JP2002038049A - Silica-based fine particles and method for producing the same - Google Patents
Silica-based fine particles and method for producing the sameInfo
- Publication number
- JP2002038049A JP2002038049A JP2000228365A JP2000228365A JP2002038049A JP 2002038049 A JP2002038049 A JP 2002038049A JP 2000228365 A JP2000228365 A JP 2000228365A JP 2000228365 A JP2000228365 A JP 2000228365A JP 2002038049 A JP2002038049 A JP 2002038049A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- silica
- based fine
- carbon atoms
- fine particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000010419 fine particle Substances 0.000 title claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 174
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- 238000004381 surface treatment Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 33
- 239000002585 base Substances 0.000 description 29
- -1 polyoxyethylene Polymers 0.000 description 29
- 239000007788 liquid Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 21
- 239000002736 nonionic surfactant Substances 0.000 description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 101100124417 Arabidopsis thaliana HLB1 gene Proteins 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 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
- 150000002170 ethers Chemical class 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Silicon Polymers (AREA)
Abstract
(57)【要約】
【課題】 母体粒子全面にわたって、突起物が化学結合
により強固に結着してなり、例えば樹脂用充填材や表面
に導電層を被覆した導電性粒子の母材などとして好適な
シリカ系微粒子、およびその製造方法を提供する。
【解決手段】 母体粒子全面に、実質上球状および／ま
たは半球状の突起物を有するシリカ系微粒子であって、
該突起物が化学結合により母体粒子に結着してなるシリ
カ系微粒子、及び（Ａ）特定のアルコキシシラン化合物
を加水分解、縮合させてポリオルガノシロキサン粒子を
生成させる工程、（Ｂ）該ポリオルガノシロキサン粒子
を、表面吸着剤により表面処理する工程、および（Ｃ）
上記（Ｂ）工程で表面処理されたポリオルガノシロキサ
ン粒子全面に、該アルコキシシラン化合物を用いて突起
を形成させる工程、を含むシリカ系微粒子の製造方法で
ある。PROBLEM TO BE SOLVED: To provide a protrusion firmly bonded by chemical bonding over the entire surface of a base particle, and suitable as, for example, a resin filler or a base material of a conductive particle having a surface coated with a conductive layer. And a method for producing the same. SOLUTION: Silica-based fine particles having substantially spherical and / or hemispherical projections on the entire surface of a base particle,
A step of (A) hydrolyzing and condensing a specific alkoxysilane compound to form polyorganosiloxane particles, and (B) a step of forming the polyorganosiloxane. A step of subjecting the siloxane particles to a surface treatment with a surface adsorbent, and (C)
A method for producing silica-based fine particles, comprising the step of forming projections using the alkoxysilane compound on the entire surface of the polyorganosiloxane particles surface-treated in the step (B).
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、シリカ系微粒子お
よびその製造方法に関する。さらに詳しくは、本発明
は、母体粒子全面に、ほぼ球状や半球状の突起物が化学
結合により強固に結着したものであって、例えば樹脂用
充填材や表面に導電層を被覆した導電性粒子の母材など
として好適なシリカ系微粒子、およびこのものを効率よ
く製造する方法に関するものである。The present invention relates to silica-based fine particles and a method for producing the same. More specifically, the present invention relates to a conductive material in which substantially spherical or hemispherical projections are firmly bound by chemical bonding over the entire surface of the base particles, for example, a resin filler or a conductive layer coated on the surface. The present invention relates to a silica-based fine particle suitable as a base material of the particle and a method for efficiently producing the fine particle.
【０００２】[0002]
【従来の技術】従来、半導体樹脂封止剤やラジアルタイ
ヤなどにおいては、性能を向上させる目的で、各種フィ
ラーが混入されている。このフィラーとしては、無機系
粒子やガラスファイバーが主に用いられている。フィラ
ーが球状粒子である場合と金平糖状粒子である場合、こ
れらが半導体樹脂封止剤やラジアルタイヤなどの充填材
として用いられた際、樹脂組成物やゴム組成物との密着
性、あるいは熱膨張係数差に起因するクラック発生の防
止効果などの点で、後者の方が優れている。2. Description of the Related Art Conventionally, various fillers have been mixed in semiconductor resin sealants and radial tires for the purpose of improving performance. As the filler, inorganic particles and glass fibers are mainly used. When the fillers are spherical particles and spinous particles, when these are used as fillers for semiconductor resin sealants or radial tires, the adhesion to the resin composition or rubber composition, or thermal expansion The latter is superior in terms of the effect of preventing the occurrence of cracks due to the coefficient difference.
【０００３】従来、金平糖状粒子の製造に関しては、例
えば、（１）分散重合法によって得た分散重合粒子の存
在下で、単量体を重合させることにより、該分散重合粒
子の表面に微小重合体粒子を付着させてなる表面に凹凸
を有する樹脂粒子（特開平５−３３１２１６号公報）、
（２）母粒子の表面に、子粒子を接着剤を用いて付着さ
せるか、直接融着させて、表面に突起物をもつ微粒子を
作製する方法、あるいは母粒子を回転する容器に入れ
て、該粒子表面に子粒子の溶液を付着させ、容器を回転
させながら溶媒を蒸発させることにより、母粒子表面に
溶質を角状に析出させて、突起物をもつ微粒子を作製す
る方法（特開平４−３６９０２号公報）、（３）溶融球
状シリカ粒子と、該シリカ粒子よりも微細な破砕状シリ
カ粒子とを高速回転気流中に投入処理し、粒子表面に突
起物を有する粒子を作製する方法（特開平３−２５９９
６０号公報）などが開示されている。Conventionally, regarding the production of spinous particles, for example, (1) the polymerization of a monomer in the presence of the dispersion-polymerized particles obtained by the dispersion polymerization method causes a minute weight on the surface of the dispersion-polymerized particles. Resin particles having irregularities on the surface obtained by adhering the coalesced particles (JP-A-5-331216);
(2) A method in which child particles are adhered to the surface of base particles using an adhesive or directly fused to produce fine particles having protrusions on the surface, or the base particles are placed in a rotating container, A method of producing fine particles having protrusions by depositing a solution of the child particles on the surface of the particles and evaporating the solvent while rotating the container, thereby precipitating solutes on the surface of the base particles in a square shape (Japanese Patent Laid-Open No. No. 36902) and (3) a method in which molten spherical silica particles and crushed silica particles finer than the silica particles are charged into a high-speed rotating airflow to produce particles having projections on the particle surface ( JP-A-3-2599
No. 60) is disclosed.
【０００４】しかしながら、前記（１）の表面に凹凸を
有する樹脂粒子は、粒子自体または突起物の剪断強度や
破壊強度に乏しいという欠点を有しており、一方、
（２）および（３）の方法により得られた表面に突起物
を有する粒子は、物理的な接着や融着により母体粒子と
突起物とが接合しているため、突起物の剪断強度や破壊
強度に乏しいという欠点を有している。また、前記
（３）の方法においては、高速回転気流下で処理が行わ
れるため、粒子自体の耐熱性や耐圧性が必要となるなど
の問題もある。このような金平糖状粒子を充填材として
用いた場合、母体粒子表面と突起物との結合強度の差に
より、得られる製品自体の破壊強度などの機械的強度に
差が生じる。[0004] However, the resin particles having irregularities on the surface of the above (1) have a drawback that the particles themselves or projections have poor shear strength and breaking strength.
In the particles having projections on the surface obtained by the methods (2) and (3), the base particles and the projections are joined by physical adhesion or fusion, so that the projections have a shear strength or fracture. It has the disadvantage of poor strength. In addition, in the method (3), since the treatment is performed under a high-speed rotating airflow, there is a problem that heat resistance and pressure resistance of the particles themselves are required. When such spinous particles are used as a filler, a difference in mechanical strength such as a breaking strength of the obtained product itself occurs due to a difference in bonding strength between the base particle surface and the projection.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、母体粒子全面にわたって、突起物が化学
結合により強固に結着してなり、例えば樹脂用充填材や
表面に導電層を被覆した導電性粒子の母材などとして好
適なシリカ系微粒子を提供することを目的とするもので
ある。SUMMARY OF THE INVENTION Under such circumstances, according to the present invention, the projections are firmly bound by chemical bonding over the entire surface of the base particles, and for example, the conductive material is applied to the resin filler or the surface. It is an object of the present invention to provide silica-based fine particles suitable as a base material of conductive particles coated with a layer.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、特定の構造の
アルコキシシラン化合物を加水分解してポリオルガノシ
ロキサン粒子を生成させる工程、このポリオルガノシロ
キサン粒子を表面処理する工程、この表面処理ポリオル
ガノシロキサン粒子をシード粒子とし、該粒子全面にア
ルコキシシラン化合物を用いて突起物を形成させる工
程、さらに場合により焼成処理工程を施すことにより、
母体粒子全面に、実質上球状や半球状の突起物が化学結
合により、強固に結着してなるシリカ系微粒子が得られ
ることを見出し、この知見に基づいて本発明を完成する
に至った。Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a step of hydrolyzing an alkoxysilane compound having a specific structure to form polyorganosiloxane particles, A step of surface-treating the polyorganosiloxane particles, a step of forming the surface-treated polyorganosiloxane particles as seed particles, and a step of forming protrusions using an alkoxysilane compound on the entire surface of the particles, and optionally a firing treatment step. ,
The present inventors have found that silica-based fine particles in which substantially spherical or hemispherical projections are firmly bound by chemical bonding over the entire surface of the base particles can be obtained, and based on this finding, the present invention has been completed.
【０００７】すなわち、本発明は、母体粒子全面に、実
質上球状および／または半球状の突起物を有するシリカ
系微粒子であって、該突起物が化学結合により母体粒子
に結着していることを特徴とするシリカ系微粒子を提供
するものである。That is, the present invention provides silica-based fine particles having substantially spherical and / or hemispherical projections on the entire surface of the base particles, wherein the projections are bound to the base particles by chemical bonding. It is intended to provide silica-based fine particles characterized by the following.
【０００８】また、上記シリカ系微粒子は、（Ａ）一般
式（Ｉ） Ｒ1ｎＳｉ（ＯＲ2）4-n ・・・（Ｉ） （式中、Ｒ1は炭素数１〜５のアルキル基、炭素数２〜
５のアルケニル基、炭素数６〜１０のアリール基または
炭素数７〜１０のアラルキル基、Ｒ2は炭素数１〜５の
アルキル基、ｎは１または２を示し、ｎが２の場合、２
つのＲ1はたがいに同一でも異なっていてもよく、ま
た、複数のＯＲ2はたがいに同一でも異なっていてもよ
い。）で表されるアルコキシシラン化合物を加水分解、
縮合させ、場合により得られた粒子をシード粒子として
粒径成長させてポリオルガノシロキサン粒子を生成させ
る工程、（Ｂ）上記（Ａ）工程で得られたポリオルガノ
シロキサン粒子を、表面吸着剤により表面処理する工
程、および（Ｃ）上記（Ｂ）工程で表面処理されたポリ
オルガノシロキサン粒子をシード粒子とし、前記一般式
（Ｉ）で表されるアルコキシシラン化合物を用いて、該
シード粒子全面に突起を形成させる工程、さらに場合に
より（Ｄ）焼成処理工程、を含む方法により、製造する
ことができる。[0008] The silica-based fine particles are represented by the following general formula (A): R 1 nSi (OR 2 ) 4-n (I) wherein R 1 is an alkyl group having 1 to 5 carbon atoms. , Carbon number 2
An alkenyl group having 5 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R 2 represents an alkyl group having 1 to 5 carbon atoms, n represents 1 or 2, and when n is 2,
One R 1 may be the same or different, and a plurality of OR 2 may be the same or different. Hydrolysis of the alkoxysilane compound represented by
Condensing and optionally growing particles as seed particles to form polyorganosiloxane particles, and (B) subjecting the polyorganosiloxane particles obtained in step (A) to a surface adsorbent And (C) using the polyorganosiloxane particles surface-treated in the above step (B) as seed particles and projecting the entire surface of the seed particles using an alkoxysilane compound represented by the general formula (I). Can be manufactured by a method including a step of forming a sintering step, and optionally (D) a baking step.
【０００９】[0009]
【発明の実施の形態】本発明のシリカ系微粒子は、母体
粒子全面にわたって、実質上球状および／または半球状
の突起物が化学結合により、強固に結着してなる金平糖
状粒子である。シリカ系微粒子においては、突起物と母
体粒子双方が、通常一般式（Ｉ） Ｒ1ｎＳｉ（ＯＲ2）4-n ・・・（Ｉ） で表されるアルコキシシラン化合物に由来する組成を有
している。この場合、突起物を形成する原料のアルコキ
シシラン化合物と、母体粒子を形成する原料のアルコキ
シシラン化合物は、同一のものであってもよいし、異な
るものであってもよい。BEST MODE FOR CARRYING OUT THE INVENTION The silica-based fine particles of the present invention are confetti-like particles in which substantially spherical and / or hemispherical projections are firmly bound by chemical bonding over the entire surface of the base particles. In the silica-based fine particles, both the projections and the base particles usually have a composition derived from the alkoxysilane compound represented by the general formula (I) R 1 nSi (OR 2 ) 4-n ... (I). ing. In this case, the raw material alkoxysilane compound that forms the projections and the raw material alkoxysilane compound that forms the base particles may be the same or different.
【００１０】前記一般式（Ｉ）において、Ｒ1は炭素数
１〜５のアルキル基、炭素数２〜５のアルケニル基、炭
素数６〜１０のアリール基または炭素数７〜１０のアラ
ルキル基を示す。ここで、炭素数１〜５のアルキル基は
直鎖状、分岐状のいずれであってもよく、その例として
は、メチル基、エチル基、ｎ−プロピル基、イソプロピ
ル基、ｎ−ブチル基、イソブチル基、sec−ブチル基、t
ert−ブチル基及び各種ペンチル基が挙げられる。炭素
数２〜５のアルケニル基は直鎖状、分岐状のいずれであ
ってもよく、その例としてはビニル基、アリル基、ブテ
ニル基、ペンテニル基などが挙げられる。炭素数６〜１
０のアリール基の例としては、フェニル基、トリル基、
キシリル基、ナフチル基などが挙げられ、炭素数７〜１
０のアラルキル基の例としては、ベンジル基、フェネチ
ル基、フェニルプロピル基、ナフチルメチル基などが挙
げられる。In the general formula (I), R 1 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Show. Here, the alkyl group having 1 to 5 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, sec-butyl group, t
Examples include an ert-butyl group and various pentyl groups. The alkenyl group having 2 to 5 carbon atoms may be linear or branched, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a pentenyl group. Carbon number 6-1
Examples of the aryl group of 0 include a phenyl group, a tolyl group,
Xylyl group, naphthyl group, etc., having 7 to 1 carbon atoms
Examples of the aralkyl group of 0 include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and the like.
【００１１】一方、Ｒ2は炭素数１〜５のアルキル基で
あり、このアルキル基は直鎖状、分岐状のいずれであっ
てもよく、その例としては、メチル基、エチル基、ｎ−
プロピル基、イソプロピル基、ｎ−ブチル基、イソブチ
ル基、sec−ブチル基、tert−ブチル基及び各種ペンチ
ル基が挙げられる。ｎは１または２であり、ｎが２の場
合、２つのＲ1はたがいに同一でも異なっていてもよ
く、また、複数のＯＲ2はたがいに同一でも異なってい
てもよい。On the other hand, R 2 is an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, and an n-alkyl group.
Examples include propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and various pentyl groups. n is 1 or 2, and when n is 2, two R 1 may be the same or different, and a plurality of OR 2 may be the same or different.
【００１２】前記一般式（Ｉ）で表されるアルコキシシ
ラン化合物の例としては、メチルトリメトキシシラン、
メチルトリエトキシシラン、メチルトリプロポキシシラ
ン、メチルトリイソプロポキシシラン、エチルトリメト
キシシラン、エチルトリエトキシシラン、プロピルトリ
エトキシシラン、ブチルトリメトキシシラン、フェニル
トリメトキシシラン、フェニルトリエトキシシラン、ビ
ニルトリメトキシシラン、ビニルトリエトキシシラン、
ジメチルジメトキシシラン、メチルフェニルジメトキシ
シランなどが挙げられる。これらの中で、特にメチルト
リメトキシシランおよびビニルトリメトキシシランが好
適である。Examples of the alkoxysilane compound represented by the general formula (I) include methyltrimethoxysilane,
Methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane , Vinyltriethoxysilane,
Examples thereof include dimethyldimethoxysilane and methylphenyldimethoxysilane. Of these, methyltrimethoxysilane and vinyltrimethoxysilane are particularly preferred.
【００１３】本発明においては、原料として、前記一般
式（Ｉ）で表されるアルコキシシラン化合物を１種用い
てもよいし、２種以上を組み合わせて用いてもよい。本
発明のシリカ系微粒子における母体粒子は、平均粒径
が、通常０．５〜３０μｍ、好ましくは２〜１０μｍで
あり、また、粒度分布の変動係数（ＣＶ値）が、通常５
％以下であって、真球状の単分散粒子である。In the present invention, as the raw material, one kind of the alkoxysilane compound represented by the general formula (I) may be used, or two or more kinds may be used in combination. The base particles of the silica-based fine particles of the present invention have an average particle size of usually 0.5 to 30 μm, preferably 2 to 10 μm, and a coefficient of variation (CV value) of the particle size distribution of usually 5 to 5.
% Or less, and are truly spherical monodisperse particles.
【００１４】なお、変動係数（ＣＶ値）は下式により求
められる。 ＣＶ値（％）＝（粒径の標準偏差／平均粒径）×１００ この母体粒子の全面に、化学結合により結着されている
突起物は、実質上球状および／または半球状の形状を有
しており、そして、突起物の高さ／母体粒子径の平均値
は、通常０．０２〜０．５の範囲である。また、１個の
母体粒子に結着している突起物の数は、上記の突起物の
高さ／母体粒子径の値により左右され、特に限定されな
い。The coefficient of variation (CV value) is obtained by the following equation. CV value (%) = (standard deviation of particle size / average particle size) × 100 The projections bonded by chemical bonding to the entire surface of the base particles have a substantially spherical and / or hemispherical shape. The average value of the height of the protrusion / the diameter of the base particle is usually in the range of 0.02 to 0.5. Further, the number of protrusions bound to one base particle depends on the value of the height of the protrusion / the base particle diameter, and is not particularly limited.
【００１５】さらに、本発明のシリカ系微粒子は、完全
にシリカ化されたものについては、同じ粒子径をもつ従
来の球状シリカ系粒子（突起をもたない）に比べて、窒
素吸着比表面積が、約２倍以上に大きくなる。このよう
な形状を有する本発明のシリカ系微粒子は、以下に示す
本発明の方法によって、効率よく製造することができ
る。Further, the silica-based fine particles of the present invention, when completely silicaized, have a nitrogen adsorption specific surface area more than that of conventional spherical silica-based particles having the same particle diameter (without protrusions). , About twice or more. The silica-based fine particles of the present invention having such a shape can be efficiently produced by the method of the present invention described below.
【００１６】本発明のシリカ系微粒子の製造方法は、
（Ａ）ポリオルガノシロキサン粒子の生成工程、（Ｂ）
該ポリオルガノシロキサン粒子の表面処理工程、（Ｃ）
突起物形成工程、および場合により施される（Ｄ）焼成
処理工程を含むものであり、次に、各工程について説明
する。The method for producing silica-based fine particles of the present invention comprises:
(A) a step of forming polyorganosiloxane particles, (B)
Surface treatment step of the polyorganosiloxane particles, (C)
It includes a projection forming step and a (D) baking step optionally performed. Next, each step will be described.
【００１７】（Ａ）ポリオルガノシロキサン粒子の生成
工程 この（Ａ）工程においては、前記一般式（Ｉ）で表され
るアルコキシシラン化合物を加水分解、縮合させ、場合
により得られた粒子をシード粒子として粒径成長させて
ポリオルガノシロキサン粒子を生成させる工程である。(A) Formation of polyorganosiloxane particles
Step In the step (A), the alkoxysilane compound represented by the general formula (I) is hydrolyzed and condensed, and the resulting particles are grown as seed particles to grow polyorganosiloxane particles. This is the step of causing
【００１８】この（Ａ）工程においては、所望によりノ
ニオン性界面活性剤を含有するアンモニアおよび／また
はアミンの水性溶液の存在下に、前記一般式（Ｉ）で表
されるアルコキシシラン化合物を加水分解・縮合させる
が、上記アンモニアやアミンは、該アルコキシシラン化
合物の加水分解・縮合反応の触媒である。ここで、アミ
ンとしては、例えばモノメチルアミン、ジメチルアミ
ン、モノエチルアミン、ジエチルアミン、エチレンジア
ミンなどを好ましく挙げることができる。このアンモニ
アやアミンは単独で用いてもよいし、２種以上を組み合
わせて用いてもよいが、毒性が少なく、除去が容易で、
かつ安価なことから、アンモニアが好適である。In the step (A), the alkoxysilane compound represented by the above formula (I) is hydrolyzed in the presence of an aqueous solution of ammonia and / or amine containing a nonionic surfactant if desired. The above-mentioned ammonia and amine are catalysts for the hydrolysis and condensation reaction of the alkoxysilane compound. Here, as the amine, for example, monomethylamine, dimethylamine, monoethylamine, diethylamine, ethylenediamine and the like can be preferably mentioned. This ammonia or amine may be used alone or in combination of two or more kinds, but is less toxic, easy to remove,
Ammonia is preferred because it is inexpensive.
【００１９】ノニオン性界面活性剤を含有するアンモニ
アおよび／またはアミンの水性溶液としては、水または
水と水混和性有機溶剤との混合溶剤にノニオン性界面活
性剤とアンモニアおよび／またはアミンを溶解した溶液
が挙げられる。ここで、水混和性有機溶剤の例として
は、メタノール、エタノール、プロパノール、ブタノー
ルなどの低級アルコール類、アセトン、ジメチルケト
ン、メチルエチルケトンなどのケトン類、ジエチルエー
テル、ジプロピルエーテルなどのエーテル類などが挙げ
られる。これらは単独で水と混合してもよいし、２種以
上を組み合わせて水と混合してもよい。アンモニアやア
ミンの使用量としては特に制限はないが、反応開始前の
水層のｐＨが、７．５〜１１．０の範囲になるように選
定するのが好ましい。The aqueous solution of ammonia and / or amine containing a nonionic surfactant is prepared by dissolving a nonionic surfactant and ammonia and / or amine in water or a mixed solvent of water and a water-miscible organic solvent. Solution. Here, examples of the water-miscible organic solvent include lower alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, dimethyl ketone and methyl ethyl ketone, and ethers such as diethyl ether and dipropyl ether. Can be These may be mixed alone with water, or may be mixed with water in combination of two or more. The amount of ammonia or amine used is not particularly limited, but is preferably selected so that the pH of the aqueous layer before the start of the reaction is in the range of 7.5 to 11.0.
【００２０】本発明においては、所望により用いられる
ノニオン性界面活性剤として、ＨＬＢ値が８〜２０の範
囲にあるものが好ましく用いられる。このＨＬＢは、親
水性と親油性のバランスを表す指標であり、その値が小
さいほど、親油性が高い。ＨＬＢ値が上記範囲を逸脱す
るものでは、本発明の効果が十分に発揮されない。本発
明の効果をよりよく発揮させるには、ＨＬＢ値が１０〜
１７の範囲にあるものが好ましい。In the present invention, nonionic surfactants having an HLB value in the range of 8 to 20 are preferably used as desired. This HLB is an index indicating the balance between hydrophilicity and lipophilicity, and the smaller the value, the higher the lipophilicity. If the HLB value is out of the above range, the effects of the present invention will not be sufficiently exhibited. In order to exhibit the effect of the present invention better, the HLB value should be 10 to 10.
Those in the range of 17 are preferred.
【００２１】反応形式としては特に制限はなく、混合均
一系反応および２層系反応のいずれも用いることができ
るが、ＣＶ値が小さく、粒径精度のよい粒子が得られ、
かつ反応操作が容易な点から２層系反応の方が有利であ
る。The type of reaction is not particularly limited, and any of a mixed homogeneous reaction and a two-layer reaction can be used. However, particles having a small CV value and high particle size accuracy can be obtained.
The two-layer reaction is more advantageous in that the reaction operation is easy.
【００２２】この２層系反応においては、原料のアルコ
キシシラン化合物として、前記一般式（Ｉ）で表される
単独物もしくは混合物の比重（２３℃）が１以下である
ものが用いられる。まず、このアルコキシシラン化合物
を、所望により用いられるノニオン性界面活性剤とアン
モニアおよび／またはアミン含有水性溶液と実質上混合
させることなく、２層状態を保持しながら、界面で反応
させる。In the two-layer reaction, as the raw material alkoxysilane compound, one having a specific gravity (23 ° C.) of 1 or a mixture represented by the above general formula (I) of 1 or less is used. First, the alkoxysilane compound is reacted at the interface while maintaining a two-layer state without substantially mixing the nonionic surfactant used as desired with the aqueous solution containing ammonia and / or amine.
【００２３】この反応においては、アルコキシシラン化
合物とアンモニアやアミン水性溶液層とが、実質上混合
することなく、２層状態を保持するように緩やかに撹拌
することが必要である。これにより、上層のアルコキシ
シラン化合物が加水分解されて下層に移行し、そこでポ
リオルガノシロキサン粒子が成長する。この際の反応温
度は、原料のアルコキシシラン化合物の種類などに左右
されるが、一般的には０〜６０℃の範囲で選ばれる。こ
の２層系反応においては、上層のアルコキシシラン化合
物が消失してから、次工程へ供給する。In this reaction, it is necessary to stir gently so that the alkoxysilane compound and the aqueous ammonia or amine solution layer do not substantially mix and maintain a two-layer state. As a result, the alkoxysilane compound in the upper layer is hydrolyzed and migrates to the lower layer, where the polyorganosiloxane particles grow. The reaction temperature at this time depends on the type of the raw material alkoxysilane compound and the like, but is generally selected in the range of 0 to 60 ° C. In this two-layer reaction, the alkoxysilane compound in the upper layer disappears before being supplied to the next step.
【００２４】本発明の（Ａ）工程においては、必要に応
じて、このようにして得られた粒子をシード粒子とし、
さらに粒径成長させてもよい。この場合、シード粒子を
生成させたのち、反応液を希釈倍率が、好ましくは２〜
２００倍、より好ましくは５〜１００倍になるように水
性媒体で希釈してシード粒子液を調製する。この際、希
釈に使用する水性媒体としては、水または水と水混和性
有機溶剤との混合溶剤が用いられるが、前記加水分解反
応において、反応媒体として用いたものと同じものを用
いるのが好ましい。In the step (A) of the present invention, if necessary, the particles thus obtained are used as seed particles,
Further, the grain size may be grown. In this case, after generating the seed particles, the dilution ratio of the reaction solution is preferably 2 to 2.
The seed particle liquid is prepared by diluting with an aqueous medium to 200 times, more preferably 5 to 100 times. At this time, as the aqueous medium used for dilution, water or a mixed solvent of water and a water-miscible organic solvent is used, and in the hydrolysis reaction, it is preferable to use the same one used as the reaction medium. .
【００２５】次に、このシード粒子液に、前記一般式
（Ｉ）で表されるアルコキシシラン化合物を添加して、
上記と同様に２層系反応を行い、シード粒子を成長させ
る。この操作は、所望の粒径に成長させるまで繰り返し
行うことができる。Next, an alkoxysilane compound represented by the general formula (I) is added to the seed particle liquid,
A two-layer reaction is performed in the same manner as described above to grow seed particles. This operation can be repeated until the particles grow to a desired particle size.
【００２６】（Ｂ）ポリオルガノシロキサン粒子の表面
処理工程 この（Ｂ）工程においては、前記（Ａ）工程で得られた
ポリオルガノシロキサン粒子を、表面吸着剤により表面
処理する工程である。(B) Surface of polyorganosiloxane particles
Treatment Step In the step (B), the polyorganosiloxane particles obtained in the step (A) are subjected to a surface treatment with a surface adsorbent.
【００２７】この際使用する表面吸着剤としては、例え
ばポリビニルアルコール、ポリビニルピロリドン及び界
面活性剤を好ましく挙げることができる。ポリビニルア
ルコールとしては、ケン化度が、好ましくは３４〜９８
モル％、より好ましくは８８〜９８モル％で、数平均分
子量が好ましくは２００〜３，５００、より好ましくは
５００〜２，４００の範囲にあるものが好適である。ま
た、ポリビニルピロリドンとしては、数平均分子量が、
好ましくは１０，０００〜３６０，０００、より好まし
くは４０，０００〜１２０，０００の範囲にあるものが
好適である。As the surface adsorbent used at this time, for example, polyvinyl alcohol, polyvinylpyrrolidone and a surfactant can be preferably mentioned. As the polyvinyl alcohol, the degree of saponification is preferably from 34 to 98.
Molar%, more preferably 88 to 98 mole%, and the number average molecular weight is preferably 200 to 3,500, more preferably 500 to 2,400. Also, as polyvinylpyrrolidone, the number average molecular weight,
Those having a range of preferably 10,000 to 360,000, more preferably 40,000 to 120,000 are suitable.
【００２８】一方、界面活性剤としては、ノニオン性お
よびアニオン性のものが好ましく用いられる。ノニオン
性界面活性剤として、ＨＬＢ値が８〜２０の範囲にある
ものが好ましく用いられる。このＨＬＢは、親水性と親
油性のバランスを表す指標であり、その値が小さいほ
ど、親油性が高い。ＨＬＢ値が上記範囲を逸脱するもの
では、本発明の効果が十分に発揮されない。本発明の効
果をよりよく発揮させるには、ＨＬＢ値が１０〜１７の
範囲にあるものが好ましい。On the other hand, nonionic and anionic surfactants are preferably used. As the nonionic surfactant, those having an HLB value in the range of 8 to 20 are preferably used. This HLB is an index indicating the balance between hydrophilicity and lipophilicity, and the smaller the value, the higher the lipophilicity. If the HLB value is out of the above range, the effects of the present invention will not be sufficiently exhibited. In order to further exert the effects of the present invention, those having an HLB value in the range of 10 to 17 are preferable.
【００２９】該ノニオン性界面活性剤としては、ＨＬＢ
値が上記の範囲にあるものであればよく、特に制限され
ず、例えばポリオキシエチレンアルキルエーテル、ポリ
オキシエチレンアルキルフェニルエーテル、ポリオキシ
エチレンステロールエーテル、ポリオキシエチレンラノ
リン誘導体、アルキルフェノールホルマリン縮合物の酸
化エチレン誘導体、ポリオキシエチレンポリオキシプロ
ピレンブロックポリマー、ポリオキシエチレンポリオキ
シプロピレンアルキルエーテルなどのエーテル型ノニオ
ン性界面活性剤、ポリオキシエチレングリセリン脂肪酸
エステル、ポリオキシエチレンヒマシ油および硬化ヒマ
シ油、ポリオキシエチレンソルビタン脂肪酸エステル、
ポリオキシエチレンソルビトール脂肪酸エステルなどの
エーテルエステル型ノニオン性界面活性剤、ポリエチレ
ングリコール脂肪酸エステル、ポリグリセリン脂肪酸エ
ステル、ソルビタン脂肪酸エステル、プロピレングリコ
ール脂肪酸エステル、ショ糖脂肪酸エステルなどのエス
テル型ノニオン性界面活性剤、ポリオキシエチレン脂肪
酸アミド、ポリオキシエチレンアルキルアミン、アルキ
ルアミンオキシドなどの含窒素型ノニオン性界面活性剤
などが挙げられるが、これらの中でエーテル型が好まし
く、特にポリオキシエチレンアルキルフェニルエーテル
が好適である。これらのノニオン性界面活性剤は、単独
で用いてもよいし、２種以上を組み合わせて用いてもよ
い。As the nonionic surfactant, HLB is used.
The value is not particularly limited as long as it is within the above range, and for example, oxidation of polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, alkylphenol formalin condensate Ether type nonionic surfactants such as ethylene derivatives, polyoxyethylene polyoxypropylene block polymers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene castor oil and hydrogenated castor oil, polyoxyethylene Sorbitan fatty acid esters,
Ether-type nonionic surfactants such as polyoxyethylene sorbitol fatty acid esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and ester nonionic surfactants such as sucrose fatty acid esters; Examples include nitrogen-containing nonionic surfactants such as polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, and alkylamine oxides. Among them, ether-type surfactants are preferable, and polyoxyethylene alkylphenyl ether is particularly preferable. is there. These nonionic surfactants may be used alone or in combination of two or more.
【００３０】また、アニオン性界面活性剤としては、Ｈ
ＬＢ値が１８〜４２の範囲にあるものが用いられる。Ｈ
ＬＢ値が上記範囲を逸脱するものでは、本発明の効果が
十分に発揮されない。このようなアニオン性界面活性剤
としては、ＨＬＢ値が１８〜４２の範囲にあればよく、
特に制限はないが、例えばアルキルアリールスルホン酸
塩、アルキル硫酸塩、脂肪酸アルカリ塩、アルキルリン
酸塩、アルキルホスホン酸塩などが挙げられる。これら
の中で、アルキル基の炭素数が８〜１８のアルキルアリ
ールスルホン酸塩、アルキル基の炭素数が８〜１８のア
ルキル硫酸塩、アルキル基の炭素数が８〜１８の脂肪酸
アルカリ塩が好ましく、特にドデシル硫酸ナトリウム、
ドデシルベンゼンスルホネート、オレイン酸カリウムが
好適である。また、このアニオン性界面活性剤は単独で
用いてもよいし、２種以上を組み合わせて用いてもよ
い。Further, as the anionic surfactant, H
Those having an LB value in the range of 18 to 42 are used. H
If the LB value is out of the above range, the effects of the present invention will not be sufficiently exhibited. Such an anionic surfactant may have an HLB value in the range of 18 to 42,
Although there is no particular limitation, examples thereof include an alkyl aryl sulfonate, an alkyl sulfate, a fatty acid alkali salt, an alkyl phosphate, and an alkyl phosphonate. Among these, an alkylaryl sulfonate having an alkyl group having 8 to 18 carbon atoms, an alkyl sulfate having an alkyl group having 8 to 18 carbon atoms, and a fatty acid alkali salt having an alkyl group having 8 to 18 carbon atoms are preferable. Especially sodium dodecyl sulfate,
Dodecylbenzene sulfonate and potassium oleate are preferred. The anionic surfactant may be used alone or in combination of two or more.
【００３１】この（Ｂ）工程においては、前記（Ａ）工
程で得られたポリオルガノシロキサン粒子液と上記表面
吸着剤を含む水性溶液を撹拌混合したのち、アンモニア
および／またはアミンを添加し、好ましくは２０〜６０
℃の温度において１〜２０時間程度熟成することによ
り、表面処理が行われる。この際、上記混合液中の表面
吸着剤の濃度は、０．１〜５重量％の範囲が好ましい。
このようにして表面処理されたポリオルガノシロキサン
粒子は、好ましくは単離したのち、次工程の突起物形成
工程に供給される。In the step (B), the polyorganosiloxane particle liquid obtained in the step (A) and the aqueous solution containing the surface adsorbent are stirred and mixed, and ammonia and / or an amine are added. Is 20-60
Surface treatment is performed by aging at a temperature of about 1 to about 20 hours. At this time, the concentration of the surface adsorbent in the mixture is preferably in the range of 0.1 to 5% by weight.
The polyorganosiloxane particles thus surface-treated are preferably isolated and then supplied to the next step of forming projections.
【００３２】（Ｃ）突起物形成工程 この（Ｃ）工程においては、前記（Ｂ）工程で表面処理
されたポリオルガノシロキサン粒子をシード粒子とし、
前記一般式（Ｉ）で表されるアルコキシシラン化合物を
加水分解、縮合させて、該シード粒子（母体粒子）の全
面に突起物を形成させる工程である。この（Ｃ）工程に
おいても、混合均一系反応および２層系反応のいずれも
用いることができるが、前記（Ａ）工程と同様に２層系
反応の方が有利である。(C) Projection Forming Step In the step (C), the polyorganosiloxane particles surface-treated in the step (B) are used as seed particles.
This is a step of hydrolyzing and condensing the alkoxysilane compound represented by the general formula (I) to form projections on the entire surface of the seed particles (base particles). In the step (C), either a mixed homogeneous reaction or a two-layer reaction can be used, but the two-layer reaction is more advantageous as in the step (A).
【００３３】この２層系反応においては、まず、所望に
より用いられるポリビニルアルコールなどの分散剤とア
ンモニアおよび／またはアミンを含有する水性溶液中
に、前記（Ｂ）工程で得られた表面処理ポリオルガノシ
ロキサン粒子を分散させてなる水性液を調製する。次い
で、一般式（Ｉ）で表されるアルコキシシラン化合物
を、該水性液と実質上混合させることなく、２層状態を
保持しながら界面で反応させる。In this two-layer reaction, first, the surface-treated polyorganoorganic compound obtained in the step (B) is placed in an aqueous solution containing a dispersant such as polyvinyl alcohol and ammonia and / or an amine, if desired. An aqueous liquid in which siloxane particles are dispersed is prepared. Next, the alkoxysilane compound represented by the general formula (I) is reacted at the interface while maintaining the two-layer state without being substantially mixed with the aqueous liquid.
【００３４】この反応においては、アルコキシシラン化
合物とアンモニアやアミン水性溶液層とが、実質上混合
することなく、２層状態を保持するように緩やかに撹拌
することが必要である。これにより、上層のアルコキシ
シラン化合物が加水分解されて下層に移行し、そこで母
体粒子のポリオルガノシロキサン粒子と化学結合し、突
起物を成長させる。この際の反応温度は、原料のアルコ
キシシラン化合物の種類などに左右されるが、一般的に
は０〜６０℃の範囲で選ばれる。In this reaction, it is necessary to gently stir the alkoxysilane compound and the aqueous ammonia or amine solution layer so as to maintain a two-layer state without substantial mixing. As a result, the alkoxysilane compound in the upper layer is hydrolyzed and migrates to the lower layer, where it is chemically bonded to the polyorganosiloxane particles of the base particles to grow protrusions. The reaction temperature at this time depends on the type of the raw material alkoxysilane compound and the like, but is generally selected in the range of 0 to 60 ° C.
【００３５】反応終了後（上層が消失後）、常法に従っ
て遠心分離および沈降分級により、粒子洗浄を行ったの
ち、乾燥処理することにより、母体粒子全面に、実質上
球状および／または半球状の突起物を有するシリカ系微
粒子が得られる。本発明においては、このようにして得
られたシリカ系微粒子は、母体粒子および突起物共に、
有機基をもつポリオルガノシロキサンから構成されてい
るので、必要に応じ、次の焼成処理を施すことができ
る。After the completion of the reaction (after the upper layer has disappeared), the particles are washed by centrifugation and sedimentation classification according to a conventional method, and then dried to form substantially spherical and / or hemispherical particles on the entire surface of the base particles. Silica-based fine particles having protrusions are obtained. In the present invention, the silica-based fine particles obtained in this manner, both the base particles and the projections,
Since it is composed of polyorganosiloxane having an organic group, the following calcination treatment can be performed as necessary.
【００３６】（Ｄ）焼成処理工程 この（Ｄ）工程においては、最終製品の用途に応じ、焼
成処理を、空気などの酸素含有ガスの存在下、好ましく
は５００〜１０００℃、より好ましくは６００〜９００
℃の範囲の温度で行い、完全シリカ化を行って高弾性率
粒子を得てもよいし、あるいは、窒素などの不活性ガス
雰囲気下または真空中において、好ましくは４００〜９
００℃、より好ましくは５００〜８００℃の範囲の温度
で焼成処理を行い、部分シリカ化または非シリカ化を行
い、低弾性率粒子を得てもよい。すなわち、必要となる
破壊強度や弾性率に応じて、最適な条件を選定すればよ
い。また、焼成装置については特に制限はなく、電気炉
やロータリーキルンなどを用いることができるが、粒子
の撹拌が可能なロータリーキルン中で焼成するのが有利
である。このようにして焼成処理してなる粒子の形状
は、焼成前と実質上相似であり、母体粒子全面にわた
り、ほぼ球状や半球状の突起物が化学結合により強固に
結着した金平糖状を有している。(D) Firing Treatment Step In this (D) step, depending on the use of the final product, the firing treatment is performed in the presence of an oxygen-containing gas such as air, preferably at 500 to 1000 ° C., more preferably at 600 to 1000 ° C. 900
C., and complete silicification may be performed to obtain high elastic modulus particles, or under an inert gas atmosphere such as nitrogen or in a vacuum, preferably 400 to 9
The baking treatment may be performed at a temperature of 00 ° C., more preferably 500 to 800 ° C., and partial or non-silica conversion may be performed to obtain low elastic modulus particles. That is, optimal conditions may be selected according to the required breaking strength and elastic modulus. The firing apparatus is not particularly limited, and an electric furnace, a rotary kiln, or the like can be used. However, firing in a rotary kiln capable of stirring particles is advantageous. The shape of the particles obtained by firing in this manner is substantially similar to that before firing, and has a spinous shape in which substantially spherical or hemispherical projections are firmly bound by chemical bonding over the entire surface of the base particles. ing.
【００３７】[0037]
【実施例】次に、本発明を実施例により、さらに詳細に
説明するが、本発明は、これらの例によってなんら限定
されるものではない。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００３８】実施例１ （１）第１シード粒子液の調製 温度調節可能なマグネチックスターラー付き恒温水槽
に、５００ミリリットル容のガラスフラスコをセット
し、これに、１モル／リットル濃度のアンモニア水１２
ミリリットル、ノニオン系界面活性剤であるポリオキシ
エチレンアルキルアリールエーテル「ノイゲンＥＡ−１
３７（ＨＬＢ１３）」［第一工業薬品（株）製］０．３
ミリリットルおよびイオン交換水３００ｇを混合した液
を入れ、温度を３０℃に保持した。次いで、この液の上
に、界面が乱れないようにメチルトリメトキシシラン
（ＭＴＭＳ）３０ｇを注ぎ込み、２層状態としてから、
下層のアンモニア水溶液をマグネチックスターラーによ
り緩やかに撹拌して、ＭＴＭＳの加水分解反応を行っ
た。時間の経過と共に、下層のアンモニア水溶液が白濁
し始め、３時間後、上層のＭＴＭＳは、加水分解により
下層のアンモニア水溶液中に移行して消失した。この白
濁液中には、平均粒径１．８５μｍの単分散ポリメチル
シルセスキオキサン（ＰＭＳＯ）粒子が生成しており、
これを第１シード粒子液とした。Example 1 (1) Preparation of First Seed Particle Liquid A 500 ml glass flask was set in a thermostatic water bath equipped with a temperature-controllable magnetic stirrer.
Milliliter, nonionic surfactant polyoxyethylene alkyl aryl ether "Neugen EA-1"
37 (HLB13) "[manufactured by Daiichi Kogyo Chemical Co., Ltd.] 0.3
A liquid obtained by mixing milliliters and 300 g of ion-exchanged water was added, and the temperature was maintained at 30 ° C. Next, 30 g of methyltrimethoxysilane (MTMS) was poured over the liquid so that the interface was not disturbed, and a two-layer state was obtained.
The aqueous ammonia solution in the lower layer was gently stirred with a magnetic stirrer to perform a hydrolysis reaction of MTMS. With the passage of time, the lower aqueous ammonia solution began to become cloudy, and after 3 hours, the upper layer of MTMS was transferred to the lower aqueous ammonia solution by hydrolysis and disappeared. In this cloudy liquid, monodispersed polymethylsilsesquioxane (PMSO) particles having an average particle size of 1.85 μm are formed,
This was used as a first seed particle liquid.
【００３９】（２）第２シード粒子液の調製 撹拌モーターおよび撹拌翼を備えた５リットルのガラス
フラスコを恒温水槽にセットし、該フラスコにイオン交
換水４５００ミリリットルを入れ、２０ｒｐｍで撹拌し
ながら、上記（１）で得られた第１シード粒子液の全量
を添加して、シードＰＭＳＯ粒子を希釈して分散させ
た。次いで、この分散液の上層にＭＴＭＳ４５０ｇを注
ぎ、反応温度を３０℃として、再び２層状態で加水分解
反応を行い、シードＰＭＳＯ粒子の成長反応を行った。
５時間後、上層のＭＴＭＳが消失した時点で、ＰＭＳＯ
粒子は、平均粒径で５．０〜５．２μｍまで成長してお
り、単分散球状粒子であった。これを第２シード粒子液
とした。(2) Preparation of Second Seed Particle Liquid A 5 liter glass flask equipped with a stirring motor and a stirring blade was set in a thermostatic water bath, and 4500 ml of ion-exchanged water was charged into the flask and stirred at 20 rpm. The whole amount of the first seed particle liquid obtained in the above (1) was added to dilute and disperse the seed PMSO particles. Next, 450 g of MTMS was poured into the upper layer of the dispersion, the reaction temperature was set to 30 ° C., the hydrolysis reaction was again performed in a two-layer state, and a seed PMSO particle growth reaction was performed.
Five hours later, when the upper MTMS disappeared, PMSO
The particles were grown to an average particle size of 5.0 to 5.2 μm and were monodisperse spherical particles. This was used as a second seed particle liquid.
【００４０】（３）表面処理 第２シード粒子液全量に対し、５重量％濃度のポリビニ
ルアルコール［完全けん化型、数平均分子量（Ｍｎ）５
００］水溶液（ＰＶＡ水溶液）１２００ミリリットルを
添加して撹拌混合し、ＰＶＡ濃度が１重量％のシードＰ
ＭＳＯ粒子分散液を調製した。次いで、２５重量％アン
モニア水１５ミリリットルを添加したのち、溶液温度を
５０℃まで昇温し、その温度で１２時間保持した。ここ
で得られたＰＶＡ吸着ＰＭＳＯ粒子（母体粒子）は、平
均粒径４．５μｍの単分散微粒子であった。次に、これ
をメタノールで洗浄後、乾燥させ、シード粉体１９０ｇ
を得た。(3) Surface treatment 5% by weight of polyvinyl alcohol [completely saponified, number average molecular weight (Mn) 5
00] An aqueous solution (aqueous PVA solution) (1200 ml) was added thereto, followed by stirring and mixing to obtain a seed P having a PVA concentration of 1% by weight.
An MSO particle dispersion was prepared. Next, after adding 15 ml of 25% by weight aqueous ammonia, the solution temperature was raised to 50 ° C. and maintained at that temperature for 12 hours. The PVA-adsorbed PMSO particles (base particles) obtained here were monodisperse fine particles having an average particle size of 4.5 μm. Next, this was washed with methanol and dried, and 190 g of seed powder was obtained.
I got
【００４１】（４）異形化処理 温度調節可能なマグネチックスターラー付き恒温水槽に
１リットルのガラスフラスコをセットし、これに上記
（３）で得たシード粉体２ｇを１重量％ＰＶＡ水溶液８
００ミリリットルに分散させた液と２５重量％アンモニ
ア水０．１ミリリットルとを混合した液を入れ、温度を
３０℃に保持した。次いで、この液の上に、界面が乱れ
ないようにメチルトリメトキシシラン（ＭＴＭＳ）７０
ｇを注ぎ込み、２層状態としてから、下層のアンモニア
水溶液をマグネチックスターラーにより緩やかに撹拌し
て、ＭＴＭＳの加水分解反応を行った。時間の経過と共
に、下層のアンモニア水溶液が白濁し始め、２時間後、
上層のＭＴＭＳは、加水分解により下層のアンモニア水
溶液中に移行して消失した。(4) Deformation treatment A 1-liter glass flask was set in a thermostatic water bath with a magnetic stirrer capable of controlling the temperature, and 2 g of the seed powder obtained in the above (3) was added to a 1% by weight aqueous solution of PVA 8
A liquid obtained by mixing a liquid dispersed in 00 ml and 0.1 ml of 25% by weight ammonia water was added, and the temperature was maintained at 30 ° C. Next, a methyltrimethoxysilane (MTMS) 70 is placed on this solution so that the interface is not disturbed.
g, the mixture was made into a two-layer state, and the aqueous ammonia solution in the lower layer was gently stirred with a magnetic stirrer to perform a hydrolysis reaction of MTMS. With the passage of time, the aqueous ammonia solution in the lower layer began to become cloudy, and two hours later,
The MTMS in the upper layer migrated into the aqueous ammonia solution in the lower layer by hydrolysis and disappeared.
【００４２】粒子を取り出し、走査型電子顕微鏡（ＳＥ
Ｍ）により形状を観察した結果、粒子全面に高さ１．４
〜３．０μｍの突起物を有し、見掛け上の平均粒径〔突
起先端まで含めた粒径（以下最終平均粒径と表記）〕が
６．５μｍの金平糖状の粒子であった。図１に、この粒
子のＳＥＭ写真図を示す。次に、遠心分離及び沈降分級
により、粒子洗浄を行い、最後にメタノールに分散させ
たのち、メタノールを除去し、１２０℃のオーブンで乾
燥させて、乾燥粒子１．８ｇを得た。The particles were taken out and scanned with a scanning electron microscope (SE).
As a result of observing the shape by M), a height of 1.4
The particles were confetti-like particles having protrusions of about 3.0 μm and an apparent average particle diameter [particle diameter including the tip of the projection (hereinafter referred to as final average particle diameter)] of 6.5 μm. FIG. 1 shows a SEM photograph of the particles. Next, the particles were washed by centrifugation and sedimentation classification, and finally dispersed in methanol. Thereafter, methanol was removed and the particles were dried in an oven at 120 ° C. to obtain 1.8 g of dry particles.
【００４３】（５）焼成処理 上記（４）で得た乾燥粒子を、焼成容器に入れ、電気炉
中にセットした後、空気を０．３リットル／分の流量で
流しながら、室温から４００℃まで１．２５時間で昇温
し、その温度で４８時間保持してから、さらに８００℃
まで０．５時間で昇温し、その温度で６時間保持した
後、室温まで降温させた。粒子の形状は、焼成前と相似
であった。ＩＲ測定の結果、メチル基のピークが観察さ
れず、シリカのみのＩＲ吸収が認められ、シリカに変化
していることが確認された。なお、乾燥粒子を、窒素を
０．３リットル／分の流量で流しながら、６９０℃で
２．５時間、あるいは６７０℃で２．５時間焼成したと
ころ、いずれもシリカ化していない低弾性率異形粒子が
得られた。(5) Baking treatment The dried particles obtained in the above (4) are placed in a baking vessel, set in an electric furnace, and then heated from room temperature to 400 ° C. while flowing air at a flow rate of 0.3 liter / min. Up to 1.25 hours, hold at that temperature for 48 hours, and then
The temperature was raised in 0.5 hours until the temperature was maintained at that temperature for 6 hours, and then lowered to room temperature. The shape of the particles was similar to that before firing. As a result of IR measurement, no peak of a methyl group was observed, and IR absorption of silica alone was recognized, confirming that the silica was changed to silica. The dried particles were calcined at 690 ° C. for 2.5 hours or at 670 ° C. for 2.5 hours while flowing nitrogen at a flow rate of 0.3 L / min. Particles were obtained.
【００４４】実施例２ 実施例１における（１）〜（３）と同様の操作を行いシ
ード粉体を得た。 （１）異形化処理 温度調節可能なマグネチックスターラー付き恒温水槽に
１リットルのガラスフラスコをセットし、これに上記シ
ード粉体２ｇを１重量％ＰＶＡ水溶液８００ミリリット
ルに分散させた液と２５重量％アンモニア水０．１ミリ
リットルとを混合した液を入れ、温度を３０℃に保持し
た。次いで、この液の上に、界面が乱れないようにメチ
ルトリメトキシシラン（ＭＴＭＳ）２０ｇを注ぎ込み、
２層状態としてから、下層のアンモニア水溶液をマグネ
チックスターラーにより緩やかに撹拌して、ＭＴＭＳの
加水分解反応を行った。上層のＭＴＭＳが消失した時点
で粒子を取り出し、ＳＥＭにより形状を観察した結果、
粒子全面に高さ０．７〜２．０μｍの突起物を有し、最
終平均粒径が５．８μｍの金平糖状粒子であった。図２
に、この粒子のＳＥＭ写真図を示す。Example 2 The same operation as (1) to (3) in Example 1 was performed to obtain a seed powder. (1) Deformation treatment A 1-liter glass flask was set in a thermostatic water tank with a temperature-controllable magnetic stirrer, and a liquid in which 2 g of the seed powder was dispersed in 800 ml of a 1% by weight aqueous PVA solution and 25% by weight were added. A liquid obtained by mixing 0.1 ml of aqueous ammonia was added, and the temperature was maintained at 30 ° C. Next, 20 g of methyltrimethoxysilane (MTMS) was poured onto the liquid so as not to disturb the interface,
After the two-layer state, the lower aqueous ammonia solution was gently stirred with a magnetic stirrer to perform a hydrolysis reaction of MTMS. When the MTMS in the upper layer disappeared, the particles were taken out and the shape was observed by SEM.
The particles were spinous particles having a height of 0.7 to 2.0 μm on the entire surface and a final average particle size of 5.8 μm. FIG.
The SEM photograph of the particles is shown in FIG.
【００４５】実施例３ 実施例１における（１）〜（３）と同様の操作を行いシ
ード粉体を得た。 （１）異形化処理 温度調節可能なマグネチックスターラー付き恒温水槽に
１リットルのガラスフラスコをセットし、これに上記シ
ード粉体１０ｇを１重量％ＰＶＡ水溶液８００ミリリッ
トルに分散させた液と２５重量％アンモニア水０．１ミ
リリットルとを混合した液を入れ、温度を３０℃に保持
した。次いで、この液の上に、界面が乱れないようにメ
チルトリメトキシシラン（ＭＴＭＳ）２０ｇを注ぎ込
み、２層状態としてから、下層のアンモニア水溶液をマ
グネチックスターラーにより緩やかに撹拌して、ＭＴＭ
Ｓの加水分解反応を行った。上層のＭＴＭＳが消失した
時点で粒子を取り出し、ＳＥＭにより形状を観察した結
果、粒子全面に高さ０．２〜１．１μｍの突起物を有
し、最終平均粒径が５．２μｍの金平糖状粒子であっ
た。図３に、この粒子のＳＥＭ写真図を示す。Example 3 The same operation as (1) to (3) in Example 1 was performed to obtain a seed powder. (1) Deformation treatment A 1-liter glass flask was set in a thermostatic water bath with a magnetic stirrer capable of adjusting the temperature, and a liquid in which 10 g of the seed powder was dispersed in 800 ml of a 1% by weight aqueous PVA solution and 25% by weight were added. A liquid obtained by mixing 0.1 ml of aqueous ammonia was added, and the temperature was maintained at 30 ° C. Next, 20 g of methyltrimethoxysilane (MTMS) was poured onto the solution so that the interface was not disturbed, and after forming a two-layer state, the aqueous ammonia solution in the lower layer was gently stirred with a magnetic stirrer to obtain an MTM.
The hydrolysis reaction of S was performed. When the MTMS in the upper layer disappeared, the particles were taken out, and the shape was observed by SEM. Particles. FIG. 3 shows a SEM photograph of the particles.
【００４６】実施例４ 実施例１における（１）、（２）と同様の操作を行い、
第２シード粒子液を調製した。 （１）表面処理 実施例１（３）において、数平均分子量（Ｍｎ）が５０
０のＰＶＡを用いる代わりに、Ｍｎが１０００のＰＶＡ
を用いた以外は、実施例１（３）と同様にして、平均粒
径４．２μｍ、ＣＶ値１．９％のシード粉体を得た。 （２）異形化処理 実施例１（４）と同条件、同方法により、ＭＴＭＳの加
水分解反応を行い、粒子全面に突起物を有する金平糖状
粒子を得た。この粒子は、粒子全面に高さ０．２〜０．
６μｍの突起物を有し、最終平均粒径が４．９μｍの金
平糖状の粒子であった。Example 4 The same operation as (1) and (2) in Example 1 was performed.
A second seed particle liquid was prepared. (1) Surface treatment In Example 1 (3), the number average molecular weight (Mn) was 50.
Instead of using PVA of 0, PVA with Mn of 1000
A seed powder having an average particle size of 4.2 μm and a CV value of 1.9% was obtained in the same manner as in Example 1 (3) except that was used. (2) Deformation treatment Under the same conditions and under the same method as in Example 1 (4), hydrolysis of MTMS was performed to obtain spinous particles having protrusions on the entire surface of the particles. The particles have a height of 0.2 to 0.
The particles were spinous particles having protrusions of 6 μm and having a final average particle size of 4.9 μm.
【００４７】実施例５、６ 実施例４において、数平均分子量（Ｍｎ）が１０００の
ＰＶＡの代わりに、Ｍｎが３５００（実施例５）および
７００００（実施例６）を用いた以外は、実施例４と同
様な操作により、金平糖状粒子が得られることを確認し
た。Examples 5 and 6 The procedure of Example 4 was repeated except that PVA having a number average molecular weight (Mn) of 1,000 was replaced by Mn of 3500 (Example 5) and 70,000 (Example 6). It was confirmed that confetti-like particles were obtained by the same operation as in Example 4.
【００４８】実施例７、８ 実施例４において、数平均分子量（Ｍｎ）が１０００の
ＰＶＡの代わりに、Ｍｎが４０，０００（実施例７）お
よび１，２００，０００（実施例８）のポリビニルピロ
リドン（ＰＶＰ）を用いた以外は、実施例４と同様な操
作により、金平糖状粒子が得られることを確認した。Examples 7 and 8 In Example 4, polyvinyl alcohols having Mn of 40,000 (Example 7) and 1,200,000 (Example 8) were used instead of PVA having a number average molecular weight (Mn) of 1000. Except that pyrrolidone (PVP) was used, it was confirmed that confetti-like particles could be obtained by the same operation as in Example 4.
【００４９】実施例９ 実施例１における（１）、（２）と同様の操作を行い、
第２シード粒子液を調製した。 （１）表面処理 撹拌モーターおよび撹拌翼を備えた５００ミリリットル
のガラスビーカーを恒温水槽にセットし、該ビーカーに
ノニオン系界面活性剤であるポリオキシエチレンアルキ
ルアリールエーテル［「ノイゲンＥＡ−１３７（ＨＬＢ
１３）」第一工業薬品（株）製］１．５ｇとイオン交換
水１４８．５ｇで１重量％に調整した水溶液に、上記第
２シード粒子液３００ミリリットルを添加して、撹拌混
合した。次いで、２５重量％アンモニア水１５ミリリッ
トルを添加したのち、１２時間保持、撹拌して、平均粒
径４．７μｍ、ＣＶ値１．４７％の界面活性剤吸着ＰＭ
ＳＯ粒子（母体粒子）を得た。 （２）異形化処理 実施例１（４）と同条件、同方法により、ＭＴＭＳの加
水分解反応を行い、粒子全面に突起物を有する金平糖状
粒子を得た。この粒子は、粒子全面に高さ０．４〜０．
９μｍの突起物を有し、最終平均粒径が５．８μｍの金
平糖状粒子であった。Example 9 The same operation as (1) and (2) in Example 1 was performed.
A second seed particle liquid was prepared. (1) Surface Treatment A 500 ml glass beaker equipped with a stirring motor and stirring blades was set in a thermostatic water bath, and a polyoxyethylene alkyl aryl ether [Neugen EA-137 (HLB) was used as a nonionic surfactant.
13) "Daiichi Kogyo Chemical Co., Ltd."] To an aqueous solution adjusted to 1% by weight with 1.5 g and 148.5 g of ion-exchanged water, 300 ml of the second seed particle liquid was added, followed by stirring and mixing. Then, 15 ml of 25% by weight ammonia water was added, and the mixture was held and stirred for 12 hours to obtain a surfactant-adsorbed PM having an average particle size of 4.7 μm and a CV value of 1.47%.
SO particles (base particles) were obtained. (2) Deformation treatment Under the same conditions and under the same method as in Example 1 (4), hydrolysis of MTMS was performed to obtain spinous particles having protrusions on the entire surface of the particles. The particles have a height of 0.4 to 0.1 mm over the entire surface of the particles.
The spinous particles had protrusions of 9 μm and a final average particle size of 5.8 μm.
【００５０】実施例１０〜１５ 実施例９において、「ノイゲンＥＡ−１３７（ＨＬＢ１
３）」の代わりに、ＨＬＢや種類の異なる第一工業薬品
（株）製のノニオン系界面活性剤である「ノイゲンＥＡ
−１５７（ＨＬＢ１５）」（実施例１０）、「ノイゲン
ＥＡ−１７７（ＨＬＢ１７）」（実施例１１）、「ノイ
ゲンＥＡ−７３（ＨＬＢ９）」（実施例１２）、「ノイ
ゲンＥＡ−１４３（ＨＬＢ１４）」（実施例１３）、
「ノイゲンＥＳ−１４９（ＨＬＢ１４）」（実施例１
４）、「ノイゲンＥＴ−１４７（ＨＬＢ１４）」（実施
例１５）を用いた以外は、実施例９と同様な操作によ
り、それぞれ金平糖状粒子が得られることを確認した。Examples 10 to 15 In Example 9, "Neugen EA-137 (HLB1
"3)" instead of HLB or "Neugen EA" which is a nonionic surfactant manufactured by Daiichi Kogyo Yakuhin Co., Ltd.
-157 (HLB15) "(Example 10)," Neugen EA-177 (HLB17) "(Example 11)," Neugen EA-73 (HLB9) "(Example 12)," Neugen EA-143 (HLB14) " (Example 13),
"Neugen ES-149 (HLB14)" (Example 1
4) Except for using "Neugen ET-147 (HLB14)" (Example 15), it was confirmed that spinous particles were obtained by the same operation as in Example 9.
【００５１】実施例１６ 実施例９において、「ノイゲンＥＡ−１３７（ＨＬＢ１
３）」の代わりに、ポリオキシエチレンアルキルフェニ
ルエーテル「エマルジット９（ＨＬＢ１８〜２０）」
［第一工業薬品（株）製］を用いた以外は、実施例９と
同様な操作により、それぞれ金平糖状粒子が得られるこ
とを確認した。Example 16 In Example 9, "Neugen EA-137 (HLB1
3) "instead of polyoxyethylene alkyl phenyl ether" Emulgit 9 (HLB18-20) "
Except that [Daiichi Kogyo Chemical Co., Ltd.] was used, it was confirmed that confetti-like particles were obtained by the same operation as in Example 9.
【００５２】実施例１７ 実施例９において、「ノイゲンＥＡ−１３７（ＨＬＢ１
３）」の代わりに、ドデシル硫酸ナトリウム［ＳＤＳ、
ＨＬＢ４０、第一工業薬品（株）製］を用いた以外は、
実施例９と同様な操作により、金平糖状粒子が得られる
ことを確認した。Example 17 In Example 9, "Neugen EA-137 (HLB1
3)], instead of sodium dodecyl sulfate [SDS,
HLB40, manufactured by Daiichi Kogyo Chemical Co., Ltd.]
It was confirmed that spinous particles were obtained by the same operation as in Example 9.
【００５３】なお、「ノイゲンＥＡ−１５７」、「ノイ
ゲンＥＡ−１７７」はポリオキシエチレンアルキルアリ
ールエーテル、「ノイゲンＥＡ−７３」、「ノイゲンＥ
Ａ−１４３」はポリオキシエチレンドデシルフェニルエ
ーテル、「ノイゲンＥＳ−１４９」はポリオキシエチレ
ンオレイン酸エステル、「ノイゲンＥＴ−１４７」はポ
リオキシエチレンアルキルエーテルである。"Neugen EA-157" and "Neugen EA-177" are polyoxyethylene alkyl aryl ethers, "Neugen EA-73" and "Neugen E
"A-143" is polyoxyethylene dodecylphenyl ether, "Neugen ES-149" is polyoxyethylene oleate, and "Neugen ET-147" is polyoxyethylene alkyl ether.
【００５４】[0054]
【発明の効果】本発明によれば、母体粒子全面にわたっ
て、ほぼ球状や半球状の突起物が化学結合により強固に
結着した金平糖状のシリカ系微粒子が容易に得られる。
このシリカ系微粒子は、例えば樹脂用充填材や表面に導
電層を被覆した導電性粒子の母材などとして好適に用い
ることができる。According to the present invention, spinous silica-like fine particles in which substantially spherical or hemispherical projections are firmly bound by chemical bonding over the entire surface of the base particles can be easily obtained.
The silica-based fine particles can be suitably used, for example, as a filler for resin or a base material of conductive particles having a surface coated with a conductive layer.
【図１】実施例１において、異形化処理で得られたシリ
カ系微粒子の走査型電子顕微鏡写真図である。FIG. 1 is a scanning electron micrograph of silica-based fine particles obtained by deforming treatment in Example 1.
【図２】実施例２において、異形化処理で得られたシリ
カ系微粒子の走査型電子顕微鏡写真図である。FIG. 2 is a scanning electron micrograph of silica-based fine particles obtained by a deforming treatment in Example 2.
【図３】実施例３において、異形化処理で得られたシリ
カ系微粒子の走査型電子顕微鏡写真図である。FIG. 3 is a scanning electron micrograph of the silica-based fine particles obtained by the deforming treatment in Example 3.
フロントページの続き Ｆターム(参考） 4G072 AA25 AA41 BB05 CC05 CC11 HH30 KK01 KK03 LL06 MM02 MM21 MM23 MM31 PP17 QQ06 RR05 TT30 UU08 4J037 AA17 AA18 CB23 CC11 CC15 DD01 DD05 DD17 DD24 EE02 EE12 EE14 EE26 EE50 FF01Continued on front page F term (reference) 4G072 AA25 AA41 BB05 CC05 CC11 HH30 KK01 KK03 LL06 MM02 MM21 MM23 MM31 PP17 QQ06 RR05 TT30 UU08 4J037 AA17 AA18 CB23 CC11 CC15 DD01 DD05 DD17 EE24 EE12 EE12 EE26 EE12 EE12 EE02 EE12 EE02 EE12 EE12 EE12 EE12 EE12 EE12 EE12 EE12 EE02 EE26
Claims (6)
たは半球状の突起物を有するシリカ系微粒子であって、
該突起物が化学結合により母体粒子に結着していること
を特徴とするシリカ系微粒子。1. Silica-based fine particles having substantially spherical and / or hemispherical projections on the entire surface of a base particle,
The silica-based fine particles, wherein the projections are bonded to the base particles by a chemical bond.
（Ｉ） Ｒ1ｎＳｉ（ＯＲ2）4-n ・・・（Ｉ） （式中、Ｒ1は炭素数１〜５のアルキル基、炭素数２〜
５のアルケニル基、炭素数６〜１０のアリール基または
炭素数７〜１０のアラルキル基、Ｒ2は炭素数１〜５の
アルキル基、ｎは１または２を示し、ｎが２の場合、２
つのＲ1はたがいに同一でも異なっていてもよく、ま
た、複数のＯＲ2はたがいに同一でも異なっていてもよ
い。）で表されるアルコキシシラン化合物に由来する組
成である請求項１に記載のシリカ系微粒子。2. The composition of both the projections and the base particles is represented by the following general formula (I): R 1 nSi (OR 2 ) 4-n (I) wherein R 1 is an alkyl having 1 to 5 carbon atoms. Group, having 2 to 2 carbon atoms
An alkenyl group having 5 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R 2 represents an alkyl group having 1 to 5 carbon atoms, n represents 1 or 2, and when n is 2,
One R 1 may be the same or different, and a plurality of OR 2 may be the same or different. 2. The silica-based fine particles according to claim 1, which has a composition derived from the alkoxysilane compound represented by the formula (1).
子径の平均値が０．０２〜０．５である請求項１または
２に記載のシリカ系微粒子。3. The silica-based fine particles according to claim 1, wherein the average value of (height of protrusions) / (base particle diameter) in the base particles is 0.02 to 0.5.
シシラン化合物を加水分解、縮合させ、場合により得ら
れた粒子をシード粒子として粒径成長させてポリオルガ
ノシロキサン粒子を生成させる工程、 （Ｂ）上記（Ａ）工程で得られたポリオルガノシロキサ
ン粒子を、表面吸着剤により表面処理する工程、および （Ｃ）上記（Ｂ）工程で表面処理されたポリオルガノシ
ロキサン粒子をシード粒子とし、前記一般式（Ｉ）で表
されるアルコキシシラン化合物を用いて、該シード粒子
全面に突起を形成させる工程、を含むことを特徴とする
シリカ系微粒子の製造方法。(A) a step of hydrolyzing and condensing the alkoxysilane compound represented by the general formula (I), and growing the obtained particles as seed particles to form polyorganosiloxane particles. (B) a step of surface-treating the polyorganosiloxane particles obtained in the step (A) with a surface adsorbent; and (C) using the polyorganosiloxane particles surface-treated in the step (B) as seed particles. Forming a projection on the entire surface of the seed particle using the alkoxysilane compound represented by the general formula (I).
項４に記載の方法。5. The method according to claim 4, further comprising (D) a baking treatment step.
ニルアルコール、ポリビニルピロリドンまたは界面活性
剤である請求項４または５に記載の方法。6. The method according to claim 4, wherein the surface adsorbent in the step (B) is polyvinyl alcohol, polyvinylpyrrolidone or a surfactant.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03208813A (en) * | 1990-01-11 | 1991-09-12 | Mitsubishi Kasei Corp | Method for producing spherical silica |
| JPH03218915A (en) * | 1989-11-29 | 1991-09-26 | Catalysts & Chem Ind Co Ltd | Production of silica powder |
| JPH03257010A (en) * | 1989-12-14 | 1991-11-15 | Nissan Chem Ind Ltd | Silica particle and its production |
| JPH03257009A (en) * | 1990-03-08 | 1991-11-15 | Tokuyama Soda Co Ltd | Silica-based filler |
| JPH04240112A (en) * | 1991-01-22 | 1992-08-27 | Ube Nitto Kasei Co Ltd | Production of silica particulates |
| JPH054812A (en) * | 1991-06-25 | 1993-01-14 | Nippon Steel Chem Co Ltd | Fine particle subspherical silica, method for producing the same, and resin film using the same |
| JPH0648720A (en) * | 1992-07-30 | 1994-02-22 | Ube Nitto Kasei Co Ltd | Production of silica particle |
| JPH0687608A (en) * | 1992-09-04 | 1994-03-29 | Ohara Inc | Production of monodispersive spherical silica |
| JPH0959014A (en) * | 1995-08-22 | 1997-03-04 | Ube Nitto Kasei Co Ltd | Hygroscopic silica particle and its production |
| JPH10203820A (en) * | 1997-01-17 | 1998-08-04 | Ube Nitto Kasei Co Ltd | Production of silica grain |
| JP2000017074A (en) * | 1998-04-28 | 2000-01-18 | Ube Nitto Kasei Co Ltd | Method for producing polyorganosiloxane fine particles |
| JP2001302227A (en) * | 2000-04-26 | 2001-10-31 | Ube Nitto Kasei Co Ltd | Method for producing silica particles |
| JP2001354408A (en) * | 2000-01-19 | 2001-12-25 | Oji Paper Co Ltd | Silica fine particle dispersion and method for producing the same |
| JP2002080598A (en) * | 2000-06-23 | 2002-03-19 | Ube Nitto Kasei Co Ltd | Method for producing polyorganosiloxane particle and method for producing silica particle |
-
2000
- 2000-07-28 JP JP2000228365A patent/JP2002038049A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03218915A (en) * | 1989-11-29 | 1991-09-26 | Catalysts & Chem Ind Co Ltd | Production of silica powder |
| JPH03257010A (en) * | 1989-12-14 | 1991-11-15 | Nissan Chem Ind Ltd | Silica particle and its production |
| JPH03208813A (en) * | 1990-01-11 | 1991-09-12 | Mitsubishi Kasei Corp | Method for producing spherical silica |
| JPH03257009A (en) * | 1990-03-08 | 1991-11-15 | Tokuyama Soda Co Ltd | Silica-based filler |
| JPH04240112A (en) * | 1991-01-22 | 1992-08-27 | Ube Nitto Kasei Co Ltd | Production of silica particulates |
| JPH054812A (en) * | 1991-06-25 | 1993-01-14 | Nippon Steel Chem Co Ltd | Fine particle subspherical silica, method for producing the same, and resin film using the same |
| JPH0648720A (en) * | 1992-07-30 | 1994-02-22 | Ube Nitto Kasei Co Ltd | Production of silica particle |
| JPH0687608A (en) * | 1992-09-04 | 1994-03-29 | Ohara Inc | Production of monodispersive spherical silica |
| JPH0959014A (en) * | 1995-08-22 | 1997-03-04 | Ube Nitto Kasei Co Ltd | Hygroscopic silica particle and its production |
| JPH10203820A (en) * | 1997-01-17 | 1998-08-04 | Ube Nitto Kasei Co Ltd | Production of silica grain |
| JP2000017074A (en) * | 1998-04-28 | 2000-01-18 | Ube Nitto Kasei Co Ltd | Method for producing polyorganosiloxane fine particles |
| JP2001354408A (en) * | 2000-01-19 | 2001-12-25 | Oji Paper Co Ltd | Silica fine particle dispersion and method for producing the same |
| JP2001302227A (en) * | 2000-04-26 | 2001-10-31 | Ube Nitto Kasei Co Ltd | Method for producing silica particles |
| JP2002080598A (en) * | 2000-06-23 | 2002-03-19 | Ube Nitto Kasei Co Ltd | Method for producing polyorganosiloxane particle and method for producing silica particle |
Cited By (32)
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|---|---|---|---|---|
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| US7476706B2 (en) | 2003-02-27 | 2009-01-13 | Ube Nitto Kasei Co., Ltd. | Method for producing polyorganosiloxane particles and for producing silica particles |
| CN100362042C (en) * | 2003-02-27 | 2008-01-16 | 宇部日东化成株式会社 | Method for producing polyorganosiloxane particles and method for producing silica particles |
| WO2004076533A1 (en) * | 2003-02-27 | 2004-09-10 | Ube Nitto Kasei Co., Ltd. | Method for producing polyorganosiloxane particles and for producing silica particles |
| US8118898B2 (en) | 2006-10-12 | 2012-02-21 | Jgc Catalysts And Chemicals Ltd. | Spinous silica-based sol and method of producing the same |
| JP2008169102A (en) * | 2006-10-12 | 2008-07-24 | Catalysts & Chem Ind Co Ltd | Konpira sugar-like sol and process for producing the same |
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| JP2008137822A (en) * | 2006-11-30 | 2008-06-19 | Catalysts & Chem Ind Co Ltd | Kinpe sugar-like inorganic oxide sol, method for producing the same, and abrasive containing the sol |
| US8187351B2 (en) | 2006-11-30 | 2012-05-29 | Jgc Catalysts And Chemicals Ltd. | Sol of spinous inorganic oxide particles, method of producing the sol, and polishing agent containing the sol |
| JP2008184371A (en) * | 2007-01-31 | 2008-08-14 | Ube Nitto Kasei Co Ltd | Method for producing metal oxide particles, metal oxide particles and resin composition |
| US10160894B2 (en) | 2007-11-30 | 2018-12-25 | Jgc Catalysts And Chemicals Ltd. | Non-spherical silica sol, process for producing the same, and composition for polishing |
| US9272916B2 (en) | 2007-11-30 | 2016-03-01 | Jgc Catalysts And Chemicals Ltd. | Non-spherical silica sol, process for producing the same, and composition for polishing |
| JP2009155180A (en) * | 2007-12-27 | 2009-07-16 | Jgc Catalysts & Chemicals Ltd | Particle-linked alumina-silica composite sol and method for producing the same |
| JP2009161371A (en) * | 2007-12-28 | 2009-07-23 | Jgc Catalysts & Chemicals Ltd | Silica sol and method for producing the same |
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| JP2010058985A (en) * | 2008-09-01 | 2010-03-18 | Jgc Catalysts & Chemicals Ltd | Silica sol and method for producing the same |
| US9416015B2 (en) | 2010-06-23 | 2016-08-16 | Fuji Xerox Co., Ltd. | Method of producing silica particles |
| US9187502B2 (en) | 2010-06-24 | 2015-11-17 | Fuji Xerox Co., Ltd. | Silica particles and method for producing the same |
| US8871344B2 (en) | 2010-06-25 | 2014-10-28 | Fuji Xerox Co., Ltd. | Hydrophobization treatment of silica particles |
| US9394413B2 (en) | 2011-01-19 | 2016-07-19 | Fuji Xerox Co., Ltd. | Resin particle and method for producing the same |
| US8962139B2 (en) | 2011-01-20 | 2015-02-24 | Fuji Xerox Co., Ltd. | Resin particle and method for producing the same |
| US8431633B2 (en) | 2011-07-06 | 2013-04-30 | Fuji Xerox Co., Ltd. | Silica particles, manufacturing method thereof and resin particles |
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