and dimensional stability within the range not impairing the effects of the present invention. May be included.
当該添加剤としては、着色剤、耐熱安定剤、紫外線安定剤、発泡剤、防錆剤、難燃剤、滑剤等の各種添加剤や、また用途に応じて、熱可塑性樹脂（Ａ）とは異なる樹脂が含まれていてもよい。例えば、ポリエステル、ポリアミド、ポリイミド、ポリエーテルイミド、ポリカーボネート、ポリフェニレンエーテル、ポリスルフォン、ポリエーテルスルフォン、ポリエーテルエーテルケトン、ポリエーテルケトン、ポリアリーレン、ポリエチレン、ポリプロピレン、ポリ四弗化エチレン、ポリ二弗化エチレン、ポリスチレン、ＡＢＳ樹脂、エポキシ樹脂、シリコーン樹脂、フェノール樹脂、ウレタン樹脂、液晶ポリマー等の合成樹脂、或いは、弗素ゴム、シリコーンゴム等のエラストマ、特にエポキシ基、アミノ基、カルボキシ基、イソシアナト基または下記の構造式（１）、構造式（２） The additive is different from the thermoplastic resin (A) according to various additives such as a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, and a lubricant, and depending on the application. Resin may be included. For example, polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoride Synthetic resins such as ethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, and liquid crystal polymer, or elastomers such as fluorine rubber and silicone rubber, particularly epoxy group, amino group, carboxy group, isocyanato group or The following structural formula (1), structural formula (2)
また、充填材としても、粒状、繊維状などさまざまな形状の充填材等が挙げられ、例えば、ガラス繊維、シランガラス繊維、セラミック繊維、アラミド繊維、チタン酸カリウム、炭化珪素、硫酸カルシウム、珪酸カルシウム等の繊維、ウォラストナイト等の天然繊維等の繊維状の充填材や、硫酸バリウム、硫酸カルシウム、クレー、パイロフィライト、ベントナイト、セリサイト、ゼオライト、マイカ、雲母、タルク、アタパルジャイト、フェライト、珪酸カルシウム、炭酸カルシウム、炭酸マグネシウム、ガラスビーズ等が挙げられる。 Examples of the filler include fillers of various shapes such as granular and fibrous, for example, glass fiber, silane glass fiber, ceramic fiber, aramid fiber, potassium titanate, silicon carbide, calcium sulfate, calcium silicate. Fiber fillers such as natural fibers such as wollastonite, barium sulfate, calcium sulfate, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, talc, attapulgite, ferrite, silicic acid Examples include calcium, calcium carbonate, magnesium carbonate, and glass beads.
これらの添加剤、充填剤の使用量は、それぞれの目的に応じて異なり、一概に規定することはできないが、熱可塑性樹脂（Ａ）１００質量部に対して０．０１〜１０００質量部の範囲で、本発明の効果を損なわないよう目的や用途に応じて適宜調整して用いればよい。また、前記充填剤の大きさは、本発明の効果を損ねない範囲であれば特に限定されるものではないが、表面外観性および表面平滑性の点から、平均粒子径が１μｍ未満の範囲であることが好ましい。一方、熱可塑性樹脂（Ａ）との濡れ性に優れ、成形性および分散性が良好となる点から、１０ｎｍ以上の範囲であることが好ましい。 The amount of these additives and fillers used varies depending on the purpose and cannot be specified in general, but is in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). Thus, it may be appropriately adjusted and used according to the purpose and application so as not to impair the effects of the present invention. Further, the size of the filler is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoint of surface appearance and surface smoothness, the average particle diameter is within a range of less than 1 μm. Preferably there is. On the other hand, the range of 10 nm or more is preferable from the viewpoint of excellent wettability with the thermoplastic resin (A) and good moldability and dispersibility.
本発明の熱可塑性樹脂組成物の製造方法は、本発明の効果を損なわなければ特に制限されず、例えば、原料である熱可塑性樹脂（Ａ）と前記複合粒子（Ｂ）を、タンブラー又はヘンシェルミキサーなどで均一に混合、次いでバンバリーミキサー、ミキシングロール、単軸または２軸の押出機およびニーダーなどを用いて溶融混練する方法などが挙げられる。なかでも十分な混練力を有する単軸または２軸の押出機を用いて溶融混練する方法が好ましい。 The method for producing the thermoplastic resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired. For example, the thermoplastic resin (A) as the raw material and the composite particles (B) are tumbled or henshell mixer. And the like, followed by melt kneading using a Banbury mixer, a mixing roll, a single or twin screw extruder, a kneader, and the like. In particular, a melt kneading method using a single or twin screw extruder having a sufficient kneading force is preferable.
具体的には、前記熱可塑性樹脂（Ａ）と前記複合粒子（Ｂ）と、更に必要に応じてその他の配合成分を、タンブラー又はヘンシェルミキサーなどで均一に混合、次いで二軸混練押出機などの溶融混練押出機に投入し、前記熱可塑性樹脂（Ａ）が溶融する温度以上に設定し、溶融混練することにより得られる。溶融混練条件としては、樹脂成分の吐出量５〜５００（ｋｇ／ｈｒ）の範囲と、スクリュー回転数１００〜５００（ｒｐｍ）と、それらの比率（吐出量／スクリュー回転数）が０．０２〜２（ｋｇ／ｈｒ／ｒｐｍ）なる条件下に溶融混練する方法が好ましい方法として挙げられる。かかる条件下に製造することによって前記熱可塑性樹脂（Ａ）をマトリックス（連続相）として、前記複合粒子（Ｂ）が微分散する熱可塑性樹脂組成物を好ましく製造することができる。 Specifically, the thermoplastic resin (A) and the composite particles (B) and, if necessary, other blending components are mixed uniformly with a tumbler or Henschel mixer, and then a twin-screw kneading extruder or the like. It is obtained by charging into a melt-kneading extruder, setting at a temperature higher than the temperature at which the thermoplastic resin (A) melts, and melt-kneading. As the melt-kneading conditions, the resin component discharge amount is in the range of 5 to 500 (kg / hr), the screw rotation speed is 100 to 500 (rpm), and the ratio thereof (discharge amount / screw rotation speed) is 0.02 to 0.02. A preferable method is melt kneading under a condition of 2 (kg / hr / rpm). By producing under such conditions, it is possible to preferably produce a thermoplastic resin composition in which the composite particles (B) are finely dispersed using the thermoplastic resin (A) as a matrix (continuous phase).
上記製造方法につき更に詳述すれば、前記した各成分を押出機内に投入し、設定温度３００℃、樹脂温度３２０℃程度の温度条件下に溶融混練する方法が好ましく挙げられる。この際、樹脂成分の吐出量は回転数２００ｒｐｍで４〜４００ｋｇ／ｈｒの範囲であることが好ましく、なかでも分散性の点から１０〜２５０ｋｇ／ｈｒであることがより好ましい。したがって、樹脂成分の吐出量（ｋｇ／ｈｒ）とスクリュー回転数（ｒｐｍ）との比率（吐出量／スクリュー回転数）は、特に０．０５〜１．２５（ｋｇ／ｈｒ／ｒｐｍ）であることが好ましい。 More specifically, the above-described production method is preferably a method in which the above-described components are put into an extruder and melt-kneaded under temperature conditions of a set temperature of 300 ° C. and a resin temperature of about 320 ° C. At this time, the discharge amount of the resin component is preferably in the range of 4 to 400 kg / hr at a rotation speed of 200 rpm, and more preferably 10 to 250 kg / hr from the viewpoint of dispersibility. Accordingly, the ratio (discharge amount / screw rotation number) between the resin component discharge amount (kg / hr) and the screw rotation speed (rpm) is particularly 0.05 to 1.25 (kg / hr / rpm). Is preferred.
このようにして溶融混練された熱可塑性樹脂組成物はその後、直接各種公知の成形法を用いて成形体へと成形されるか、一旦、ペレットとして成形された後、次いで、これを各種成形機に供して溶融成形することにより、目的とする熱可塑性樹脂成形体に成形することができる。公知の成形法としては、射出成形法、プレス成形法、カレンダー成形法、ロール成形法、押出成形法、注型成形法およびブロー成形法などが挙げられる。 The thermoplastic resin composition melt-kneaded in this way is then directly molded into a molded body using various known molding methods, or once molded as pellets, and then molded into various molding machines. By subjecting it to melt molding, it can be molded into the desired thermoplastic resin molding. Known molding methods include injection molding, press molding, calendar molding, roll molding, extrusion molding, cast molding, and blow molding.
そして得られた成形体は、熱可塑性樹脂（Ａ）からなるマトリックス（連続相）中に、電気伝導性フィラーをシリカで被覆した複合粒子（Ｂ）が微分散してなるものであって、前記複合粒子が、さらにシリカをマトリックスとして、当該マトリックス中に前記電気伝導性フィラーの２粒子以上が分散した分散体であることから、電気伝導性を安定して付与することができる。 The obtained molded body is obtained by finely dispersing composite particles (B) obtained by coating an electrically conductive filler with silica in a matrix (continuous phase) made of a thermoplastic resin (A), Since the composite particles are a dispersion in which two or more particles of the electrically conductive filler are further dispersed in the matrix using silica as a matrix, the electrical conductivity can be stably imparted.
その理由は定かではないが、電気伝導性フィラー単独のものを使用した場合には、成形時に当該フィラーが再凝集し易く、成形条件により成形体の電気抵抗が大きく変動する。前記複合粒子（Ｂ）は電気伝導性フィラーをシリカで被覆・固定しているため再凝集が生じず、複合粒子自体も電気伝導性フィラーより大粒子径のため凝集し難く、更にシリカが電気伝導の障壁となるため、安定した導電性成形体を得ることが出来たものと考えられる。 The reason for this is not clear, but when an electrically conductive filler alone is used, the filler easily re-aggregates during molding, and the electrical resistance of the molded body varies greatly depending on molding conditions. Since the composite particles (B) are coated and fixed with an electrically conductive filler with silica, re-aggregation does not occur, and the composite particles themselves are more difficult to aggregate due to the larger particle size than the electrically conductive filler. Therefore, it is considered that a stable conductive molded body could be obtained.
目的とする形状に成形するためには、熱可塑性樹脂組成物のペレットをさらに成形機に供して押出成形法、射出成形法、圧縮成形法、吹込成形法、射出圧縮成形法などの公知の各種成形法に適用して、シートまたはフィルムとして得る（成形工程）。 In order to form the desired shape, the pellets of the thermoplastic resin composition are further subjected to a molding machine, and various known methods such as extrusion molding, injection molding, compression molding, blow molding, and injection compression molding are used. Apply to the molding method to obtain a sheet or film (molding process).
特に配合量が少ない添加剤は、成形工程直前に添加・混合してもよい。
本発明の熱可塑性樹脂成形体は、熱可塑性樹脂（Ａ）の本来有する機械的強度、耐熱性、寸法安定性等の諸性能を活かして、例えば、センサ、ＬＥＤランプ、コネクタ、ソケット、抵抗器、リレーケース、スイッチ、コイルボビン、コンデンサ、バリコンケース、発振子、各種端子板、変成器、プラグ、プリント基板、チューナ、スピーカ、マイクロフォン、ヘッドフォン、小型モータ、磁気ヘッドベース、半導体、液晶、ＦＤＤキャリッジ、ＦＤＤシャーシ、モーターブラッシュホルダ、パラボラアンテナ、コンピュータ関連部品などに代表される電気・電子部品、ＶＴＲ部品、テレビ部品、アイロン、ヘアードライヤ、炊飯器部品、電子レンジ部品、音響部品、オーディオ・レーザディスク・コンパクトディスクなどの音声機器部品、照明部品、冷蔵庫部品、エアコン部品、タイプライタ部品、ワードプロセッサ部品などに代表される家庭、事務電気製品部品や、オフィスコンピュータ関連部品、電話器関連部品、ファクシミリ関連部品、複写機関連部品、洗浄用治具、モータ部品、ライタ、タイプライタなどに代表される機械関連部品や、顕微鏡、双眼鏡、カメラ、時計などに代表される光学機器、精密機械関連部品や、水道蛇口コマ、混合水栓、ポンプ部品、パイプジョイント、水量調節弁、逃がし弁、湯温センサ、水量センサ、水道メーターハウジングなどの水廻り部品や、バルブオルタネーターターミナル、オルタネーターコネクタ，ＩＣレギュレータ、ライトディヤ用ポテンシオメーターベース、排気ガスバルブなどの各種バルブ、燃料関係・排気系・吸気系各種パイプ、エアーインテークノズルスノーケル、インテークマニホールド、燃料ポンプ、エンジン冷却水ジョイント、キャブレターメインボディ、キャブレタースペーサ、排気ガスセンサ、冷却水センサ、油温センサ、スロットルポジションセンサ、クランクシャフトポジションセンサ、エアーフローメータ、ブレーキパッド摩耗センサ、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモータ用ブラッシュホルダ、ウォーターポンプインペラ、タービンベイン、ワイパーモータ関係部品、デュストリビュータ、スタータースイッチ、スターターリレ、トランスミッション用ワイヤーハーネス、ウィンドウォッシャーノズル、エアコンパネルスイッチ基板、燃料関係電磁気弁用コイル、ヒューズ用コネクタ、ホーンターミナル、電装部品絶縁板、ステップモーターロータ、ランプソケット、ランプリフレクタ、ランプハウジング、ブレーキピストン、ソレノイドボビン、エンジンオイルフィルタ、点火装置ケース、ＨＥＶ用コンデンサーケース、車速センサ、ケーブルライナ、プラスチックギヤなどの自動車・車両関連部品など各種用途あるいはバグフィルター、保温衣料、不織布や縫い糸等の繊維若しくは粘着フィルム用基材、離型フィルム、回路基板、フィルムコンデンサ、モーター・トランス用絶縁フィルム、転写ベルト、回路基板、燃料チューブ等、フィルム用の材料、電磁波の遮蔽材などとして幅広く有用である。
In particular, additives with a small amount may be added and mixed immediately before the molding step.
The thermoplastic resin molded article of the present invention utilizes various performances such as mechanical strength, heat resistance, and dimensional stability inherent to the thermoplastic resin (A), for example, sensors, LED lamps, connectors, sockets, resistors. , Relay case, switch, coil bobbin, capacitor, variable capacitor case, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, semiconductor, liquid crystal, FDD carriage, Electrical / electronic parts such as FDD chassis, motor brush holder, parabolic antenna, computer-related parts, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio laser discs Audio equipment parts such as compact discs, lighting Houses represented by parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, office electrical product parts, office computer related parts, telephone equipment related parts, facsimile related parts, copying machine related parts, cleaning jigs Machine parts represented by motor parts, writers, typewriters, optical equipment represented by microscopes, binoculars, cameras, watches, precision machine parts, water taps, mixing faucets, pump parts, Various parts such as pipe joints, water volume control valves, relief valves, hot water temperature sensors, water volume sensors, water meter housings, valve alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, exhaust gas valves, etc. Various valves, fuel-related, exhaust system, intake system Air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake Pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, wire harness for transmission, window Washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, ho Automobile terminals such as electrical terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, HEV condenser cases, vehicle speed sensors, cable liners, plastic gears, etc.・ Various applications such as vehicle-related parts, bag filters, heat insulation clothing, non-woven fabric and sewing thread fibers, adhesive film substrates, release films, circuit boards, film capacitors, motor / transformer insulation films, transfer belts, circuit boards, It is widely useful as a material for film such as a fuel tube, and as a shielding material for electromagnetic waves.
以下、本発明を実施例により具体的に説明するが、本発明はこれら実施例にのみ限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited only to these examples.
［複合粒子の平均粒子径］
ＪＩＳ−Ｚ８８２５に準拠し、レーザー回折散乱式粒度分布測定装置(日機装株式会社 製 マイクロトラックＭＴ３３００ＥＸ ＩＩ)により測定し、得られた写真像から任意の１００点を測定し、体積分布基準の５０％粒度（メジアン径）を測定した。
[Average particle diameter of composite particles]
Based on JIS-Z8825, measured with a laser diffraction scattering type particle size distribution measuring device (Microtrack MT3300EX II manufactured by Nikkiso Co., Ltd.), 100 arbitrary points were measured from the obtained photographic image, and 50% particle size based on volume distribution (Median diameter) was measured.
［複合粒子中の電気伝導性フィラーの一次粒子の平均粒子径］
複合粒子中の電気伝導性フィラー（カーボンブラック）の一次粒子径は透過型電子顕微鏡（ＴＥＭ）により観察し、得られた写真像から任意の１００点を測定し、体積分布基準の５０％粒度（メジアン径）を測定した。
[Average particle diameter of primary particles of electrically conductive filler in composite particles]
The primary particle diameter of the electrically conductive filler (carbon black) in the composite particles is observed with a transmission electron microscope (TEM), and an arbitrary 100 points are measured from the obtained photographic image. The median diameter was measured.
（調製例１〜４）複合粒子の調製
電気伝導性ファイラー（１）〜（４）の水分散液（フィラー固形分：２５質量％＋ポリカルボン酸型高分子界面活性剤：１．７質量％）をジルコニアビーズミルにより調製した。この水分散液にテトラメトキシシラン及びコロイダルシリカ（日本化学工業社製：シリカドール（登録商標）３０）を混合し、混合ゾルを得た。さらに、フィラー、シリカ、分散剤等の固形分が１８．４％になるように純水を使って混合ゾルを希釈した。混合ゾルの無機固形分中のフィラーの含有率は、５０〜７８質量％の範囲であった。
(Preparation Examples 1 to 4) Preparation of composite particles Aqueous dispersion of electrically conductive filers (1) to (4) (filler solid content: 25% by mass + polycarboxylic acid type polymer surfactant: 1.7% by mass) ) Was prepared with a zirconia bead mill. Tetramethoxysilane and colloidal silica (manufactured by Nippon Chemical Industry Co., Ltd .: Silica Doll (registered trademark) 30) were mixed with this aqueous dispersion to obtain a mixed sol. Further, the mixed sol was diluted with pure water so that the solid content of the filler, silica, dispersant and the like was 18.4%. The filler content in the inorganic solid content of the mixed sol was in the range of 50 to 78 mass%.
次に、スプレードライヤー（藤崎電機社製ＭＤＬ−０５０）を用いて混合ゾルを乾燥させ、電気伝導性フィラー内包シリカ粒子を作製した。平均粒径が０．１〜１０μｍの範囲に収まるように噴霧条件を設定した（推奨条件：ゾル送量＝３０ｇ／分）。その後、６００℃で７時間焼成して電気伝導性フィラーを含むシリカからなる複合粒子（ｂ１）〜（ｂ４）を得た。得られた複合粒子（ｂ１）の走査型電子顕微鏡（ＳＥＭ）写真（倍率１０００）を図１に、複合粒子（ｂ１）の透過型電子顕微鏡（ＴＥＭ）写真（倍率１００００）を図２に示した。 Next, the mixed sol was dried using a spray dryer (MDL-050 manufactured by Fujisaki Electric Co., Ltd.) to produce electrically conductive filler-encapsulated silica particles. The spraying conditions were set so that the average particle size was within the range of 0.1 to 10 μm (recommended condition: sol feed amount = 30 g / min). Then, it baked at 600 degreeC for 7 hours, and obtained the composite particle (b1)-(b4) which consists of a silica containing an electroconductive filler. A scanning electron microscope (SEM) photograph (magnification 1000) of the obtained composite particles (b1) is shown in FIG. 1, and a transmission electron microscope (TEM) photograph (magnification 10000) of the composite particles (b1) is shown in FIG. .
電気伝導性フィラー（２）：カーボン（電気化学工業株式会社製「デンカブラックＨＳ−１００」平均粒子径４８ｎｍ）
電気伝導性フィラー（３）：カーボン（ライオン株式会社製「ライオナイトＥＣ２００Ｌ」平均粒子径４０ｎｍ）
Electrically conductive filler (2): Carbon (“DENKA BLACK HS-100” average particle size 48 nm, manufactured by Denki Kagaku Kogyo Co., Ltd.)
Electrically conductive filler (3): Carbon (“Lionite EC200L” average particle size 40 nm, manufactured by Lion Corporation)
（実施例１〜４／参考例１〜３）
下記表２〜３に示した熱可塑性樹脂（ａ１）と、複合粒子（ｂ１〜b４）、更に必要に応じてその他の配合成分をタンブラーで均一に混合し、配合材料とした。その後、株式会社日本製鋼所製ベント付き２軸押出機「ＴＥＸ−３０」に前記配合材料を投入し、樹脂成分吐出量１５ｋｇ／ｈｒ、スクリュー回転数２００ｒｐｍ、樹脂成分の吐出量（ｋｇ／ｈｒ）とスクリュー回転数（ｒｐｍ）との比率（吐出量／スクリュー回転数）＝０．０７５（ｋｇ／ｈｒ／ｒｐｍ）、最大トルク４０（Ａ）、設定樹脂温度３００℃で溶融混練して樹脂組成物のペレットを得た。
(Examples 1-4 / Reference Examples 1-3)
The thermoplastic resin (a1) shown in Tables 2 to 3 below, the composite particles (b1 to b4), and, if necessary, other blending components were uniformly mixed with a tumbler to obtain a blending material. Thereafter, the blended material was charged into a vented twin-screw extruder “TEX-30” manufactured by Nippon Steel Works, Ltd., resin component discharge rate 15 kg / hr, screw rotation speed 200 rpm, resin component discharge rate (kg / hr) And screw rotation speed (rpm) ratio (discharge amount / screw rotation speed) = 0.075 (kg / hr / rpm), maximum torque 40 (A), and melt kneading at a set resin temperature of 300 ° C. Pellets were obtained.
成形品の引張特性、表面光沢、表面抵抗率、体積抵抗率、表面外観性を測定するため、Ｔダイ押出機を用いて前記ペレットを設定温度３００℃で溶融混練し、ロール温度７０℃で押出成形して、厚み８０〜１００μｍのフィルムを作製した。測定は以下の方法で行った。それらの結果を表２〜３に示す。なお、表中の単位は特に断りがない限り質量部である。 In order to measure the tensile properties, surface gloss, surface resistivity, volume resistivity, and surface appearance of the molded product, the pellets were melt-kneaded at a set temperature of 300 ° C using a T-die extruder and extruded at a roll temperature of 70 ° C. Molded to prepare a film having a thickness of 80 to 100 μm. The measurement was performed by the following method. The results are shown in Tables 2-3. In addition, the unit in a table | surface is a mass part unless there is particular notice.
［引張特性］
フィルムを１５×１１０ｍｍに切り出し、測定温度２３℃、標線間距離５０ｍｍ、試験速度１０ｍｍ／ｍｉｎで、引張試験機（ＡＧＳ−５ｋＮＸ：株式会社 島津製作所製）により、引張強度を測定した。
[Tensile properties]
The film was cut into 15 × 110 mm, and the tensile strength was measured with a tensile tester (AGS-5kNX: manufactured by Shimadzu Corporation) at a measurement temperature of 23 ° C., a distance between marked lines of 50 mm, and a test speed of 10 mm / min.
［表面光沢］
（光沢値の測定）
光沢計「ＶＧ２０００」（日本電色製）で光沢の測定を行い、その結果をグロスで示した。光沢の測定条件は入射角２０度とした。
[Surface gloss]
(Gloss value measurement)
The gloss was measured with a gloss meter “VG2000” (manufactured by Nippon Denshoku), and the result was shown in gloss. The gloss measurement condition was an incident angle of 20 degrees.
＜表面抵抗率、体積抵抗率＞
表面抵抗率（Ω／□）及び体積抵抗率（Ω・cｍ）は、三菱化学株式会社製の抵抗測定器「ハイレスタＵＰ・ＵＲＳブローブ」を用いて２３℃、５５％ＲＨ環境下で測定した。実施例１〜５及び比較例１〜２で作製したフィルムを、縦方向に長さ３００ｍｍにカットしたベルトをサンプルとし、該サンプルの幅方向に等ピッチで任意の３ヶ所、縦方向に任意の４カ所の合計１２ヶ所について、印加電圧１００Ｖ、１０秒後に表面抵抗率及び体積抵抗率をそれぞれ測定し、その平均値の常用対数値で示した。なお該測定サンプルは２３℃、５５％ＲＨ環境下で２４時間放置してから測定した。
<Surface resistivity, volume resistivity>
The surface resistivity (Ω / □) and the volume resistivity (Ω · cm) were measured in a 23 ° C., 55% RH environment using a resistance measuring instrument “HIRESTA UP / URS probe” manufactured by Mitsubishi Chemical Corporation. The films produced in Examples 1 to 5 and Comparative Examples 1 and 2 were used as samples with belts cut in the longitudinal direction to a length of 300 mm, and arbitrary three locations in the longitudinal direction at arbitrary pitches in the longitudinal direction. The surface resistivity and the volume resistivity were measured at an applied voltage of 100 V and 10 seconds at a total of 12 locations of 4 locations, respectively, and the average values were shown as common logarithmic values. The measurement sample was measured after being left for 24 hours in an environment of 23 ° C. and 55% RH.
［表面抵抗率のばらつき］
上記１２ヶ所の最大値と最小値の差をΔρsとした。
［体積抵抗率のばらつき］
上記１２ヶ所の最大値と最小値の差をΔρvとした。
＜表面抵抗率、体積抵抗率の電圧依存性＞
上記１２ヶ所について、印加電圧１００Ｖ、２５０Ｖ、５００Ｖにおける表面抵抗率及び体積抵抗率を測定し、その平均値を算出した。
[表面抵抗率の電圧依存性]
印加電圧１００Ｖ、５００Ｖの表面抵抗率の差を電圧依存性（Δρｓ１００−５００）とした。
[体積抵抗率の電圧依存性]
印加電圧１００Ｖ、５００Ｖの体積抵抗率の差を電圧依存性(Δρｖ１００−５００)とした。
[Variation of surface resistivity]
The difference between the maximum value and the minimum value at the 12 locations was defined as Δρs.
[Variation of volume resistivity]
The difference between the maximum value and the minimum value at the 12 locations was defined as Δρv.
<Voltage dependence of surface resistivity and volume resistivity>
The surface resistivity and volume resistivity at applied voltages of 100 V, 250 V, and 500 V were measured at the 12 locations, and the average values were calculated.
[Voltage dependence of surface resistivity]
The difference in surface resistivity between the applied voltages of 100 V and 500 V was defined as voltage dependency (Δρs 100-500 ).
[Voltage resistivity voltage dependency]
The difference in volume resistivity between the applied voltages of 100V and 500V was defined as voltage dependency (Δρv 100−500 ).
熱可塑性樹脂（Ａ）成分
ＰＰＳ（a１）：ＤＩＣ株式会社製ポリアリーレンスルフィド樹脂（熱伝導率０．２（Ｗ／ｍ・Ｋ）、Ｖ６溶融粘度１５〔Ｐａ・ｓ〕
ＰＡ６（a２）：宇部興産株式会社製ポリアミド６樹脂（熱伝導率０．２５（Ｗ／ｍ・Ｋ））
Thermoplastic resin (A) component PPS (a1): DIC Corporation polyarylene sulfide resin (thermal conductivity 0.2 (W / m · K), V6 melt viscosity 15 [Pa · s]
PA6 (a2): Polyamide 6 resin (thermal conductivity 0.25 (W / m · K)) manufactured by Ube Industries, Ltd.
（実施例５〜８／参考例４〜６）
混練時の二軸押出機の設定温度を２６０℃、成形時のＴダイ押出機の設定温度を２７０℃、ロールを５０℃とした以外は実施例１〜４／参考例１〜３と同様に、サンプルを作製、評価を行なった。
(Examples 5-8 / Reference Examples 4-6)
Examples 1-4 / Reference Examples 1-3 except that the setting temperature of the twin-screw extruder during kneading was 260 ° C., the setting temperature of the T-die extruder during molding was 270 ° C., and the roll was 50 ° C. Samples were prepared and evaluated.
Claims (10)
熱可塑性樹脂（Ａ）が５０〜９９質量％の範囲であり、前記複合粒子（Ｂ）が１〜５０質量％の範囲であること、かつ、
前記複合粒子（Ｂ）の平均粒子径が０．１〜２０μｍの範囲であること、かつ、前記複合粒子が、シリカをマトリックスとして、当該マトリックス中に前記電気伝導性フィラーの２粒子以上が分散した分散体であることを特徴とし、
前記電気伝導性フィラーが、ニッケル、銅、金、銀、アルミニウム、亜鉛、スズ、鉛、クロム、プラチナ、パラジウム、タングステン、モリブデン、もしくはこれら２種以上の合金、人造黒鉛、天然黒鉛、ガラス状カーボン、カーボンブラック、アセチレンブラック、ケッチェンブラック、炭素繊維、カーボンナノファイバー、またはこれら２種以上の混合体である、熱可塑性樹脂組成物。 A thermoplastic resin composition comprising as essential components a thermoplastic resin (A) and composite particles (B) in which an electrically conductive filler is coated with silica,
The thermoplastic resin (A) is in the range of 50 to 99% by mass, the composite particles (B) are in the range of 1 to 50% by mass, and
The composite particles (B) have an average particle size in the range of 0.1 to 20 μm, and the composite particles have silica as a matrix, and two or more particles of the electrically conductive filler are dispersed in the matrix. It is a dispersion ,
The electrically conductive filler is nickel, copper, gold, silver, aluminum, zinc, tin, lead, chromium, platinum, palladium, tungsten, molybdenum, or an alloy of two or more thereof, artificial graphite, natural graphite, glassy carbon , Carbon black, acetylene black, ketjen black, carbon fiber, carbon nanofiber, or a mixture of two or more thereof.
前記複合粒子（Ｂ）の平均粒子径が０．１〜２０μｍの範囲であること、かつ、
前記複合粒子が、シリカをマトリックスとして、当該マトリックス中に前記電気伝導性フィラーの２粒子以上が分散した分散体であることを特徴とし、
前記電気伝導性フィラーが、ニッケル、銅、金、銀、アルミニウム、亜鉛、スズ、鉛、クロム、プラチナ、パラジウム、タングステン、モリブデン、もしくはこれら２種以上の合金、人造黒鉛、天然黒鉛、ガラス状カーボン、カーボンブラック、アセチレンブラック、ケッチェンブラック、炭素繊維、カーボンナノファイバー、またはこれら２種以上の混合体である、熱可塑性樹脂組成物の製造方法。 A thermoplastic resin (A) and a composite particle (B) are charged into a melt-kneading extruder and melt-kneaded for producing a thermoplastic resin composition,
The average particle size of the composite particles (B) is in the range of 0.1 to 20 μm, and
The composite particle is a dispersion in which two or more particles of the electrically conductive filler are dispersed in the matrix using silica as a matrix ,
The electrically conductive filler is nickel, copper, gold, silver, aluminum, zinc, tin, lead, chromium, platinum, palladium, tungsten, molybdenum, or an alloy of two or more thereof, artificial graphite, natural graphite, glassy carbon , Carbon black, acetylene black, ketjen black, carbon fiber, carbon nanofiber, or a mixture of two or more thereof, a method for producing a thermoplastic resin composition.
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