WO2022202583A1 - Inorganic oxide powder, resin composition, and compression molded article - Google Patents
Inorganic oxide powder, resin composition, and compression molded article Download PDFInfo
- Publication number
- WO2022202583A1 WO2022202583A1 PCT/JP2022/012146 JP2022012146W WO2022202583A1 WO 2022202583 A1 WO2022202583 A1 WO 2022202583A1 JP 2022012146 W JP2022012146 W JP 2022012146W WO 2022202583 A1 WO2022202583 A1 WO 2022202583A1
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- WIPO (PCT)
- Prior art keywords
- region
- cumulative frequency
- inorganic oxide
- particle size
- oxide powder
- Prior art date
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- 239000000843 powder Substances 0.000 title claims abstract description 93
- 229910052809 inorganic oxide Inorganic materials 0.000 title claims abstract description 66
- 239000011342 resin composition Substances 0.000 title claims abstract description 59
- 230000006835 compression Effects 0.000 title claims abstract description 7
- 238000007906 compression Methods 0.000 title claims abstract description 7
- 230000001186 cumulative effect Effects 0.000 claims abstract description 118
- 239000002245 particle Substances 0.000 claims abstract description 92
- 238000009826 distribution Methods 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 24
- 229920000647 polyepoxide Polymers 0.000 description 22
- 239000003822 epoxy resin Substances 0.000 description 21
- 238000000748 compression moulding Methods 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007751 thermal spraying Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 3
- -1 polybutylene terephthalate Polymers 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
- C01F7/022—Classification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
- C01F7/027—Treatment involving fusion or vaporisation
Definitions
- Patent Document 1 a spherical alumina powder having a predetermined average particle size and having at least two or more maximum frequency peaks within a predetermined range in the particle size distribution and a spherical silica powder having a predetermined average particle size and specific surface area are combined into a predetermined A highly thermally conductive inorganic powder containing a proportion of According to this highly thermally conductive inorganic powder, it is possible to prepare a highly thermally conductive resin composition that does not easily become highly viscous even when highly filled in a resin, and has high fluidity and low burr characteristics.
- the present invention provides an inorganic oxide powder, a resin composition containing an inorganic oxide powder, and a resin composition that can provide a resin composition having a low ratio of low-shear viscosity to high-shear viscosity.
- An object of the present invention is to provide a compression-molded product that is
- the present invention has the following aspects.
- the second region located in the range of 0.001 ⁇ m to 20 ⁇ m in particle size with respect to the cumulative frequency of the first region located in the range of 0.001 ⁇ m to 10 ⁇ m in particle size
- the value of the cumulative frequency ratio (cumulative frequency of the second region / cumulative frequency of the first region) is 1.2 to 1.4, and the grain size is in the range of 0.001 ⁇ m or more and 10 ⁇ m or less.
- the inorganic oxide powder has a particle size in the range of 0.001 to 20 ⁇ m with respect to the cumulative frequency in the first region in which the particle size is in the range of 0.001 to 10 ⁇ m.
- the value of the ratio of the cumulative frequencies of the regions is 1.2 to 1.4.
- the inorganic oxide powder according to the present embodiment not only has excellent fluidity, but can also provide a resin composition with low viscosity under low shear.
- the inorganic oxide powder preferably has a cumulative frequency in the 1a region of 30 to 70%, more preferably 35 to 70%, and further preferably 40 to 65%. preferable.
- the cumulative frequency of region 1a can be 42-58%.
- the cumulative frequency of the 2a region is preferably 40 to 80%, more preferably 45 to 75%, and further preferably 50 to 70%. preferable.
- the cumulative frequency of region 2a can be 54-75%.
- the inorganic oxide powder has a particle size in the range of 0.1 to 20 ⁇ m with respect to the cumulative frequency of region 1b in which the particle size is in the range of 0.1 to 10 ⁇ m in the volume-based frequency particle size distribution.
- the value of the ratio of the cumulative frequency of a certain 2b region (cumulative frequency of the 2b region/cumulative frequency of the 1b region) is 1.2 to 1.4.
- the ratio of the cumulative frequency of the 2b region to the cumulative frequency of the 1b region (cumulative frequency of the 2b region/cumulative frequency of the 1b region) is 1.2 to 1.3 or 1.3 to 1.4.
- the inorganic oxide powder preferably has a cumulative frequency in the 1b region of 30 to 70%, more preferably 35 to 70%, and further preferably 40 to 65%. preferable.
- the cumulative frequency of region 1b can be 42-58%.
- the cumulative frequency of the 2b region is preferably 40 to 80%, more preferably 45 to 75%, and further preferably 50 to 70%. preferable.
- the cumulative frequency of region 2b can be 54-75%.
- the inorganic oxide powder has a particle size in the range of 0.001 to 35 ⁇ m with respect to the cumulative frequency in the first region in which the particle size is in the range of 0.001 to 10 ⁇ m.
- the value of the ratio of the cumulative frequencies of the regions is preferably 1.4 to 2.2, more preferably 1.5 to 2.0. preferable.
- the inorganic oxide powder contains 90% by mass or more, or 92% by mass or more of alumina. In one embodiment, the inorganic oxide powder contains 90% by mass or more, or 92% by mass or more of spherical amorphous alumina.
- the inorganic oxide powder preferably has a BET specific surface area of 0.5 to 2.0 m 2 /g, more preferably 0.8 to 1.8 m 2 /g, and more preferably 1.0 to 1.0 m 2 /g. It is more preferably 1.5 m 2 /g, particularly preferably 1.1 to 1.5 m 2 /g.
- the specific surface area by the BET method can be measured using a specific surface area measuring instrument such as "Macsorb HM model-1208" (manufactured by MACSORB).
- the specific surface area can be adjusted by changing the particle size and ratio of the inorganic oxide powder to be blended.
- the inorganic oxide powder preferably has a cumulative frequency of 90% or more, more preferably 95% or more, in a particle size range of 0.01 ⁇ m or more and 70 ⁇ m or less. , more preferably 98% or more.
- the inorganic oxide powder may have a cumulative frequency of 100% with a particle size in the range of 0.01 ⁇ m to 70 ⁇ m.
- the inorganic oxide powder preferably has a cumulative frequency of 90% or more, more preferably 95% or more, in a particle size range of 0.01 ⁇ m or more and 60 ⁇ m or less. , more preferably 98% or more.
- the inorganic oxide powder preferably has a volume-based cumulative 50 % diameter D50 of 5 to 20 ⁇ m, more preferably 5 to 15 ⁇ m, from the viewpoint of fluidity and viscosity of the resin composition.
- the volume-based cumulative 50% diameter D50 is a particle size corresponding to a cumulative value of 50% in a volume-based cumulative particle size distribution measured by a laser diffraction light scattering method (refractive index: 1.68).
- additives can be added to the resin composition as needed.
- Other additives include rubber-like substances such as silicone rubber, polysulfide rubber, acrylic rubber, butadiene rubber, styrenic block copolymers and saturated elastomers, and various thermoplastics other than the above-mentioned resins.
- resins resinous materials such as silicone resins, and resins obtained by partially or entirely modifying epoxy resins and phenolic resins with aminosilicone, epoxysilicone, alkoxysilicone, etc., and flame retardant aids such as Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 and the like; flame retardants such as halogenated epoxy resins and phosphorus compounds; and coloring agents such as carbon black, iron oxide, dyes and pigments.
- the viscosity of the resin composition at low shear is preferably 45 to 70 Pa s, preferably 45 to 65 Pa s, measured at a temperature of 30 ° C. and a rotation speed of 1 rpm using an E-type viscometer. is more preferable.
- the viscosity at low shear is kept low at the beginning of pressing the work against the resin composition, so the effect on wire deformation less, and has excellent moldability.
- the viscosity of the resin composition under high shear is preferably 35 to 55 Pa s, preferably 40 to 55 Pa s, measured at a temperature of 30° C. and a rotation speed of 10 rpm using an E-type viscometer. is more preferable.
- the viscosity at high shear is kept low, resulting in excellent moldability.
- a compression-molded article according to the present embodiment includes the resin composition described above.
- a known compression molding method can be used as a method for manufacturing the compression-molded product.
- the resin composition can be produced by compression molding by heat curing under conditions of a temperature of 180° C. and a pressure of 8 MPa.
- the compression-molded product contains a resin composition having a small ratio of the viscosity at low shear and the viscosity at high shear, it is possible to seal workpieces such as semiconductor chips without gaps and with extremely few voids. has the characteristics of Therefore, the compression-molded product can be preferably used as a semiconductor encapsulant, an adhesive member, a heat dissipation sheet, and the like for electronic devices.
- Examples 1 to 6, Comparative Examples 1 to 6 Alumina raw material powder having an average particle size (D 50 ) having a maximum value in the range of 2 to 45 ⁇ m is introduced into a high-temperature flame formed by using LPG as a fuel gas and oxygen as a combustion support gas, and is melted and spheroidized. Inorganic oxide powder (spherical alumina powder) was thus produced. The cumulative frequency of each particle size range was adjusted to the value shown in Table 1 by adjusting the blending amount of the raw material powder, sieving, classification, and the like.
- the resulting inorganic oxide powder was measured for viscosity (at low shear and at high shear) when blended with an epoxy resin by the method described below. Using the obtained values, the value of the ratio of the viscosity at low shear to the viscosity at high shear was calculated. Table 1 shows the results.
- a resin composition comprising 20% by mass of a bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: Epicoat 807, epoxy equivalent 170, viscosity 4 Pa s) and 80% by mass of the spherical alumina powder prepared above was prepared.
- the viscosity of the resin composition was measured using an E-type viscometer (trade name “TVE-10” manufactured by Toki Sangyo Co., Ltd.) at a temperature of 30° C. and a rotation speed of 1 rpm.
- the viscosity of the resin composition under high shear was measured using an E-type viscometer (trade name "TVE-10” manufactured by Toki Sangyo Co., Ltd.) at a temperature of 30° C. and a rotation speed of 10 rpm.
Abstract
[Problem] To provide: an inorganic oxide powder that makes it possible to provide a resin composition in which the ratio between viscosity during low shear and viscosity during high shear is low; a resin composition that contains the inorganic oxide powder; and a compression molded article that is obtained by molding the resin composition. [Solution] An inorganic oxide powder wherein: in a particle size frequency distribution based on volume, the value of the ratio (second region cumulative frequency / first region cumulative frequency) of the cumulative frequency in a second region in which particle diameter is within the range of 0.001-20 μm to the cumulative frequency in a first region in which particle diameter is within the range of 0.001-10 μm is 1.2-1.4; the value of the ratio (third region cumulative frequency / first region cumulative frequency) of the cumulative frequency in a third region in which particle diameter is within the range of 0.001-35 μm to the cumulative frequency in the first region in which the particle diameter in within the range of 0.001-10 μm is 1.4-2.2; and the cumulative frequency in the third region is 70-95 vol%.
Description
本発明は、無機酸化物粉末、樹脂組成物及び圧縮成形品に関する。
The present invention relates to inorganic oxide powders, resin compositions and compression molded articles.
近年、ＩＣの高機能化及び高速化の進展に伴い、その発熱量は増大傾向にあり、封止材等の電子部品に用いられる樹脂に対しても高い熱放散性を実現する要求が高まっている。従来、樹脂の高い熱放散性を実現するために、樹脂中に熱伝導性が高い無機粉末を高含有量で充填することが行われている。熱伝導性が高い無機粉末としては、窒化アルミニウム、酸化アルミニウム、結晶シリカ等が知られている。しかし、熱伝導性が高い無機粉末を樹脂中に高充填すると樹脂の流動性が低下してしまい、成形性に劣る場合がある。
特許文献１には、粒度分布において所定の範囲内に少なくとも２つ以上の頻度極大ピークを有する所定の平均粒子径の球状アルミナ粉末と所定の平均粒径及び比表面積の球状シリカ粉末とを所定の割合で含有する高熱伝導性無機質粉末が記載されている。この高熱伝導性無機粉末によれば、樹脂に高充填しても容易に高粘度化しない、高流動性かつ低バリ特性を有する高熱伝導性樹脂組成物を調製することができる。 In recent years, the amount of heat generated by ICs has tended to increase with the development of high-performance and high-speed ICs. there is Conventionally, in order to realize high heat dissipation of resin, a high content of inorganic powder having high heat conductivity is filled in resin. Aluminum nitride, aluminum oxide, crystalline silica, and the like are known as inorganic powders with high thermal conductivity. However, if the resin is highly filled with an inorganic powder having high thermal conductivity, the fluidity of the resin may be lowered, resulting in poor moldability.
In Patent Document 1, a spherical alumina powder having a predetermined average particle size and having at least two or more maximum frequency peaks within a predetermined range in the particle size distribution and a spherical silica powder having a predetermined average particle size and specific surface area are combined into a predetermined A highly thermally conductive inorganic powder containing a proportion of According to this highly thermally conductive inorganic powder, it is possible to prepare a highly thermally conductive resin composition that does not easily become highly viscous even when highly filled in a resin, and has high fluidity and low burr characteristics.
特許文献１には、粒度分布において所定の範囲内に少なくとも２つ以上の頻度極大ピークを有する所定の平均粒子径の球状アルミナ粉末と所定の平均粒径及び比表面積の球状シリカ粉末とを所定の割合で含有する高熱伝導性無機質粉末が記載されている。この高熱伝導性無機粉末によれば、樹脂に高充填しても容易に高粘度化しない、高流動性かつ低バリ特性を有する高熱伝導性樹脂組成物を調製することができる。 In recent years, the amount of heat generated by ICs has tended to increase with the development of high-performance and high-speed ICs. there is Conventionally, in order to realize high heat dissipation of resin, a high content of inorganic powder having high heat conductivity is filled in resin. Aluminum nitride, aluminum oxide, crystalline silica, and the like are known as inorganic powders with high thermal conductivity. However, if the resin is highly filled with an inorganic powder having high thermal conductivity, the fluidity of the resin may be lowered, resulting in poor moldability.
In Patent Document 1, a spherical alumina powder having a predetermined average particle size and having at least two or more maximum frequency peaks within a predetermined range in the particle size distribution and a spherical silica powder having a predetermined average particle size and specific surface area are combined into a predetermined A highly thermally conductive inorganic powder containing a proportion of According to this highly thermally conductive inorganic powder, it is possible to prepare a highly thermally conductive resin composition that does not easily become highly viscous even when highly filled in a resin, and has high fluidity and low burr characteristics.
電子部品の樹脂封止の成形方法として、トランスファーモールド法とコンプレッションモールド（圧縮成形）法とが知られている。トランスファーモールド法は、予め保温された金型のポット内にタブレット状の樹脂を投入し、溶融された樹脂をブランジャーでキャビティ内へ充填する成形方法である。コンプレッションモールド法は、パウダー又は顆粒状の樹脂組成物をキャビティ内に供給し、溶融された樹脂組成物にワークを押し当てて圧縮成形する方法である。コスト低減の観点からは、コンプレッションモールド法が望ましい。コンプレッションモールド法において成形性を高めるためには、用いられる樹脂組成物は、高せん断時の流動性に優れるだけでなく、低せん断時の流動性にも優れることが求められる。すなわち、低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物を与えることができる無機酸化物粉末が求められている。
Transfer molding and compression molding are known as molding methods for resin encapsulation of electronic components. The transfer molding method is a molding method in which tablet-shaped resin is put into a pot of a mold that has been kept warm in advance, and the melted resin is filled into the cavity using a plunger. The compression molding method is a method in which a powder or granular resin composition is supplied into a cavity, and a workpiece is pressed against the melted resin composition to perform compression molding. From the viewpoint of cost reduction, the compression molding method is desirable. In order to improve the moldability in the compression molding method, the resin composition to be used is required to have not only excellent fluidity under high shear but also excellent fluidity under low shear. That is, there is a demand for an inorganic oxide powder that can provide a resin composition having a low ratio of low-shear viscosity to high-shear viscosity.
本発明は、低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物を与えることができる無機酸化物粉末、無機酸化物粉末を含む樹脂組成物、樹脂組成物を成形してなる圧縮成形品を提供することを課題とする。
The present invention provides an inorganic oxide powder, a resin composition containing an inorganic oxide powder, and a resin composition that can provide a resin composition having a low ratio of low-shear viscosity to high-shear viscosity. An object of the present invention is to provide a compression-molded product that is
本発明は以下の態様を有する。
［１］体積基準の頻度粒度分布において、粒径が０．００１μｍ以上１０μｍ以下の範囲に位置する第１領域の累積頻度に対する、粒径が０．００１μｍ以上２０μｍ以下の範囲に位置する第２領域の累積頻度の比の値（第２領域の累積頻度／第１領域の累積頻度）が１．２～１．４であり、粒径が０．００１μｍ以上１０μｍ以下の範囲に位置する第１領域の累積頻度に対する、粒径が０．００１μｍ以上３５μｍ以下の範囲に位置する第３領域の累積頻度の比の値（第３領域の累積頻度／第１領域の累積頻度）が１．４～２．２であり、前記第３領域の累積頻度が、７０～９５体積％である、無機酸化物粉末。
［２］ＢＥＴ法による比表面積が、０．５～２．０ｍ２／ｇである、［１］に記載の無機酸化物粉末。
［３］粒径が０．０１μｍ以上７０μｍ以下の範囲の累積頻度が９０体積％以上である、［１］又は［２］に記載の無機酸化物粉末。
［４］［１］から［３］のいずれかに記載の無機酸化物粉末と樹脂とを含む、樹脂組成物。
［５］圧縮成形品の製造に用いられる、［４］に記載の樹脂組成物。
［６］［４］又は［５］に記載の樹脂組成物を含む、圧縮成形品。 The present invention has the following aspects.
[1] In the volume-based frequency particle size distribution, the second region located in the range of 0.001 μm to 20 μm in particle size with respect to the cumulative frequency of the first region located in the range of 0.001 μm to 10 μm in particle size The value of the cumulative frequency ratio (cumulative frequency of the second region / cumulative frequency of the first region) is 1.2 to 1.4, and the grain size is in the range of 0.001 μm or more and 10 μm or less. The value of the ratio of the cumulative frequency of the third region located in the range of 0.001 μm to 35 μm in particle size to the cumulative frequency of (cumulative frequency of the third region / cumulative frequency of the first region) is 1.4 to 2 .2, and the cumulative frequency of the third region is 70 to 95% by volume.
[2] The inorganic oxide powder according to [1], which has a BET specific surface area of 0.5 to 2.0 m 2 /g.
[3] The inorganic oxide powder according to [1] or [2], wherein the cumulative frequency of particle sizes in the range of 0.01 μm to 70 μm is 90% by volume or more.
[4] A resin composition comprising the inorganic oxide powder according to any one of [1] to [3] and a resin.
[5] The resin composition according to [4], which is used for producing a compression-molded product.
[6] A compression-molded article containing the resin composition according to [4] or [5].
［１］体積基準の頻度粒度分布において、粒径が０．００１μｍ以上１０μｍ以下の範囲に位置する第１領域の累積頻度に対する、粒径が０．００１μｍ以上２０μｍ以下の範囲に位置する第２領域の累積頻度の比の値（第２領域の累積頻度／第１領域の累積頻度）が１．２～１．４であり、粒径が０．００１μｍ以上１０μｍ以下の範囲に位置する第１領域の累積頻度に対する、粒径が０．００１μｍ以上３５μｍ以下の範囲に位置する第３領域の累積頻度の比の値（第３領域の累積頻度／第１領域の累積頻度）が１．４～２．２であり、前記第３領域の累積頻度が、７０～９５体積％である、無機酸化物粉末。
［２］ＢＥＴ法による比表面積が、０．５～２．０ｍ２／ｇである、［１］に記載の無機酸化物粉末。
［３］粒径が０．０１μｍ以上７０μｍ以下の範囲の累積頻度が９０体積％以上である、［１］又は［２］に記載の無機酸化物粉末。
［４］［１］から［３］のいずれかに記載の無機酸化物粉末と樹脂とを含む、樹脂組成物。
［５］圧縮成形品の製造に用いられる、［４］に記載の樹脂組成物。
［６］［４］又は［５］に記載の樹脂組成物を含む、圧縮成形品。 The present invention has the following aspects.
[1] In the volume-based frequency particle size distribution, the second region located in the range of 0.001 μm to 20 μm in particle size with respect to the cumulative frequency of the first region located in the range of 0.001 μm to 10 μm in particle size The value of the cumulative frequency ratio (cumulative frequency of the second region / cumulative frequency of the first region) is 1.2 to 1.4, and the grain size is in the range of 0.001 μm or more and 10 μm or less. The value of the ratio of the cumulative frequency of the third region located in the range of 0.001 μm to 35 μm in particle size to the cumulative frequency of (cumulative frequency of the third region / cumulative frequency of the first region) is 1.4 to 2 .2, and the cumulative frequency of the third region is 70 to 95% by volume.
[2] The inorganic oxide powder according to [1], which has a BET specific surface area of 0.5 to 2.0 m 2 /g.
[3] The inorganic oxide powder according to [1] or [2], wherein the cumulative frequency of particle sizes in the range of 0.01 μm to 70 μm is 90% by volume or more.
[4] A resin composition comprising the inorganic oxide powder according to any one of [1] to [3] and a resin.
[5] The resin composition according to [4], which is used for producing a compression-molded product.
[6] A compression-molded article containing the resin composition according to [4] or [5].
本発明によれば、低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物を与えることができる無機酸化物粉末、無機酸化物粉末を含む樹脂組成物、樹脂組成物を成形してなる圧縮成形品を提供することができる。
According to the present invention, an inorganic oxide powder, a resin composition containing an inorganic oxide powder, and a resin composition that can provide a resin composition having a low ratio of viscosity at low shear to viscosity at high shear are molded. A compression-molded product can be provided.
以下、本発明の一実施形態について詳細に説明する。本発明は、以下の実施形態に限定されるものではなく、本発明の効果を阻害しない範囲で適宜変更を加えて実施することができる。本明細書において、数値範囲に関する「Ｘ～Ｙ」との記載は、Ｘ以上Ｙ以下であることを意味している。
An embodiment of the present invention will be described in detail below. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope that does not impair the effects of the present invention. In this specification, the description “X to Y” regarding the numerical range means X or more and Y or less.
［無機酸化物粉末］
本実施形態に係る無機酸化物粉末は、体積基準の頻度粒度分布において、
粒径が０．００１μｍ以上１０μｍ以下の範囲に位置する第１領域の累積頻度に対する、粒径が０．００１μｍ以上２０μｍ以下の範囲に位置する第２領域の累積頻度の比の値（第２領域の累積頻度／第１領域の累積頻度）が１．２～１．４であり、
粒径が０．００１μｍ以上１０μｍ以下の範囲に位置する第１領域の累積頻度に対する、粒径が０．００１μｍ以上３５μｍ以下の範囲に位置する第３領域の累積頻度の比の値（第３領域の累積頻度／第１領域の累積頻度）が１．４～２．２であり、
前記第３領域の累積頻度が、７０～９５体積％である。
このように設計された無機酸化物粉末は、低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物を与えることができる。低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物は、コンプレッションモールド法において、樹脂にワークを押し当てる際に初めから終わりまで粘度が低く保たれるので、成形性に優れている。
加えて、このように設計された無機酸化物粉末は、溶融時の流動性に優れる樹脂組成物を与えることができる。その結果、コンプレッションモールド法においてより成形性を高めることができる。 [Inorganic oxide powder]
In the volume-based frequency particle size distribution, the inorganic oxide powder according to the present embodiment has
The value of the ratio of the cumulative frequency of the second region located in the range of 0.001 μm to 20 μm in particle size to the cumulative frequency of the first region located in the range of 0.001 μm to 10 μm in particle size (second region Cumulative frequency of / Cumulative frequency of the first region) is 1.2 to 1.4,
The value of the ratio of the cumulative frequency of the third region located in the range of 0.001 μm to 35 μm in particle size to the cumulative frequency of the first region located in the range of 0.001 μm to 10 μm in particle size (third region Cumulative frequency of / Cumulative frequency of the first region) is 1.4 to 2.2,
The cumulative frequency of the third region is 70-95% by volume.
An inorganic oxide powder designed in this way can provide a resin composition having a low ratio of low-shear viscosity to high-shear viscosity. A resin composition with a small ratio of low-shear viscosity to high-shear viscosity is excellent in moldability because the viscosity is kept low from the beginning to the end when the workpiece is pressed against the resin in the compression molding method. ing.
In addition, the inorganic oxide powder designed in this way can provide a resin composition with excellent fluidity when melted. As a result, the moldability can be further improved in the compression molding method.
本実施形態に係る無機酸化物粉末は、体積基準の頻度粒度分布において、
粒径が０．００１μｍ以上１０μｍ以下の範囲に位置する第１領域の累積頻度に対する、粒径が０．００１μｍ以上２０μｍ以下の範囲に位置する第２領域の累積頻度の比の値（第２領域の累積頻度／第１領域の累積頻度）が１．２～１．４であり、
粒径が０．００１μｍ以上１０μｍ以下の範囲に位置する第１領域の累積頻度に対する、粒径が０．００１μｍ以上３５μｍ以下の範囲に位置する第３領域の累積頻度の比の値（第３領域の累積頻度／第１領域の累積頻度）が１．４～２．２であり、
前記第３領域の累積頻度が、７０～９５体積％である。
このように設計された無機酸化物粉末は、低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物を与えることができる。低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物は、コンプレッションモールド法において、樹脂にワークを押し当てる際に初めから終わりまで粘度が低く保たれるので、成形性に優れている。
加えて、このように設計された無機酸化物粉末は、溶融時の流動性に優れる樹脂組成物を与えることができる。その結果、コンプレッションモールド法においてより成形性を高めることができる。 [Inorganic oxide powder]
In the volume-based frequency particle size distribution, the inorganic oxide powder according to the present embodiment has
The value of the ratio of the cumulative frequency of the second region located in the range of 0.001 μm to 20 μm in particle size to the cumulative frequency of the first region located in the range of 0.001 μm to 10 μm in particle size (second region Cumulative frequency of / Cumulative frequency of the first region) is 1.2 to 1.4,
The value of the ratio of the cumulative frequency of the third region located in the range of 0.001 μm to 35 μm in particle size to the cumulative frequency of the first region located in the range of 0.001 μm to 10 μm in particle size (third region Cumulative frequency of / Cumulative frequency of the first region) is 1.4 to 2.2,
The cumulative frequency of the third region is 70-95% by volume.
An inorganic oxide powder designed in this way can provide a resin composition having a low ratio of low-shear viscosity to high-shear viscosity. A resin composition with a small ratio of low-shear viscosity to high-shear viscosity is excellent in moldability because the viscosity is kept low from the beginning to the end when the workpiece is pressed against the resin in the compression molding method. ing.
In addition, the inorganic oxide powder designed in this way can provide a resin composition with excellent fluidity when melted. As a result, the moldability can be further improved in the compression molding method.
「体積基準の頻度粒度分布」は、レーザー回折光散乱法（屈折率：１．６８）により測定され、横軸を粒径（μｍ）、縦軸を体積基準の頻度（％）とする分布曲線で表される。無機酸化物粉末は、体積基準の頻度粒度分布において、少なくとも一つのピークを有していることが好ましい。ピークはショルダーを有していてもよい。
「粒径」は、体積基準の頻度粒度分布の横軸に表される数値とする。
「ピーク」は、体積基準の頻度粒度分布において一つの極大値を有している分布曲線を意味している。
「ショルダー」は、ピークから完全に分離していない不完全なピーク（すなわち、ピークを構成する分布曲線の傾斜の途中に膨らみが形成されている段差部分）であり一つの極大値を有する又は有しない分布曲線を意味している。
「極大値」は、体積基準の頻度粒度分布において曲線の傾きが正から負へと変わる境界のことを意味している。 "Volume-based frequency particle size distribution" is measured by a laser diffraction light scattering method (refractive index: 1.68), with a distribution curve in which the horizontal axis is the particle size (μm) and the vertical axis is the volume-based frequency (%). is represented by The inorganic oxide powder preferably has at least one peak in the volume-based frequency particle size distribution. A peak may have a shoulder.
"Particle size" is a numerical value represented on the horizontal axis of the volume-based frequency particle size distribution.
"Peak" means a distribution curve having one maximum in the volume-based frequency particle size distribution.
"Shoulder" is an incomplete peak that is not completely separated from the peak (i.e., a stepped portion in which a bulge is formed in the middle of the slope of the distribution curve that constitutes the peak) and has one maximum value. does not mean a distribution curve.
"Maximum" means the boundary where the slope of the curve changes from positive to negative in the volume-based frequency particle size distribution.
「粒径」は、体積基準の頻度粒度分布の横軸に表される数値とする。
「ピーク」は、体積基準の頻度粒度分布において一つの極大値を有している分布曲線を意味している。
「ショルダー」は、ピークから完全に分離していない不完全なピーク（すなわち、ピークを構成する分布曲線の傾斜の途中に膨らみが形成されている段差部分）であり一つの極大値を有する又は有しない分布曲線を意味している。
「極大値」は、体積基準の頻度粒度分布において曲線の傾きが正から負へと変わる境界のことを意味している。 "Volume-based frequency particle size distribution" is measured by a laser diffraction light scattering method (refractive index: 1.68), with a distribution curve in which the horizontal axis is the particle size (μm) and the vertical axis is the volume-based frequency (%). is represented by The inorganic oxide powder preferably has at least one peak in the volume-based frequency particle size distribution. A peak may have a shoulder.
"Particle size" is a numerical value represented on the horizontal axis of the volume-based frequency particle size distribution.
"Peak" means a distribution curve having one maximum in the volume-based frequency particle size distribution.
"Shoulder" is an incomplete peak that is not completely separated from the peak (i.e., a stepped portion in which a bulge is formed in the middle of the slope of the distribution curve that constitutes the peak) and has one maximum value. does not mean a distribution curve.
"Maximum" means the boundary where the slope of the curve changes from positive to negative in the volume-based frequency particle size distribution.
「領域」は、ここでは、体積基準の頻度粒度分布において、極大値の有無及び数に関わらず、所定の粒径を有する範囲に位置する分布曲線を意味している。
「第１領域」は、体積基準の頻度粒度分布において粒径が０．００１～１０μｍの範囲に位置する分布曲線の一領域を意味している。
「第２領域」は、体積基準の頻度粒度分布において粒径が０．００１～２０μｍの範囲に位置する分布曲線の一領域を意味している。なお、第２領域には第１領域が含まれている。
「累積頻度」は、体積基準の頻度粒度分布の所定の粒径範囲における頻度（％）の累積値のことを意味している。
「低せん断時の粘度」は、Ｅ型粘度計を用い、温度３０℃、１ｒｐｍの回転数により測定した粘度を意味している。
「高せん断時の粘度」は、Ｅ型粘度計を用い、温度３０℃、１０ｒｐｍの回転数により測定した粘度を意味している。 A "region" here means a distribution curve located in a range having a given particle size in the volume-based frequency particle size distribution, regardless of the presence or absence and number of local maxima.
The “first region” means one region of the distribution curve in which the particle size is located in the range of 0.001 to 10 μm in the volume-based frequency particle size distribution.
"Second region" means a region of the distribution curve in which the particle size is located in the range of 0.001 to 20 µm in the volume-based frequency particle size distribution. Note that the second area includes the first area.
"Cumulative frequency" means the cumulative value of frequency (%) in a predetermined particle size range of the volume-based frequency particle size distribution.
"Low-shear viscosity" means a viscosity measured at a temperature of 30°C and a rotation speed of 1 rpm using an E-type viscometer.
"Viscosity at high shear" means the viscosity measured at a temperature of 30°C and a rotation speed of 10 rpm using an E-type viscometer.
「第１領域」は、体積基準の頻度粒度分布において粒径が０．００１～１０μｍの範囲に位置する分布曲線の一領域を意味している。
「第２領域」は、体積基準の頻度粒度分布において粒径が０．００１～２０μｍの範囲に位置する分布曲線の一領域を意味している。なお、第２領域には第１領域が含まれている。
「累積頻度」は、体積基準の頻度粒度分布の所定の粒径範囲における頻度（％）の累積値のことを意味している。
「低せん断時の粘度」は、Ｅ型粘度計を用い、温度３０℃、１ｒｐｍの回転数により測定した粘度を意味している。
「高せん断時の粘度」は、Ｅ型粘度計を用い、温度３０℃、１０ｒｐｍの回転数により測定した粘度を意味している。 A "region" here means a distribution curve located in a range having a given particle size in the volume-based frequency particle size distribution, regardless of the presence or absence and number of local maxima.
The “first region” means one region of the distribution curve in which the particle size is located in the range of 0.001 to 10 μm in the volume-based frequency particle size distribution.
"Second region" means a region of the distribution curve in which the particle size is located in the range of 0.001 to 20 µm in the volume-based frequency particle size distribution. Note that the second area includes the first area.
"Cumulative frequency" means the cumulative value of frequency (%) in a predetermined particle size range of the volume-based frequency particle size distribution.
"Low-shear viscosity" means a viscosity measured at a temperature of 30°C and a rotation speed of 1 rpm using an E-type viscometer.
"Viscosity at high shear" means the viscosity measured at a temperature of 30°C and a rotation speed of 10 rpm using an E-type viscometer.
（第２領域の累積頻度／第１領域の累積頻度）
無機酸化物粉末は、体積基準の頻度粒度分布において、粒径が０．００１～１０μｍの範囲に位置する第１領域の累積頻度に対する、粒径が０．００１～２０μｍの範囲に位置する第２領域の累積頻度の比の値（第２領域の累積頻度／第１領域の累積頻度）が、１．２～１．４である。第１領域の累積頻度に対する第２領域の累積頻度の比の値を１．２～１．４とすることで、低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物を与えることができる。 (cumulative frequency in second area/cumulative frequency in first area)
In the volume-based frequency particle size distribution, the inorganic oxide powder has a particle size in the range of 0.001 to 20 μm with respect to the cumulative frequency in the first region in which the particle size is in the range of 0.001 to 10 μm. The value of the ratio of the cumulative frequencies of the regions (cumulative frequency of the second region/cumulative frequency of the first region) is 1.2 to 1.4. By setting the value of the ratio of the cumulative frequency of the second region to the cumulative frequency of the first region to 1.2 to 1.4, a resin composition having a low ratio of the viscosity at low shear and the viscosity at high shear can be obtained. can give.
無機酸化物粉末は、体積基準の頻度粒度分布において、粒径が０．００１～１０μｍの範囲に位置する第１領域の累積頻度に対する、粒径が０．００１～２０μｍの範囲に位置する第２領域の累積頻度の比の値（第２領域の累積頻度／第１領域の累積頻度）が、１．２～１．４である。第１領域の累積頻度に対する第２領域の累積頻度の比の値を１．２～１．４とすることで、低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物を与えることができる。 (cumulative frequency in second area/cumulative frequency in first area)
In the volume-based frequency particle size distribution, the inorganic oxide powder has a particle size in the range of 0.001 to 20 μm with respect to the cumulative frequency in the first region in which the particle size is in the range of 0.001 to 10 μm. The value of the ratio of the cumulative frequencies of the regions (cumulative frequency of the second region/cumulative frequency of the first region) is 1.2 to 1.4. By setting the value of the ratio of the cumulative frequency of the second region to the cumulative frequency of the first region to 1.2 to 1.4, a resin composition having a low ratio of the viscosity at low shear and the viscosity at high shear can be obtained. can give.
従来、粒径が異なる小径粒子、中径粒子、及び大径粒子の複数の無機酸化物粉末を配合して中径粒子及び／又は大径粒子の隙間を小径粒子で埋めることで最密充填構造を形成させ流動性に優れた樹脂組成物とすることが試みられている。本実施形態に係る無機酸化物粉末は、流動性に優れるだけでなく、低せん断時の粘度が低い樹脂組成物を与えることができる。この理由は現段階では明らかではないが、第１領域の累積頻度に対する第２領域の累積頻度の比の値を１．２～１．４とすることで、小径粒子（粒径が１０μｍ以下の微粒子）の凝集が抑制されて低せん断時における粒子の動きやすさが向上するためであると推測される。
Conventionally, a plurality of inorganic oxide powders of small, medium, and large diameters with different particle sizes are blended, and the gaps between the medium and/or large particles are filled with small particles to form a close-packed structure. Attempts have been made to form a resin composition having excellent fluidity. The inorganic oxide powder according to the present embodiment not only has excellent fluidity, but can also provide a resin composition with low viscosity under low shear. The reason for this is not clear at this stage, but by setting the ratio of the cumulative frequency of the second region to the cumulative frequency of the first region to be 1.2 to 1.4, small-diameter particles (particle diameters of 10 μm or less) It is presumed that this is because aggregation of fine particles is suppressed and the easiness of movement of particles is improved at the time of low shear.
第１領域の累積頻度に対する第２領域の累積頻度の比の値（第２領域の累積頻度／第１領域の累積頻度）は、１．２～１．３、又は１．３～１．４とすることもできる。
The value of the ratio of the cumulative frequency of the second region to the cumulative frequency of the first region (cumulative frequency of the second region/cumulative frequency of the first region) is 1.2 to 1.3, or 1.3 to 1.4 can also be
無機酸化物粉末は、流動性の観点から、第１領域の累積頻度が、３０～７０％であることが好ましく、３５～７０％であることがより好ましく、４０～６５％であることがさらに好ましい。一実施形態において、第１領域の累積頻度は、４２～５８％である。
From the viewpoint of fluidity, the inorganic oxide powder preferably has a cumulative frequency of the first region of 30 to 70%, more preferably 35 to 70%, and further preferably 40 to 65%. preferable. In one embodiment, the cumulative frequency of the first region is 42-58%.
無機酸化物粉末は、流動性の観点から、第２領域の累積頻度が、４０～８０％であることが好ましく、４５～７５％であることがより好ましく、５０～７０％であることがさらに好ましい。一実施形態において、第２領域の累積頻度は、５４～７５％である。
From the viewpoint of fluidity, the inorganic oxide powder preferably has a cumulative frequency of the second region of 40 to 80%, more preferably 45 to 75%, and further preferably 50 to 70%. preferable. In one embodiment, the cumulative frequency of the second region is 54-75%.
一実施形態において、無機酸化物粉末は、体積基準の頻度粒度分布において、粒径が０．０１～１０μｍの範囲である第１ａ領域の累積頻度に対する、粒径が０．０１～２０μｍの範囲である第２ａ領域の累積頻度の比の値（第２ａ領域の累積頻度／第１ａ領域の累積頻度）が、１．２～１．４である。第１ａ領域の累積頻度に対する第２ａ領域の累積頻度の比の値（第２ａ領域の累積頻度／第１ａ領域の累積頻度）は、１．２～１．３又は１．３～１．４とすることもできる。
無機酸化物粉末は、流動性の観点から、第１ａ領域の累積頻度が、３０～７０％であることが好ましく、３５～７０％であることがより好ましく、４０～６５％であることがさらに好ましい。一実施形態において、第１ａ領域の累積頻度は、４２～５８％であり得る。
無機酸化物粉末は、流動性の観点から、第２ａ領域の累積頻度が、４０～８０％であることが好ましく、４５～７５％であることがより好ましく、５０～７０％であることがさらに好ましい。一実施形態において、第２ａ領域の累積頻度は、５４～７５％であり得る。 In one embodiment, the inorganic oxide powder has a particle size in the range of 0.01 to 20 μm with respect to the cumulative frequency of region 1a in which the particle size is in the range of 0.01 to 10 μm in the volume-based frequency particle size distribution. The value of the ratio of the cumulative frequency of a certain 2a region (cumulative frequency of the 2a region/cumulative frequency of the 1a region) is 1.2 to 1.4. The ratio of the cumulative frequency of the 2a region to the cumulative frequency of the 1a region (cumulative frequency of the 2a region/cumulative frequency of the 1a region) is 1.2 to 1.3 or 1.3 to 1.4. You can also
From the viewpoint of fluidity, the inorganic oxide powder preferably has a cumulative frequency in the 1a region of 30 to 70%, more preferably 35 to 70%, and further preferably 40 to 65%. preferable. In one embodiment, the cumulative frequency of region 1a can be 42-58%.
In the inorganic oxide powder, from the viewpoint of fluidity, the cumulative frequency of the 2a region is preferably 40 to 80%, more preferably 45 to 75%, and further preferably 50 to 70%. preferable. In one embodiment, the cumulative frequency of region 2a can be 54-75%.
無機酸化物粉末は、流動性の観点から、第１ａ領域の累積頻度が、３０～７０％であることが好ましく、３５～７０％であることがより好ましく、４０～６５％であることがさらに好ましい。一実施形態において、第１ａ領域の累積頻度は、４２～５８％であり得る。
無機酸化物粉末は、流動性の観点から、第２ａ領域の累積頻度が、４０～８０％であることが好ましく、４５～７５％であることがより好ましく、５０～７０％であることがさらに好ましい。一実施形態において、第２ａ領域の累積頻度は、５４～７５％であり得る。 In one embodiment, the inorganic oxide powder has a particle size in the range of 0.01 to 20 μm with respect to the cumulative frequency of region 1a in which the particle size is in the range of 0.01 to 10 μm in the volume-based frequency particle size distribution. The value of the ratio of the cumulative frequency of a certain 2a region (cumulative frequency of the 2a region/cumulative frequency of the 1a region) is 1.2 to 1.4. The ratio of the cumulative frequency of the 2a region to the cumulative frequency of the 1a region (cumulative frequency of the 2a region/cumulative frequency of the 1a region) is 1.2 to 1.3 or 1.3 to 1.4. You can also
From the viewpoint of fluidity, the inorganic oxide powder preferably has a cumulative frequency in the 1a region of 30 to 70%, more preferably 35 to 70%, and further preferably 40 to 65%. preferable. In one embodiment, the cumulative frequency of region 1a can be 42-58%.
In the inorganic oxide powder, from the viewpoint of fluidity, the cumulative frequency of the 2a region is preferably 40 to 80%, more preferably 45 to 75%, and further preferably 50 to 70%. preferable. In one embodiment, the cumulative frequency of region 2a can be 54-75%.
一実施形態において、無機酸化物粉末は、体積基準の頻度粒度分布において、粒径が０．１～１０μｍの範囲である第１ｂ領域の累積頻度に対する、粒径が０．１～２０μｍの範囲である第２ｂ領域の累積頻度の比の値（第２ｂ領域の累積頻度／第１ｂ領域の累積頻度）が、１．２～１．４である。第１ｂ領域の累積頻度に対する第２ｂ領域の累積頻度の比の値（第２ｂ領域の累積頻度／第１ｂ領域の累積頻度）は、１．２～１．３又は１．３～１．４とすることもできる。
無機酸化物粉末は、流動性の観点から、第１ｂ領域の累積頻度が、３０～７０％であることが好ましく、３５～７０％であることがより好ましく、４０～６５％であることがさらに好ましい。一実施形態において、第１ｂ領域の累積頻度は、４２～５８％であり得る。
無機酸化物粉末は、流動性の観点から、第２ｂ領域の累積頻度が、４０～８０％であることが好ましく、４５～７５％であることがより好ましく、５０～７０％であることがさらに好ましい。一実施形態において、第２ｂ領域の累積頻度は、５４～７５％であり得る。 In one embodiment, the inorganic oxide powder has a particle size in the range of 0.1 to 20 μm with respect to the cumulative frequency of region 1b in which the particle size is in the range of 0.1 to 10 μm in the volume-based frequency particle size distribution. The value of the ratio of the cumulative frequency of a certain 2b region (cumulative frequency of the 2b region/cumulative frequency of the 1b region) is 1.2 to 1.4. The ratio of the cumulative frequency of the 2b region to the cumulative frequency of the 1b region (cumulative frequency of the 2b region/cumulative frequency of the 1b region) is 1.2 to 1.3 or 1.3 to 1.4. You can also
From the viewpoint of fluidity, the inorganic oxide powder preferably has a cumulative frequency in the 1b region of 30 to 70%, more preferably 35 to 70%, and further preferably 40 to 65%. preferable. In one embodiment, the cumulative frequency of region 1b can be 42-58%.
In the inorganic oxide powder, from the viewpoint of fluidity, the cumulative frequency of the 2b region is preferably 40 to 80%, more preferably 45 to 75%, and further preferably 50 to 70%. preferable. In one embodiment, the cumulative frequency of region 2b can be 54-75%.
無機酸化物粉末は、流動性の観点から、第１ｂ領域の累積頻度が、３０～７０％であることが好ましく、３５～７０％であることがより好ましく、４０～６５％であることがさらに好ましい。一実施形態において、第１ｂ領域の累積頻度は、４２～５８％であり得る。
無機酸化物粉末は、流動性の観点から、第２ｂ領域の累積頻度が、４０～８０％であることが好ましく、４５～７５％であることがより好ましく、５０～７０％であることがさらに好ましい。一実施形態において、第２ｂ領域の累積頻度は、５４～７５％であり得る。 In one embodiment, the inorganic oxide powder has a particle size in the range of 0.1 to 20 μm with respect to the cumulative frequency of region 1b in which the particle size is in the range of 0.1 to 10 μm in the volume-based frequency particle size distribution. The value of the ratio of the cumulative frequency of a certain 2b region (cumulative frequency of the 2b region/cumulative frequency of the 1b region) is 1.2 to 1.4. The ratio of the cumulative frequency of the 2b region to the cumulative frequency of the 1b region (cumulative frequency of the 2b region/cumulative frequency of the 1b region) is 1.2 to 1.3 or 1.3 to 1.4. You can also
From the viewpoint of fluidity, the inorganic oxide powder preferably has a cumulative frequency in the 1b region of 30 to 70%, more preferably 35 to 70%, and further preferably 40 to 65%. preferable. In one embodiment, the cumulative frequency of region 1b can be 42-58%.
In the inorganic oxide powder, from the viewpoint of fluidity, the cumulative frequency of the 2b region is preferably 40 to 80%, more preferably 45 to 75%, and further preferably 50 to 70%. preferable. In one embodiment, the cumulative frequency of region 2b can be 54-75%.
第１領域（粒径：０．００１～１０μｍ）の累積頻度に対する第２領域（０．００１～２０μｍ）の累積頻度の比の値を１．２～１．４に調整する方法としては、例えば、第１及び第２領域の累積頻度を上記した好ましい範囲に調整する方法等が挙げられる。
なお、累積頻度の調整は、粒度を調整した原料粉末の配合量を調整することや、篩分けや分級等で行うことができる。 As a method for adjusting the ratio of the cumulative frequency of the second region (0.001 to 20 μm) to the cumulative frequency of the first region (particle size: 0.001 to 10 μm) to 1.2 to 1.4, for example , a method of adjusting the cumulative frequencies of the first and second regions to the preferred ranges described above, and the like.
The cumulative frequency can be adjusted by adjusting the blending amount of the raw material powder whose particle size is adjusted, or by sieving, classifying, or the like.
なお、累積頻度の調整は、粒度を調整した原料粉末の配合量を調整することや、篩分けや分級等で行うことができる。 As a method for adjusting the ratio of the cumulative frequency of the second region (0.001 to 20 μm) to the cumulative frequency of the first region (particle size: 0.001 to 10 μm) to 1.2 to 1.4, for example , a method of adjusting the cumulative frequencies of the first and second regions to the preferred ranges described above, and the like.
The cumulative frequency can be adjusted by adjusting the blending amount of the raw material powder whose particle size is adjusted, or by sieving, classifying, or the like.
（第３領域の累積頻度／第１領域の累積頻度）
無機酸化物粉末は、体積基準の頻度粒度分布において、粒径が０．００１～１０μｍの範囲に位置する第１領域の累積頻度に対する、粒径が０．００１～３５μｍの範囲に位置する第３領域の累積頻度の比の値（第３領域の累積頻度／第１領域の累積頻度）が、１．４～２．２であることが好ましく、１．５～２．０であることがより好ましい。
第１領域の累積頻度に対する第３領域の累積頻度の比の値を１．４～２．２とすることで、流動性の高い樹脂組成物を与えることができる。
「第３領域」は、体積基準の頻度粒度分布において粒径が０．００１～３５μｍの範囲に位置する分布曲線の一領域を意味している。「第１領域」については、上述のとおりである。なお、第３領域には第１領域及び第２領域が含まれている。 (cumulative frequency in the third area/cumulative frequency in the first area)
In the volume-based frequency particle size distribution, the inorganic oxide powder has a particle size in the range of 0.001 to 35 μm with respect to the cumulative frequency in the first region in which the particle size is in the range of 0.001 to 10 μm. The value of the ratio of the cumulative frequencies of the regions (cumulative frequency of the third region / cumulative frequency of the first region) is preferably 1.4 to 2.2, more preferably 1.5 to 2.0. preferable.
By setting the ratio of the cumulative frequency of the third region to the cumulative frequency of the first region to 1.4 to 2.2, a resin composition with high fluidity can be obtained.
The “third region” means a region of the distribution curve in which the particle size is located in the range of 0.001 to 35 μm in the volume-based frequency particle size distribution. The "first area" is as described above. Note that the third area includes the first area and the second area.
無機酸化物粉末は、体積基準の頻度粒度分布において、粒径が０．００１～１０μｍの範囲に位置する第１領域の累積頻度に対する、粒径が０．００１～３５μｍの範囲に位置する第３領域の累積頻度の比の値（第３領域の累積頻度／第１領域の累積頻度）が、１．４～２．２であることが好ましく、１．５～２．０であることがより好ましい。
第１領域の累積頻度に対する第３領域の累積頻度の比の値を１．４～２．２とすることで、流動性の高い樹脂組成物を与えることができる。
「第３領域」は、体積基準の頻度粒度分布において粒径が０．００１～３５μｍの範囲に位置する分布曲線の一領域を意味している。「第１領域」については、上述のとおりである。なお、第３領域には第１領域及び第２領域が含まれている。 (cumulative frequency in the third area/cumulative frequency in the first area)
In the volume-based frequency particle size distribution, the inorganic oxide powder has a particle size in the range of 0.001 to 35 μm with respect to the cumulative frequency in the first region in which the particle size is in the range of 0.001 to 10 μm. The value of the ratio of the cumulative frequencies of the regions (cumulative frequency of the third region / cumulative frequency of the first region) is preferably 1.4 to 2.2, more preferably 1.5 to 2.0. preferable.
By setting the ratio of the cumulative frequency of the third region to the cumulative frequency of the first region to 1.4 to 2.2, a resin composition with high fluidity can be obtained.
The “third region” means a region of the distribution curve in which the particle size is located in the range of 0.001 to 35 μm in the volume-based frequency particle size distribution. The "first area" is as described above. Note that the third area includes the first area and the second area.
無機酸化物粉末は、樹脂組成物の流動性の観点から、第３領域の累積頻度が、７０～９５％であり、７５～９５％であることが好ましく、７５～９０％であることがより好ましい。第１領域の累積頻度については上述のとおりである。一実施形態において、第３領域の累積頻度は、７７～９４％であり得る。
From the viewpoint of the fluidity of the resin composition, the inorganic oxide powder has a cumulative frequency in the third region of 70 to 95%, preferably 75 to 95%, more preferably 75 to 90%. preferable. The cumulative frequency of the first area is as described above. In one embodiment, the cumulative frequency of the third region can be 77-94%.
第１領域（粒径：０．００１～１０μｍ）の累積頻度に対する第３領域（粒径：０．００１～３５μｍ）の累積頻度の比の値を１．４～２．２に調整する方法としては、例えば、第１～３領域の累積頻度を上記した好ましい範囲に調整する方法等が挙げられる。なお、累積頻度の調整は、粒度を調整した原料粉末の配合量を調整することや、篩分けや分級等で行うことができる。
As a method of adjusting the ratio of the cumulative frequency of the third region (particle size: 0.001 to 35 μm) to the cumulative frequency of the first region (particle size: 0.001 to 10 μm) to 1.4 to 2.2 For example, a method of adjusting the cumulative frequencies of the first to third regions to the preferred ranges described above, and the like can be mentioned. The cumulative frequency can be adjusted by adjusting the blending amount of the raw material powder whose particle size is adjusted, or by sieving, classifying, or the like.
無機酸化物粉末は、体積基準の頻度粒度分布において、少なくとも、一つのピークを有していることが好まく、２以上のピークを有する場合、流動性に優れた樹脂組成物を与えることができる。
The inorganic oxide powder preferably has at least one peak in the volume-based frequency particle size distribution, and when it has two or more peaks, a resin composition having excellent fluidity can be obtained. .
（無機酸化物粉末）
無機酸化物粉末としては、金属酸化物粉末が挙げられる。金属酸化物粉末としては、シリカ（ＳｉＯ２）、アルミナ（Ａｌ２Ｏ３）、チタニア（ＴｉＯ２）、マグネシア（ＭｇＯ）、カルシア（ＣａＯ）等の無機質粉末が挙げられる。無機質粉末は、これらから選択される１以上の金属酸化物粉末を含むことが好ましく、アルミナを含むことがより好ましく、アルミナであることがさらに好ましい。樹脂への高充填化の観点から、球状のアルミナを含むことが好ましい。「球状」とは、走査型電子顕微鏡を用いて１００倍で観察したときに円形状又は丸みを帯びた粒形状に観察されることを意味する。一実施形態において、無機酸化物粉末は、アルミナを９０質量％以上、又は９２質量％以上含む。一実施形態において、無機酸化物粉末は、球状非晶質アルミナを９０質量％以上、又は９２質量％以上含む。 (Inorganic oxide powder)
Examples of inorganic oxide powders include metal oxide powders. Examples of metal oxide powders include inorganic powders such as silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), magnesia (MgO) and calcia (CaO). The inorganic powder preferably contains one or more metal oxide powders selected from these, more preferably alumina, and still more preferably alumina. From the viewpoint of high filling of the resin, it is preferable to contain spherical alumina. "Spherical" means that when observed with a scanning electron microscope at a magnification of 100, the particles are observed to have a circular or rounded grain shape. In one embodiment, the inorganic oxide powder contains 90% by mass or more, or 92% by mass or more of alumina. In one embodiment, the inorganic oxide powder contains 90% by mass or more, or 92% by mass or more of spherical amorphous alumina.
無機酸化物粉末としては、金属酸化物粉末が挙げられる。金属酸化物粉末としては、シリカ（ＳｉＯ２）、アルミナ（Ａｌ２Ｏ３）、チタニア（ＴｉＯ２）、マグネシア（ＭｇＯ）、カルシア（ＣａＯ）等の無機質粉末が挙げられる。無機質粉末は、これらから選択される１以上の金属酸化物粉末を含むことが好ましく、アルミナを含むことがより好ましく、アルミナであることがさらに好ましい。樹脂への高充填化の観点から、球状のアルミナを含むことが好ましい。「球状」とは、走査型電子顕微鏡を用いて１００倍で観察したときに円形状又は丸みを帯びた粒形状に観察されることを意味する。一実施形態において、無機酸化物粉末は、アルミナを９０質量％以上、又は９２質量％以上含む。一実施形態において、無機酸化物粉末は、球状非晶質アルミナを９０質量％以上、又は９２質量％以上含む。 (Inorganic oxide powder)
Examples of inorganic oxide powders include metal oxide powders. Examples of metal oxide powders include inorganic powders such as silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), magnesia (MgO) and calcia (CaO). The inorganic powder preferably contains one or more metal oxide powders selected from these, more preferably alumina, and still more preferably alumina. From the viewpoint of high filling of the resin, it is preferable to contain spherical alumina. "Spherical" means that when observed with a scanning electron microscope at a magnification of 100, the particles are observed to have a circular or rounded grain shape. In one embodiment, the inorganic oxide powder contains 90% by mass or more, or 92% by mass or more of alumina. In one embodiment, the inorganic oxide powder contains 90% by mass or more, or 92% by mass or more of spherical amorphous alumina.
無機酸化物粉末は、ＢＥＴ法による比表面積が、０．５～２．０ｍ２／ｇであることが好ましく、０．８～１．８ｍ２／ｇであることがより好ましく、１．０～１．５ｍ２／ｇであることがさらに好ましく、１．１～１．５ｍ２／ｇであることが特に好ましい。ＢＥＴ法による比表面積が、０．５～２．０ｍ２／ｇであることで、粘度を所定の範囲に調整することができる。
ＢＥＴ法による比表面積は、例えば「Ｍａｃｓｏｒｂ ＨＭ ｍｏｄｅｌ－１２０８」（ＭＡＣＳＯＲＢ社製）等の比表面積測定機を用いて測定することができる。
比表面積の調整方法は、配合する無機酸化物粉末の粒径、比率を変えることで行うことができる。 The inorganic oxide powder preferably has a BET specific surface area of 0.5 to 2.0 m 2 /g, more preferably 0.8 to 1.8 m 2 /g, and more preferably 1.0 to 1.0 m 2 /g. It is more preferably 1.5 m 2 /g, particularly preferably 1.1 to 1.5 m 2 /g. When the specific surface area by the BET method is 0.5 to 2.0 m 2 /g, the viscosity can be adjusted within a predetermined range.
The specific surface area by the BET method can be measured using a specific surface area measuring instrument such as "Macsorb HM model-1208" (manufactured by MACSORB).
The specific surface area can be adjusted by changing the particle size and ratio of the inorganic oxide powder to be blended.
ＢＥＴ法による比表面積は、例えば「Ｍａｃｓｏｒｂ ＨＭ ｍｏｄｅｌ－１２０８」（ＭＡＣＳＯＲＢ社製）等の比表面積測定機を用いて測定することができる。
比表面積の調整方法は、配合する無機酸化物粉末の粒径、比率を変えることで行うことができる。 The inorganic oxide powder preferably has a BET specific surface area of 0.5 to 2.0 m 2 /g, more preferably 0.8 to 1.8 m 2 /g, and more preferably 1.0 to 1.0 m 2 /g. It is more preferably 1.5 m 2 /g, particularly preferably 1.1 to 1.5 m 2 /g. When the specific surface area by the BET method is 0.5 to 2.0 m 2 /g, the viscosity can be adjusted within a predetermined range.
The specific surface area by the BET method can be measured using a specific surface area measuring instrument such as "Macsorb HM model-1208" (manufactured by MACSORB).
The specific surface area can be adjusted by changing the particle size and ratio of the inorganic oxide powder to be blended.
無機酸化物粉末は、体積基準の頻度粒度分布において、好ましくは粒径が０．０１μｍ以上７０μｍ以下の範囲における累積頻度が、９０％以上であることが好ましく、９５％以上であることがより好ましく、９８％以上であることがさらに好ましい。一実施形態において、無機酸化物粉末は、粒径が０．０１μｍ以上７０μｍ以下の範囲の累積頻度が１００％であり得る。
無機酸化物粉末は、体積基準の頻度粒度分布において、好ましくは粒径が０．０１μｍ以上６０μｍ以下の範囲おける累積頻度が、９０％以上であることが好ましく、９５％以上であることがより好ましく、９８％以上であることがさらに好ましい。一実施形態において、無機酸化物粉末は、粒径が０．０１μｍ以上６０μｍ以下の範囲の累積頻度が１００％であり得る。
無機酸化物粉末は、体積基準の頻度粒度分布において、好ましくは粒径が１μｍ以上５０μｍ以下の範囲における累積頻度が、９０％以上であることが好ましく、９５％以上であることがより好ましく、９８％以上であることがさらに好ましい。一実施形態において、無機酸化物粉末は、粒径が１～５０μｍの範囲の累積頻度が１００％であり得る。 In the volume-based frequency particle size distribution, the inorganic oxide powder preferably has a cumulative frequency of 90% or more, more preferably 95% or more, in a particle size range of 0.01 μm or more and 70 μm or less. , more preferably 98% or more. In one embodiment, the inorganic oxide powder may have a cumulative frequency of 100% with a particle size in the range of 0.01 μm to 70 μm.
In the volume-based frequency particle size distribution, the inorganic oxide powder preferably has a cumulative frequency of 90% or more, more preferably 95% or more, in a particle size range of 0.01 μm or more and 60 μm or less. , more preferably 98% or more. In one embodiment, the inorganic oxide powder may have a cumulative frequency of 100% with a particle size in the range of 0.01 μm to 60 μm.
In the volume-based frequency particle size distribution, the inorganic oxide powder preferably has a cumulative frequency of 90% or more, more preferably 95% or more, in a particle size range of 1 μm or more and 50 μm or less. % or more is more preferable. In one embodiment, the inorganic oxide powder may have a cumulative frequency of 100% in the particle size range of 1-50 μm.
無機酸化物粉末は、体積基準の頻度粒度分布において、好ましくは粒径が０．０１μｍ以上６０μｍ以下の範囲おける累積頻度が、９０％以上であることが好ましく、９５％以上であることがより好ましく、９８％以上であることがさらに好ましい。一実施形態において、無機酸化物粉末は、粒径が０．０１μｍ以上６０μｍ以下の範囲の累積頻度が１００％であり得る。
無機酸化物粉末は、体積基準の頻度粒度分布において、好ましくは粒径が１μｍ以上５０μｍ以下の範囲における累積頻度が、９０％以上であることが好ましく、９５％以上であることがより好ましく、９８％以上であることがさらに好ましい。一実施形態において、無機酸化物粉末は、粒径が１～５０μｍの範囲の累積頻度が１００％であり得る。 In the volume-based frequency particle size distribution, the inorganic oxide powder preferably has a cumulative frequency of 90% or more, more preferably 95% or more, in a particle size range of 0.01 μm or more and 70 μm or less. , more preferably 98% or more. In one embodiment, the inorganic oxide powder may have a cumulative frequency of 100% with a particle size in the range of 0.01 μm to 70 μm.
In the volume-based frequency particle size distribution, the inorganic oxide powder preferably has a cumulative frequency of 90% or more, more preferably 95% or more, in a particle size range of 0.01 μm or more and 60 μm or less. , more preferably 98% or more. In one embodiment, the inorganic oxide powder may have a cumulative frequency of 100% with a particle size in the range of 0.01 μm to 60 μm.
In the volume-based frequency particle size distribution, the inorganic oxide powder preferably has a cumulative frequency of 90% or more, more preferably 95% or more, in a particle size range of 1 μm or more and 50 μm or less. % or more is more preferable. In one embodiment, the inorganic oxide powder may have a cumulative frequency of 100% in the particle size range of 1-50 μm.
無機酸化物粉末は、体積基準累積５０％径Ｄ５０が、樹脂組成物の流動性、粘度の観点から、５～２０μｍであることが好ましく、５～１５μｍであることがより好ましい。体積基準累積５０％径Ｄ５０は、レーザー回折光散乱法（屈折率：１．６８）により測定される体積基準の累積粒度分布において、累積値が５０％に相当する粒子径である。
The inorganic oxide powder preferably has a volume-based cumulative 50 % diameter D50 of 5 to 20 μm, more preferably 5 to 15 μm, from the viewpoint of fluidity and viscosity of the resin composition. The volume-based cumulative 50% diameter D50 is a particle size corresponding to a cumulative value of 50% in a volume-based cumulative particle size distribution measured by a laser diffraction light scattering method (refractive index: 1.68).
無機酸化物粉末の製造は、市販の所定の粒度分布を有する無機酸化物粉末を混合して製造してもよく、既存の溶射技術によって製造してもよい。生産性、生産コストの観点から、溶射技術によることが好ましい。既存の溶射技術は、例えば「製綱窯炉に対する溶射捕集技術について 製鉄研究１９８２第３１０号」を基本とし、水素、メタン、天然ガス、アセチレンガス、プロパンガス、ブタン等の燃料ガスとで形成された高温火炎中に原料粉末を投入し、溶融球状化させることが挙げられる。製造装置の一例は、球状化炉と、その炉に接続された捕集装置とを基本構成としているものである。球状化炉で製造された球状無機酸化物粉末は、ブロワー等にて空気輸送され捕集装置で回収される。球状無機酸化物粉末は、捕集装置による捕集前及び／又は捕集後に、必要に応じて、分級される。球状化炉本体と輸送配管等は水冷ジャケット方式で水冷されていることが好ましい。捕集装置としては、サイクロン、重力沈降、ルーバー、バグフィルター等が用いられる。捕集温度は、可燃ガスの量による発熱量とブロワーの吸引量によって決定され、その調整は冷却水量や、ライン内に設けられた外気の取り入れ量等で行われる。球状アルミナ粉末の製造用原料としては、水酸化アルミニウム、アルミナ、金属アルミニウム等が使用される。
原料粉末はあらかじめ粒度を製品粒度（目的とする無機酸化物粉末と同じ粒度）に調整しておくことが望ましいが、球状化処理後に分級処理して粒度調整を行うこともできる。また、同じ組成を有する球状無機質粉末であっても粒径が異なる数種の原料を分別して溶融球状し、後に混合し調整して得ることもできる。
混合は、例えば、常温の条件下で、既知のブレンダー、ミキサー等の機器を用いて行うことができる。 The inorganic oxide powder may be produced by mixing commercially available inorganic oxide powders having a predetermined particle size distribution, or may be produced by existing thermal spraying techniques. From the viewpoint of productivity and production cost, thermal spraying technology is preferable. Existing thermal spraying technology is based on, for example, "About thermal spraying and collection technology for steel kiln steel research 1982 No. 310", and is formed with fuel gas such as hydrogen, methane, natural gas, acetylene gas, propane gas, and butane. For example, the raw material powder is put into a high-temperature flame that has been heated to be melted and spheroidized. An example of the manufacturing apparatus is basically composed of a spheroidizing furnace and a collection device connected to the furnace. The spherical inorganic oxide powder produced in the spheroidizing furnace is pneumatically transported by a blower or the like and collected by a collection device. The spherical inorganic oxide powder is classified as necessary before and/or after collection by the collection device. It is preferable that the main body of the spheroidizing furnace, the transportation piping, etc. are water-cooled by a water-cooling jacket system. A cyclone, gravity sedimentation, louver, bag filter, or the like is used as a collection device. The collection temperature is determined by the amount of heat generated by the amount of combustible gas and the suction amount of the blower, and is adjusted by the amount of cooling water, the intake amount of outside air provided in the line, and the like. Aluminum hydroxide, alumina, metal aluminum and the like are used as raw materials for producing spherical alumina powder.
It is desirable to adjust the particle size of the raw material powder in advance to the product particle size (the same particle size as the target inorganic oxide powder), but the particle size can be adjusted by classifying after the spheroidizing treatment. Further, even if the spherical inorganic powder has the same composition, several kinds of raw materials with different particle diameters can be separated, melted into spheres, and then mixed and adjusted.
Mixing can be performed, for example, under normal temperature conditions using a known device such as a blender or mixer.
原料粉末はあらかじめ粒度を製品粒度（目的とする無機酸化物粉末と同じ粒度）に調整しておくことが望ましいが、球状化処理後に分級処理して粒度調整を行うこともできる。また、同じ組成を有する球状無機質粉末であっても粒径が異なる数種の原料を分別して溶融球状し、後に混合し調整して得ることもできる。
混合は、例えば、常温の条件下で、既知のブレンダー、ミキサー等の機器を用いて行うことができる。 The inorganic oxide powder may be produced by mixing commercially available inorganic oxide powders having a predetermined particle size distribution, or may be produced by existing thermal spraying techniques. From the viewpoint of productivity and production cost, thermal spraying technology is preferable. Existing thermal spraying technology is based on, for example, "About thermal spraying and collection technology for steel kiln steel research 1982 No. 310", and is formed with fuel gas such as hydrogen, methane, natural gas, acetylene gas, propane gas, and butane. For example, the raw material powder is put into a high-temperature flame that has been heated to be melted and spheroidized. An example of the manufacturing apparatus is basically composed of a spheroidizing furnace and a collection device connected to the furnace. The spherical inorganic oxide powder produced in the spheroidizing furnace is pneumatically transported by a blower or the like and collected by a collection device. The spherical inorganic oxide powder is classified as necessary before and/or after collection by the collection device. It is preferable that the main body of the spheroidizing furnace, the transportation piping, etc. are water-cooled by a water-cooling jacket system. A cyclone, gravity sedimentation, louver, bag filter, or the like is used as a collection device. The collection temperature is determined by the amount of heat generated by the amount of combustible gas and the suction amount of the blower, and is adjusted by the amount of cooling water, the intake amount of outside air provided in the line, and the like. Aluminum hydroxide, alumina, metal aluminum and the like are used as raw materials for producing spherical alumina powder.
It is desirable to adjust the particle size of the raw material powder in advance to the product particle size (the same particle size as the target inorganic oxide powder), but the particle size can be adjusted by classifying after the spheroidizing treatment. Further, even if the spherical inorganic powder has the same composition, several kinds of raw materials with different particle diameters can be separated, melted into spheres, and then mixed and adjusted.
Mixing can be performed, for example, under normal temperature conditions using a known device such as a blender or mixer.
無機酸化物粉末は、シランカップリング剤等の表面処理を行うことによって、粉末の吸水率を低減させ、樹脂組成物の高強度化、更には樹脂と粉末との間の界面抵抗を低下させ、熱伝導率を一段と向上させることができる。
シランカップリング剤としては、ビニルトリクロルシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、β（３，４－エポキシシンクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシリメトキシプロピルメチルジエトキシシラン、Ｎ－β（アミノエチル）γ－アミノプロピルトリメトキシシラン、Ｎ－β（アミノエチル）γ－アミノプロピルメチルジメトキシシラン、γ－アミノプロピルトリエトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－クロロプロピルトリメトキシシラン等、その他表面処理剤として、Ｚｒキレート、チタネートカップリング剤、アルミニウム系カップリング剤等を用いることができる。 The inorganic oxide powder is subjected to surface treatment with a silane coupling agent or the like to reduce the water absorption of the powder, increase the strength of the resin composition, and further reduce the interfacial resistance between the resin and the powder. Thermal conductivity can be further improved.
Silane coupling agents include vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β(3,4-epoxysynchrohexyl)ethyltrimethoxysilane, γ-glycidoxysilane. Propyltrimethoxysilane, γ-glycylimethoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc. Other surface treatment agents such as Zr chelate, titanate coupling agent, aluminum cup A ring agent or the like can be used.
シランカップリング剤としては、ビニルトリクロルシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、β（３，４－エポキシシンクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシリメトキシプロピルメチルジエトキシシラン、Ｎ－β（アミノエチル）γ－アミノプロピルトリメトキシシラン、Ｎ－β（アミノエチル）γ－アミノプロピルメチルジメトキシシラン、γ－アミノプロピルトリエトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－クロロプロピルトリメトキシシラン等、その他表面処理剤として、Ｚｒキレート、チタネートカップリング剤、アルミニウム系カップリング剤等を用いることができる。 The inorganic oxide powder is subjected to surface treatment with a silane coupling agent or the like to reduce the water absorption of the powder, increase the strength of the resin composition, and further reduce the interfacial resistance between the resin and the powder. Thermal conductivity can be further improved.
Silane coupling agents include vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β(3,4-epoxysynchrohexyl)ethyltrimethoxysilane, γ-glycidoxysilane. Propyltrimethoxysilane, γ-glycylimethoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc. Other surface treatment agents such as Zr chelate, titanate coupling agent, aluminum cup A ring agent or the like can be used.
（用途）
無機酸化物粉末は、電子機器用の半導体封止材、接着剤、放熱シート等の製造に好ましく用いることができる。特に、低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物を与えることができるので、圧縮成形品の製造に好ましく用いることができる。 (Application)
Inorganic oxide powders can be preferably used in the production of semiconductor encapsulating materials, adhesives, heat-dissipating sheets, and the like for electronic devices. In particular, since a resin composition having a low ratio of viscosity under low shear to viscosity under high shear can be obtained, it can be preferably used for the production of compression-molded articles.
無機酸化物粉末は、電子機器用の半導体封止材、接着剤、放熱シート等の製造に好ましく用いることができる。特に、低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物を与えることができるので、圧縮成形品の製造に好ましく用いることができる。 (Application)
Inorganic oxide powders can be preferably used in the production of semiconductor encapsulating materials, adhesives, heat-dissipating sheets, and the like for electronic devices. In particular, since a resin composition having a low ratio of viscosity under low shear to viscosity under high shear can be obtained, it can be preferably used for the production of compression-molded articles.
［樹脂組成物］
本実施形態に係る樹脂組成物は、上記した無機酸化物粉末と樹脂とを含む。無機酸化物粉末については、上述のとおりである。
無機酸化物粉末の含有量は、耐熱性、機械強度等の観点から、樹脂組成物中に、好ましくは８０～９５質量％であり、より好ましくは８５～９５質量％であり、さらに好ましくは９０～９５質量％である。一実施形態において、無機酸化物粉末の含有量は、樹脂組成物中に８０質量％を超え９５質量％以下であり得る。 [Resin composition]
The resin composition according to the present embodiment contains the above inorganic oxide powder and resin. The inorganic oxide powder is as described above.
The content of the inorganic oxide powder in the resin composition is preferably 80 to 95% by mass, more preferably 85 to 95% by mass, and still more preferably 90% by mass, from the viewpoint of heat resistance, mechanical strength, etc. ~95% by mass. In one embodiment, the content of the inorganic oxide powder may be more than 80% by mass and 95% by mass or less in the resin composition.
本実施形態に係る樹脂組成物は、上記した無機酸化物粉末と樹脂とを含む。無機酸化物粉末については、上述のとおりである。
無機酸化物粉末の含有量は、耐熱性、機械強度等の観点から、樹脂組成物中に、好ましくは８０～９５質量％であり、より好ましくは８５～９５質量％であり、さらに好ましくは９０～９５質量％である。一実施形態において、無機酸化物粉末の含有量は、樹脂組成物中に８０質量％を超え９５質量％以下であり得る。 [Resin composition]
The resin composition according to the present embodiment contains the above inorganic oxide powder and resin. The inorganic oxide powder is as described above.
The content of the inorganic oxide powder in the resin composition is preferably 80 to 95% by mass, more preferably 85 to 95% by mass, and still more preferably 90% by mass, from the viewpoint of heat resistance, mechanical strength, etc. ~95% by mass. In one embodiment, the content of the inorganic oxide powder may be more than 80% by mass and 95% by mass or less in the resin composition.
樹脂としては、エポキシ樹脂、シリコーン樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル、フッ素樹脂、ポリイミド、ポリアミドイミド、ポリエーテルイミド等のポリアミド、ポリブチレンテレフタレート、ポリエチレンテレフタレート等のポリエステル、ポリフェニレンエーテル、ポリフェニレンスルフィド、全芳香族ポリエステル、ポリスルホン、液晶ポリマー、ポリエーテルスルホン、ポリカーボネート、マレイミド変性樹脂、ＡＢＳ樹脂、ＡＡＳ（アクリロニトリル－アクリルゴム・スチレン）樹脂、ＡＥＳ（アクリロニトリル・エチレン・プロピレン・ジエンゴム－スチレン）樹脂等が挙げられ、これらから選択される１以上を含むことが好ましい。
Resins include epoxy resins, silicone resins, phenolic resins, melamine resins, urea resins, unsaturated polyesters, fluorine resins, polyamides such as polyimides, polyamideimides and polyetherimides, polyesters such as polybutylene terephthalate and polyethylene terephthalate, and polyphenylene ethers. , polyphenylene sulfide, wholly aromatic polyester, polysulfone, liquid crystal polymer, polyethersulfone, polycarbonate, maleimide-modified resin, ABS resin, AAS (acrylonitrile-acrylic rubber-styrene) resin, AES (acrylonitrile-ethylene-propylene-diene rubber-styrene) Examples include resins, and it is preferable to include one or more selected from these.
樹脂組成物が封止用成形材料である場合、樹脂にはエポキシ樹脂が用いられることが好ましい。エポキシ樹脂としては、一分子中にエポキシ基を二個以上有するエポキシ樹脂であればいかなるものでも使用可能である。その具体例をあげれば、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、フェノール類とアルデヒド類のノボラック樹脂をエポキシ化したもの、ビスフェノールＡ、ビスフェノールＦ及びビスフェノールＳなどのグリシジルエーテル、フタル酸やダイマー酸などの多塩基酸とエポクロルヒドリンとの反応により得られるグリシジルエステル酸エポキシ樹脂、線状脂肪族エポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、アルキル変性多官能エポキシ樹脂、β－ナフトールノボラック型エオキシ樹脂、１，６－ジヒドロキシナフタレン型エポキシ樹脂、２，７－ジヒドロキシナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスヒドロキシビフェニル型エポキシ樹脂、更には難燃性を付与するために臭素などのハロゲンを導入したエポキシ樹脂等である。
When the resin composition is a sealing molding material, it is preferable to use an epoxy resin as the resin. Any epoxy resin having two or more epoxy groups in one molecule can be used as the epoxy resin. Specific examples thereof include phenol novolak type epoxy resins, ortho-cresol novolak type epoxy resins, epoxidized novolak resins of phenols and aldehydes, glycidyl ethers such as bisphenol A, bisphenol F and bisphenol S, phthalic acid and the like. Glycidyl ester acid epoxy resins obtained by reacting polybasic acids such as dimer acid with epochlorhydrin, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, alkyl-modified polyfunctional epoxy resins, β-naphthol novolac type epoxy resin, 1,6-dihydroxynaphthalene type epoxy resin, 2,7-dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, bishydroxybiphenyl type epoxy resin, and for imparting flame retardancy Epoxy resin into which halogen such as bromine is introduced.
樹脂の含有量は、好ましくは５～２０質量％であり、より好ましくは５～１５質量％であり、さらに好ましくは５～１０質量％である。
The resin content is preferably 5-20% by mass, more preferably 5-15% by mass, and even more preferably 5-10% by mass.
エポキシ樹脂を含む場合の硬化剤としては、例えば、フェノールアラルキル樹脂；フェノール、クレゾール、キシレノール、レゾルシノール、クロロフェノール、ｔ－ブチルフェノール、ノニルフェノール、イソプロピルフェノール、オクチルフェノール等の群から選ばれた１種又は２種以上の混合物をホルムアルデヒド、パラホルムアルデヒド又はパラキシレンとともに酸化触媒下で反応させて得られるフェノールノボラック型樹脂；ポリパラヒドロキシスチレン樹脂；ビスフェノールＡやビスフェノールＳ等のビスフェノール化合物；ピロガロールやフロログルシノール等の３官能フェノール類；無水マレイン酸、無水フタル酸や無水ピロメリット酸等の酸無水物；メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族アミン等が挙げられる。
硬化剤との反応を促進させるために硬化促進剤を配合することができる。硬化促進剤としては、１，８－ジアザビシクロ（５，４，０）ウンデセン－７，トリフェニルホスフィン、ベンジルジメチルアミン、２－メチルイミダゾール等が挙げられる。 As a curing agent when an epoxy resin is contained, for example, phenol aralkyl resin; Phenol novolac type resin obtained by reacting the above mixture with formaldehyde, paraformaldehyde or paraxylene in the presence of an oxidation catalyst; polyparahydroxystyrene resin; bisphenol compounds such as bisphenol A and bisphenol S; functional phenols; acid anhydrides such as maleic anhydride, phthalic anhydride and pyromellitic anhydride; and aromatic amines such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone.
A curing accelerator can be added to accelerate the reaction with the curing agent. Curing accelerators include 1,8-diazabicyclo(5,4,0)undecene-7, triphenylphosphine, benzyldimethylamine, 2-methylimidazole and the like.
硬化剤との反応を促進させるために硬化促進剤を配合することができる。硬化促進剤としては、１，８－ジアザビシクロ（５，４，０）ウンデセン－７，トリフェニルホスフィン、ベンジルジメチルアミン、２－メチルイミダゾール等が挙げられる。 As a curing agent when an epoxy resin is contained, for example, phenol aralkyl resin; Phenol novolac type resin obtained by reacting the above mixture with formaldehyde, paraformaldehyde or paraxylene in the presence of an oxidation catalyst; polyparahydroxystyrene resin; bisphenol compounds such as bisphenol A and bisphenol S; functional phenols; acid anhydrides such as maleic anhydride, phthalic anhydride and pyromellitic anhydride; and aromatic amines such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone.
A curing accelerator can be added to accelerate the reaction with the curing agent. Curing accelerators include 1,8-diazabicyclo(5,4,0)undecene-7, triphenylphosphine, benzyldimethylamine, 2-methylimidazole and the like.
樹脂組成物には、必要に応じてその他の添加剤を配合することができる。その他の添加剤としては、低応力化剤として、シリコーンゴム、ポリサルファイドゴム、アクリル系ゴム、ブタジエン系ゴム、スチレン系ブロックコポリマーや飽和型エラストマー等のゴム状物質、上述した樹脂以外の、各種熱可塑性樹脂、シリコーン樹脂等の樹脂状物質、更にはエポキシ樹脂やフェノール樹脂の一部又は全部をアミノシリコーン、エポキシシリコーン、アルコキシシリコーンなどで変性した樹脂等、難燃助剤として、Ｓｂ２Ｏ３、Ｓｂ２Ｏ４、Ｓｂ２Ｏ５等、難燃剤として、ハロゲン化エポキシ樹脂やリン化合物等、着色剤として、カーボンブラック、酸化鉄、染料、顔料等が挙げられる。
Other additives can be added to the resin composition as needed. Other additives include rubber-like substances such as silicone rubber, polysulfide rubber, acrylic rubber, butadiene rubber, styrenic block copolymers and saturated elastomers, and various thermoplastics other than the above-mentioned resins. resins, resinous materials such as silicone resins, and resins obtained by partially or entirely modifying epoxy resins and phenolic resins with aminosilicone, epoxysilicone, alkoxysilicone, etc., and flame retardant aids such as Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 and the like; flame retardants such as halogenated epoxy resins and phosphorus compounds; and coloring agents such as carbon black, iron oxide, dyes and pigments.
樹脂組成物は、低せん断時の粘度と高せん断時の粘度との比が小さいので、圧縮成形する場合でも成形性に優れており、半導体チップ等の被加工材（ワーク）を隙間なく封止することができる。
Since the resin composition has a small ratio of viscosity at low shear and high shear, it has excellent moldability even when compression molding is performed, and it can seal workpieces such as semiconductor chips without gaps. can do.
樹脂組成物は、低せん断時の粘度として、Ｅ型粘度計を用い、温度３０℃、１ｒｐｍの回転数により測定した粘度が４５～７０Ｐａ・ｓであることが好ましく、４５～６５Ｐａ・ｓであることがより好ましい。低せん断時の粘度を４５～７０Ｐａ・ｓにすることで、コンプレッションモールド（圧縮成形）法において、樹脂組成物にワークを押し当て始めの段階で粘度が低く保たれるので、ワイヤー変形への影響が少なく、成形性に優れている。
The viscosity of the resin composition at low shear is preferably 45 to 70 Pa s, preferably 45 to 65 Pa s, measured at a temperature of 30 ° C. and a rotation speed of 1 rpm using an E-type viscometer. is more preferable. By setting the viscosity at low shear to 45 to 70 Pa s, in the compression mold (compression molding) method, the viscosity is kept low at the beginning of pressing the work against the resin composition, so the effect on wire deformation less, and has excellent moldability.
樹脂組成物は、高せん断時の粘度として、Ｅ型粘度計を用い、温度３０℃、１０ｒｐｍの回転数により測定した粘度が３５～５５Ｐａ・ｓであることが好ましく、４０～５５Ｐａ・ｓであることがより好ましい。高せん断時の粘度を３５～５５Ｐａ・ｓにすることで、コンプレッションモールド（圧縮成形）法における高せん断時の粘度が低く保たれるので、成形性に優れている。
The viscosity of the resin composition under high shear is preferably 35 to 55 Pa s, preferably 40 to 55 Pa s, measured at a temperature of 30° C. and a rotation speed of 10 rpm using an E-type viscometer. is more preferable. By setting the viscosity at high shear to 35 to 55 Pa·s, the viscosity at high shear in compression molding (compression molding) is kept low, resulting in excellent moldability.
樹脂組成物は、上記した低せん断時の粘度と高せん断時の粘度との比の値（低せん断時の粘度／高せん断時の粘度）が、１．５未満であることが好ましく、１．４以下であることがより好ましく、１．３以下であることがさらに好ましい。低せん断時の粘度と高せん断時の粘度との比の値が１．５未満である場合は、コンプレッションモールド（圧縮成形）法において、樹脂組成物にワークを押し当てる際に初めから終わりまで粘度が低く保たれるので、成形性に優れている。
The resin composition preferably has a ratio of viscosity at low shear to viscosity at high shear (viscosity at low shear/viscosity at high shear) of less than 1.5. It is more preferably 4 or less, and even more preferably 1.3 or less. If the value of the ratio of the viscosity at low shear and the viscosity at high shear is less than 1.5, in the compression molding method, the viscosity from the beginning to the end when pressing the work against the resin composition is kept low, so it is excellent in moldability.
樹脂組成物の製造は、上記各材料の所定量を撹拌、溶解、混合、分散させることにより行うことができる。これらの混合物の混合、撹拌、分散等の装置としては、撹拌、加熱装置を備えたライカイ機、３本ロール、ボールミル、プラネタリーミキサー等を用いることができる。またこれらの装置を適宜組み合わせて使用してもよい。
The production of the resin composition can be carried out by stirring, dissolving, mixing, and dispersing predetermined amounts of each of the above materials. As a device for mixing, stirring and dispersing these mixtures, a laikai machine equipped with a stirring and heating device, a three-roll mill, a ball mill, a planetary mixer and the like can be used. Moreover, you may use these apparatuses in combination suitably.
（用途）
樹脂組成物は、電子機器用の半導体封止材、接着剤、放熱シート等の製造に好ましく用いることができる。特に、低せん断時の粘度と高せん断時の粘度との比が小さいので、圧縮成形品の製造に好ましく用いることができる。 (Application)
The resin composition can be preferably used for producing semiconductor encapsulating materials, adhesives, heat-dissipating sheets, and the like for electronic devices. In particular, since the ratio of the viscosity at low shear to the viscosity at high shear is small, it can be preferably used for the production of compression molded articles.
樹脂組成物は、電子機器用の半導体封止材、接着剤、放熱シート等の製造に好ましく用いることができる。特に、低せん断時の粘度と高せん断時の粘度との比が小さいので、圧縮成形品の製造に好ましく用いることができる。 (Application)
The resin composition can be preferably used for producing semiconductor encapsulating materials, adhesives, heat-dissipating sheets, and the like for electronic devices. In particular, since the ratio of the viscosity at low shear to the viscosity at high shear is small, it can be preferably used for the production of compression molded articles.
［圧縮成形品］
本実施形態に係る圧縮成形品は、上記した樹脂組成物を含む。圧縮成形品の製造方法は、公知のコンプレッションモールド法を用いることができる。例えば、圧縮成型機を用いて、温度１８０℃、圧力８ＭＰａの条件下で、加熱硬化させることにより樹脂組成物を圧縮成形して製造することができる。 [Compression molded product]
A compression-molded article according to the present embodiment includes the resin composition described above. A known compression molding method can be used as a method for manufacturing the compression-molded product. For example, using a compression molding machine, the resin composition can be produced by compression molding by heat curing under conditions of a temperature of 180° C. and a pressure of 8 MPa.
本実施形態に係る圧縮成形品は、上記した樹脂組成物を含む。圧縮成形品の製造方法は、公知のコンプレッションモールド法を用いることができる。例えば、圧縮成型機を用いて、温度１８０℃、圧力８ＭＰａの条件下で、加熱硬化させることにより樹脂組成物を圧縮成形して製造することができる。 [Compression molded product]
A compression-molded article according to the present embodiment includes the resin composition described above. A known compression molding method can be used as a method for manufacturing the compression-molded product. For example, using a compression molding machine, the resin composition can be produced by compression molding by heat curing under conditions of a temperature of 180° C. and a pressure of 8 MPa.
圧縮成形品は、低せん断時の粘度と高せん断時の粘度との比が小さい樹脂組成物を含むので、半導体チップ等の被加工材を隙間なく、ボイドが極めて少なく封止することができる等の特性を有している。そのため、圧縮成形品は、電子機器用の半導体封止材、接着性部材、放熱シート等として好ましく用いることができる。
Since the compression-molded product contains a resin composition having a small ratio of the viscosity at low shear and the viscosity at high shear, it is possible to seal workpieces such as semiconductor chips without gaps and with extremely few voids. has the characteristics of Therefore, the compression-molded product can be preferably used as a semiconductor encapsulant, an adhesive member, a heat dissipation sheet, and the like for electronic devices.
以下に実施例を示して本発明を更に具体的に説明するが、これらの実施例により本発明の解釈が限定されるものではない。
Although the present invention will be described more specifically by showing examples below, the interpretation of the present invention is not limited by these examples.
［実施例１～６、比較例１～６］
平均粒径（Ｄ５０）が２～４５μｍの範囲に極大値を有するアルミナ原料粉末を、燃料ガスとしてＬＰＧ、助燃ガスとして、酸素を用いて形成された高温火炎中に投入し、溶融球状化させることによって無機酸化物粉末（球状アルミナ粉末）を作製した。
各粒度領域の累積頻度は、原料粉末の配合量を調整することや、篩分けや分級等で行うことで、表１に記載の値に調整した。 [Examples 1 to 6, Comparative Examples 1 to 6]
Alumina raw material powder having an average particle size (D 50 ) having a maximum value in the range of 2 to 45 μm is introduced into a high-temperature flame formed by using LPG as a fuel gas and oxygen as a combustion support gas, and is melted and spheroidized. Inorganic oxide powder (spherical alumina powder) was thus produced.
The cumulative frequency of each particle size range was adjusted to the value shown in Table 1 by adjusting the blending amount of the raw material powder, sieving, classification, and the like.
平均粒径（Ｄ５０）が２～４５μｍの範囲に極大値を有するアルミナ原料粉末を、燃料ガスとしてＬＰＧ、助燃ガスとして、酸素を用いて形成された高温火炎中に投入し、溶融球状化させることによって無機酸化物粉末（球状アルミナ粉末）を作製した。
各粒度領域の累積頻度は、原料粉末の配合量を調整することや、篩分けや分級等で行うことで、表１に記載の値に調整した。 [Examples 1 to 6, Comparative Examples 1 to 6]
Alumina raw material powder having an average particle size (D 50 ) having a maximum value in the range of 2 to 45 μm is introduced into a high-temperature flame formed by using LPG as a fuel gas and oxygen as a combustion support gas, and is melted and spheroidized. Inorganic oxide powder (spherical alumina powder) was thus produced.
The cumulative frequency of each particle size range was adjusted to the value shown in Table 1 by adjusting the blending amount of the raw material powder, sieving, classification, and the like.
（頻度粒度分布）
得られた無機酸化物粉末について、粒度分布測定機（ベックマン・コールター株式会社製、「ＬＳ－１３２３０」）を用いて、屈折率１．６８及び測定溶媒として、水を用い、前処理条件として、６０秒間、超音波ホモジナイザー２００Ｗの条件で、レーザー回折光散乱法による体積基準の頻度粒度分布を測定した。
得られた頻度粒度分布から、第１領域～第３領域の各領域における累積頻度を求めた。また、第１領域の累積頻度に対する第２領域の累積頻度の比の値、及び、第１領域の累積頻度に対する第３領域の累積頻度の比の値をそれぞれ算出した。結果を表１に示す。なお、実施例及び比較例のいずれも粒径が０．０１μｍ以上７０μｍ以下の範囲の累積頻度が９０％以上であった。 (Frequency particle size distribution)
For the obtained inorganic oxide powder, using a particle size distribution analyzer (manufactured by Beckman Coulter Co., Ltd., "LS-13230"), using water as a refractive index of 1.68 and a measurement solvent, as pretreatment conditions, A volume-based frequency particle size distribution was measured by a laser diffraction light scattering method for 60 seconds under the condition of an ultrasonic homogenizer of 200 W.
From the obtained frequency particle size distribution, the cumulative frequency in each region of the first region to the third region was determined. Also, the value of the ratio of the cumulative frequency of the second region to the cumulative frequency of the first region and the value of the ratio of the cumulative frequency of the third region to the cumulative frequency of the first region were calculated. Table 1 shows the results. In addition, in both the examples and the comparative examples, the cumulative frequency of particles having a particle size in the range of 0.01 μm or more and 70 μm or less was 90% or more.
得られた無機酸化物粉末について、粒度分布測定機（ベックマン・コールター株式会社製、「ＬＳ－１３２３０」）を用いて、屈折率１．６８及び測定溶媒として、水を用い、前処理条件として、６０秒間、超音波ホモジナイザー２００Ｗの条件で、レーザー回折光散乱法による体積基準の頻度粒度分布を測定した。
得られた頻度粒度分布から、第１領域～第３領域の各領域における累積頻度を求めた。また、第１領域の累積頻度に対する第２領域の累積頻度の比の値、及び、第１領域の累積頻度に対する第３領域の累積頻度の比の値をそれぞれ算出した。結果を表１に示す。なお、実施例及び比較例のいずれも粒径が０．０１μｍ以上７０μｍ以下の範囲の累積頻度が９０％以上であった。 (Frequency particle size distribution)
For the obtained inorganic oxide powder, using a particle size distribution analyzer (manufactured by Beckman Coulter Co., Ltd., "LS-13230"), using water as a refractive index of 1.68 and a measurement solvent, as pretreatment conditions, A volume-based frequency particle size distribution was measured by a laser diffraction light scattering method for 60 seconds under the condition of an ultrasonic homogenizer of 200 W.
From the obtained frequency particle size distribution, the cumulative frequency in each region of the first region to the third region was determined. Also, the value of the ratio of the cumulative frequency of the second region to the cumulative frequency of the first region and the value of the ratio of the cumulative frequency of the third region to the cumulative frequency of the first region were calculated. Table 1 shows the results. In addition, in both the examples and the comparative examples, the cumulative frequency of particles having a particle size in the range of 0.01 μm or more and 70 μm or less was 90% or more.
（比表面積）
得られた無機酸化物粉末を１．０ｇ計量し、測定用のセルに投入、前処理後、ＢＥＴ比表面積値を測定した。結果を表１に示す。測定機はＭＡＣＳＯＲＢ社製「Ｍａｃｓｏｒｂ ＨＭ ｍｏｄｅｌ－１２０８」を使用した。以下に前処理条件を示す。
脱気温度：３００℃
脱気時間：１８分
冷却時間：４分 (Specific surface area)
1.0 g of the obtained inorganic oxide powder was weighed, put into a measurement cell, and after pretreatment, the BET specific surface area value was measured. Table 1 shows the results. As a measuring machine, "Macsorb HM model-1208" manufactured by MACSORB was used. The pretreatment conditions are shown below.
Deaeration temperature: 300°C
Degassing time: 18 minutes Cooling time: 4 minutes
得られた無機酸化物粉末を１．０ｇ計量し、測定用のセルに投入、前処理後、ＢＥＴ比表面積値を測定した。結果を表１に示す。測定機はＭＡＣＳＯＲＢ社製「Ｍａｃｓｏｒｂ ＨＭ ｍｏｄｅｌ－１２０８」を使用した。以下に前処理条件を示す。
脱気温度：３００℃
脱気時間：１８分
冷却時間：４分 (Specific surface area)
1.0 g of the obtained inorganic oxide powder was weighed, put into a measurement cell, and after pretreatment, the BET specific surface area value was measured. Table 1 shows the results. As a measuring machine, "Macsorb HM model-1208" manufactured by MACSORB was used. The pretreatment conditions are shown below.
Deaeration temperature: 300°C
Degassing time: 18 minutes Cooling time: 4 minutes
次いで、得られた各無機酸化物粉末を以下の材料と、以下の配合量で、ヘンシェルミキサ（日本コークス工業社製「ＦＭ－２０Ｃ／Ｉ」）を用いて、常温、回転数２０００ｒｐｍの条件下で混合し、樹脂組成物を得た。作製した上記の球状アルミナ粉末９０質量部と、ビフェニル型エポキシ樹脂（ジャパンエポキシレジン株式会社製ＹＸ－４０００ＨＫ）５．５質量部と、フェノール樹脂（フェノールアラルキル樹脂、明和化成株式会社製ＭＥＨＣ－７８００Ｓ）４．８質量部と、トリフェニルホスフィン（北興化学工業株式会社製：ＴＰＰ）０．１５質量部と、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン信越化学工業株式会社製：ＫＢＭ－５７３）０．３５質量部とをドライブレンドした。その後、同方向噛み合い二軸押出混練機（スクリュー径Ｄ＝２５ｍｍ、Ｌ／Ｄ＝１０．２、パドル回転数５０～１２０ｒｐｍ、吐出量３．０ｋｇ／Ｈｒ、混練物温度９８～１００℃）で加熱混練し、樹脂組成物を得た。
Next, each of the obtained inorganic oxide powders was mixed with the following materials in the following amounts using a Henschel mixer ("FM-20C/I" manufactured by Nippon Coke Kogyo Co., Ltd.) at room temperature and a rotation speed of 2000 rpm. to obtain a resin composition. 90 parts by mass of the spherical alumina powder prepared above, 5.5 parts by mass of biphenyl type epoxy resin (YX-4000HK manufactured by Japan Epoxy Resin Co., Ltd.), and phenol resin (phenol aralkyl resin, MEHC-7800S manufactured by Meiwa Kasei Co., Ltd.) 4.8 parts by mass, triphenylphosphine (manufactured by Hokko Chemical Co., Ltd.: TPP) 0.15 parts by mass, and N-phenyl-3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-573) 0 .35 parts by weight were dry blended. After that, heat with a co-meshing twin-screw extruder kneader (screw diameter D = 25 mm, L/D = 10.2, paddle rotation speed 50-120 rpm, discharge rate 3.0 kg/Hr, kneaded material temperature 98-100°C). The mixture was kneaded to obtain a resin composition.
（流動性）
得られた各樹脂組成物について、以下に示す方法で流動性を測定した。結果を表１に示す。
スパイラルフロー金型を用い、ＥＭＭＩ－１－６６（Ｅｐｏｘｙ Ｍｏｌｄｉｎｇ Ｍａｔｅｒｉａｌ Ｉｎｓｔｉｔｕｔｅ；Ｓｏｃｉｅｔｙ ｏｆ Ｐｌａｓｔｉｃ Ｉｎｄｕｓｔｒｙ）に準拠して行った。金型温度は１７５℃、成型圧力７．４ＭＰａ、保圧時間９０秒とした。２００ｃｍ以上であるものを○（優）として、２００ｃｍ未満であるものと不良（×）として評価した。 (Liquidity)
The fluidity of each resin composition obtained was measured by the method described below. Table 1 shows the results.
Using a spiral flow mold, it was carried out in accordance with EMMI-1-66 (Epoxy Molding Material Institute; Society of Plastic Industry). The mold temperature was 175° C., the molding pressure was 7.4 MPa, and the pressure holding time was 90 seconds. Those having a length of 200 cm or more were evaluated as ◯ (excellent), and those having a length of less than 200 cm were evaluated as poor (×).
得られた各樹脂組成物について、以下に示す方法で流動性を測定した。結果を表１に示す。
スパイラルフロー金型を用い、ＥＭＭＩ－１－６６（Ｅｐｏｘｙ Ｍｏｌｄｉｎｇ Ｍａｔｅｒｉａｌ Ｉｎｓｔｉｔｕｔｅ；Ｓｏｃｉｅｔｙ ｏｆ Ｐｌａｓｔｉｃ Ｉｎｄｕｓｔｒｙ）に準拠して行った。金型温度は１７５℃、成型圧力７．４ＭＰａ、保圧時間９０秒とした。２００ｃｍ以上であるものを○（優）として、２００ｃｍ未満であるものと不良（×）として評価した。 (Liquidity)
The fluidity of each resin composition obtained was measured by the method described below. Table 1 shows the results.
Using a spiral flow mold, it was carried out in accordance with EMMI-1-66 (Epoxy Molding Material Institute; Society of Plastic Industry). The mold temperature was 175° C., the molding pressure was 7.4 MPa, and the pressure holding time was 90 seconds. Those having a length of 200 cm or more were evaluated as ◯ (excellent), and those having a length of less than 200 cm were evaluated as poor (×).
（粘度）
得られた無機酸化物粉末について、以下に示す方法でエポキシ樹脂に配合した際の粘度（低せん断時及び高せん断時）を測定した。得られた値を用いて低せん断時の粘度と高せん断時の粘度との比の値を算出した。結果を表１に示す。
ビスフェノールＦ型であるエポキシ樹脂（三菱化学社製：エピコート８０７、エポキシ当量１７０、粘度４Ｐａ・ｓ）２０質量％と作製した上記の球状アルミナ粉末８０質量％とからなる樹脂組成物を作製し、低せん断時の粘度として、Ｅ型粘度計（東機産業社製商品名「ＴＶＥ－１０」）を用い、温度３０℃、１ｒｐｍの回転数により樹脂組成物の粘度測定を行った。高せん断時の粘度として、Ｅ型粘度計（東機産業社製商品名「ＴＶＥ－１０」）を用い、温度３０℃、１０ｒｐｍの回転数により樹脂組成物の粘度測定を行った。 (viscosity)
The resulting inorganic oxide powder was measured for viscosity (at low shear and at high shear) when blended with an epoxy resin by the method described below. Using the obtained values, the value of the ratio of the viscosity at low shear to the viscosity at high shear was calculated. Table 1 shows the results.
A resin composition comprising 20% by mass of a bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: Epicoat 807, epoxy equivalent 170, viscosity 4 Pa s) and 80% by mass of the spherical alumina powder prepared above was prepared. As the viscosity during shearing, the viscosity of the resin composition was measured using an E-type viscometer (trade name “TVE-10” manufactured by Toki Sangyo Co., Ltd.) at a temperature of 30° C. and a rotation speed of 1 rpm. The viscosity of the resin composition under high shear was measured using an E-type viscometer (trade name "TVE-10" manufactured by Toki Sangyo Co., Ltd.) at a temperature of 30° C. and a rotation speed of 10 rpm.
得られた無機酸化物粉末について、以下に示す方法でエポキシ樹脂に配合した際の粘度（低せん断時及び高せん断時）を測定した。得られた値を用いて低せん断時の粘度と高せん断時の粘度との比の値を算出した。結果を表１に示す。
ビスフェノールＦ型であるエポキシ樹脂（三菱化学社製：エピコート８０７、エポキシ当量１７０、粘度４Ｐａ・ｓ）２０質量％と作製した上記の球状アルミナ粉末８０質量％とからなる樹脂組成物を作製し、低せん断時の粘度として、Ｅ型粘度計（東機産業社製商品名「ＴＶＥ－１０」）を用い、温度３０℃、１ｒｐｍの回転数により樹脂組成物の粘度測定を行った。高せん断時の粘度として、Ｅ型粘度計（東機産業社製商品名「ＴＶＥ－１０」）を用い、温度３０℃、１０ｒｐｍの回転数により樹脂組成物の粘度測定を行った。 (viscosity)
The resulting inorganic oxide powder was measured for viscosity (at low shear and at high shear) when blended with an epoxy resin by the method described below. Using the obtained values, the value of the ratio of the viscosity at low shear to the viscosity at high shear was calculated. Table 1 shows the results.
A resin composition comprising 20% by mass of a bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: Epicoat 807, epoxy equivalent 170, viscosity 4 Pa s) and 80% by mass of the spherical alumina powder prepared above was prepared. As the viscosity during shearing, the viscosity of the resin composition was measured using an E-type viscometer (trade name “TVE-10” manufactured by Toki Sangyo Co., Ltd.) at a temperature of 30° C. and a rotation speed of 1 rpm. The viscosity of the resin composition under high shear was measured using an E-type viscometer (trade name "TVE-10" manufactured by Toki Sangyo Co., Ltd.) at a temperature of 30° C. and a rotation speed of 10 rpm.
表１に示すように、実施例で得られた無機酸化物粉末（球状アルミナ粉末）を含む樹脂組成物は、低せん断時の粘度と高せん断時の粘度との比が１．５未満であり、低せん断時の粘度と高せん断時の粘度との比が小さい。そのため、コンプレッションモールド法において樹脂組成物にワークを押し当てる際に初めから終わりまで粘度が低く保たれる。その結果、優れた成形性で圧縮成形品を製造することができる。
As shown in Table 1, the resin compositions containing the inorganic oxide powder (spherical alumina powder) obtained in Examples had a ratio of viscosity at low shear to viscosity at high shear of less than 1.5. , the ratio of low-shear viscosity to high-shear viscosity is small. Therefore, the viscosity is kept low from the beginning to the end when the work is pressed against the resin composition in the compression molding method. As a result, a compression-molded article can be produced with excellent moldability.
Claims (6)
- 体積基準の頻度粒度分布において、粒径が０．００１μｍ以上１０μｍ以下の範囲に位置する第１領域の累積頻度に対する、粒径が０．００１μｍ以上２０μｍ以下の範囲に位置する第２領域の累積頻度の比の値（第２領域の累積頻度／第１領域の累積頻度）が１．２～１．４であり、
粒径が０．００１μｍ以上１０μｍ以下の範囲に位置する第１領域の累積頻度に対する、粒径が０．００１μｍ以上３５μｍ以下の範囲に位置する第３領域の累積頻度の比の値（第３領域の累積頻度／第１領域の累積頻度）が１．４～２．２であり、
前記第３領域の累積頻度が、７０～９５体積％である、無機酸化物粉末。 In the volume-based frequency particle size distribution, the cumulative frequency of the second region in which the particle size is in the range of 0.001 μm to 20 μm with respect to the cumulative frequency of the first region in which the particle size is in the range of 0.001 μm to 10 μm The value of the ratio (cumulative frequency of the second region / cumulative frequency of the first region) is 1.2 to 1.4,
The value of the ratio of the cumulative frequency of the third region located in the range of 0.001 μm to 35 μm in particle size to the cumulative frequency of the first region located in the range of 0.001 μm to 10 μm in particle size (third region Cumulative frequency of / Cumulative frequency of the first region) is 1.4 to 2.2,
The inorganic oxide powder, wherein the cumulative frequency of the third region is 70 to 95% by volume. - ＢＥＴ法による比表面積が、０．５～２．０ｍ２／ｇである、請求項１に記載の無機酸化物粉末。 2. The inorganic oxide powder according to claim 1, having a BET specific surface area of 0.5 to 2.0 m 2 /g.
- 粒径が０．０１μｍ以上７０μｍ以下の範囲の累積頻度が９０体積％以上である、請求項１又は２に記載の無機酸化物粉末。 The inorganic oxide powder according to claim 1 or 2, wherein the cumulative frequency of particle sizes in the range of 0.01 µm to 70 µm is 90% by volume or more.
- 請求項１から３のいずれか一項に記載の無機酸化物粉末と樹脂とを含む、樹脂組成物。 A resin composition comprising the inorganic oxide powder according to any one of claims 1 to 3 and a resin.
- 圧縮成形品の製造に用いられる、請求項４に記載の樹脂組成物。 The resin composition according to claim 4, which is used for manufacturing compression molded products.
- 請求項４又は５に記載の樹脂組成物を含む、圧縮成形品。 A compression-molded article containing the resin composition according to claim 4 or 5.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07278415A (en) * | 1994-04-13 | 1995-10-24 | Shin Etsu Chem Co Ltd | Resin composition for semiconductor sealing and semiconductor device sealed therewith |
| JPH09194242A (en) * | 1996-01-16 | 1997-07-29 | Denki Kagaku Kogyo Kk | Alumina cement and monolithic refractory using the same |
| JPH09210570A (en) * | 1995-11-30 | 1997-08-12 | Kawasaki Steel Corp | Flame injection method |
| JP2001064522A (en) * | 1999-08-27 | 2001-03-13 | Toray Ind Inc | Semiconductor sealing resin composition |
| JP2002128520A (en) * | 2000-10-20 | 2002-05-09 | Shiraishi Chuo Kenkyusho:Kk | Spherical calcium aluminate and method of manufacturing it |
| JP2003003074A (en) * | 2001-06-20 | 2003-01-08 | Mitsui Chemicals Inc | Silica-containing resin composition and its precision molding |
| JP2005089293A (en) * | 2003-08-13 | 2005-04-07 | Sakai Chem Ind Co Ltd | Method for producing perovskite compound powder |
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- 2022-03-17 WO PCT/JP2022/012146 patent/WO2022202583A1/en active Application Filing
- 2022-03-17 JP JP2023509089A patent/JPWO2022202583A1/ja active Pending
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07278415A (en) * | 1994-04-13 | 1995-10-24 | Shin Etsu Chem Co Ltd | Resin composition for semiconductor sealing and semiconductor device sealed therewith |
| JPH09210570A (en) * | 1995-11-30 | 1997-08-12 | Kawasaki Steel Corp | Flame injection method |
| JPH09194242A (en) * | 1996-01-16 | 1997-07-29 | Denki Kagaku Kogyo Kk | Alumina cement and monolithic refractory using the same |
| JP2001064522A (en) * | 1999-08-27 | 2001-03-13 | Toray Ind Inc | Semiconductor sealing resin composition |
| JP2002128520A (en) * | 2000-10-20 | 2002-05-09 | Shiraishi Chuo Kenkyusho:Kk | Spherical calcium aluminate and method of manufacturing it |
| JP2003003074A (en) * | 2001-06-20 | 2003-01-08 | Mitsui Chemicals Inc | Silica-containing resin composition and its precision molding |
| JP2005089293A (en) * | 2003-08-13 | 2005-04-07 | Sakai Chem Ind Co Ltd | Method for producing perovskite compound powder |
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