JP4271725B1 - Method for producing confetti particles - Google Patents
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- JP4271725B1 JP4271725B1 JP2008544696A JP2008544696A JP4271725B1 JP 4271725 B1 JP4271725 B1 JP 4271725B1 JP 2008544696 A JP2008544696 A JP 2008544696A JP 2008544696 A JP2008544696 A JP 2008544696A JP 4271725 B1 JP4271725 B1 JP 4271725B1
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- 239000002245 particle Substances 0.000 title claims abstract description 271
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 229920005989 resin Polymers 0.000 claims abstract description 73
- 239000011347 resin Substances 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 239000011246 composite particle Substances 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 19
- 230000018044 dehydration Effects 0.000 claims description 16
- 238000006297 dehydration reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000006482 condensation reaction Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 229920005990 polystyrene resin Polymers 0.000 claims description 11
- 229920005749 polyurethane resin Polymers 0.000 claims description 11
- 239000004925 Acrylic resin Substances 0.000 claims description 9
- 229920000178 Acrylic resin Polymers 0.000 claims description 9
- 229920006122 polyamide resin Polymers 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 40
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 25
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 18
- 230000032683 aging Effects 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 58
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 238000000635 electron micrograph Methods 0.000 description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 18
- 239000010931 gold Substances 0.000 description 18
- 229910052737 gold Inorganic materials 0.000 description 18
- 238000010992 reflux Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000007771 core particle Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- -1 oxides Chemical class 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
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- 239000002585 base Substances 0.000 description 5
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- 230000004927 fusion Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- YTJUXOIAXOQWBV-UHFFFAOYSA-N butoxy(trimethyl)silane Chemical compound CCCCO[Si](C)(C)C YTJUXOIAXOQWBV-UHFFFAOYSA-N 0.000 description 2
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- PHPGKIATZDCVHL-UHFFFAOYSA-N trimethyl(propoxy)silane Chemical compound CCCO[Si](C)(C)C PHPGKIATZDCVHL-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N trimethylsilyl-trifluoromethansulfonate Natural products C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- VJAVYPBHLPJLSN-UHFFFAOYSA-N 3-dimethoxysilylpropan-1-amine Chemical compound CO[SiH](OC)CCCN VJAVYPBHLPJLSN-UHFFFAOYSA-N 0.000 description 1
- BYIMSFXYUSZVLI-UHFFFAOYSA-N 3-methoxysilylpropan-1-amine Chemical compound CO[SiH2]CCCN BYIMSFXYUSZVLI-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
- NTHKCSDJQGWPJY-UHFFFAOYSA-N CCCC[SiH](OC)OC Chemical compound CCCC[SiH](OC)OC NTHKCSDJQGWPJY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZPECUSGQPIKHLT-UHFFFAOYSA-N bis(ethenyl)-dimethoxysilane Chemical compound CO[Si](OC)(C=C)C=C ZPECUSGQPIKHLT-UHFFFAOYSA-N 0.000 description 1
- AMSAPKJTBARTTR-UHFFFAOYSA-N butan-2-yl(trimethoxy)silane Chemical compound CCC(C)[Si](OC)(OC)OC AMSAPKJTBARTTR-UHFFFAOYSA-N 0.000 description 1
- NPVKWWQBIVSLRO-UHFFFAOYSA-N butan-2-yloxy(trimethyl)silane Chemical compound CCC(C)O[Si](C)(C)C NPVKWWQBIVSLRO-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HVHRIKGOFGJBFM-UHFFFAOYSA-N di(butan-2-yl)-dimethoxysilane Chemical compound CCC(C)[Si](OC)(OC)C(C)CC HVHRIKGOFGJBFM-UHFFFAOYSA-N 0.000 description 1
- DERJYZOBOMCDCS-UHFFFAOYSA-N di(butan-2-yloxy)-dimethylsilane Chemical compound CCC(C)O[Si](C)(C)OC(C)CC DERJYZOBOMCDCS-UHFFFAOYSA-N 0.000 description 1
- GQNWJCQWBFHQAO-UHFFFAOYSA-N dibutoxy(dimethyl)silane Chemical compound CCCCO[Si](C)(C)OCCCC GQNWJCQWBFHQAO-UHFFFAOYSA-N 0.000 description 1
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- JVUVKQDVTIIMOD-UHFFFAOYSA-N dimethoxy(dipropyl)silane Chemical compound CCC[Si](OC)(OC)CCC JVUVKQDVTIIMOD-UHFFFAOYSA-N 0.000 description 1
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 1
- BGPNEHJZZDIFND-UHFFFAOYSA-N dimethyl-bis[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(C)OC(C)(C)C BGPNEHJZZDIFND-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 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
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BKXVGDZNDSIUAI-UHFFFAOYSA-N methoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC)C1=CC=CC=C1 BKXVGDZNDSIUAI-UHFFFAOYSA-N 0.000 description 1
- FUMSHFZKHQOOIX-UHFFFAOYSA-N methoxy(tripropyl)silane Chemical compound CCC[Si](CCC)(CCC)OC FUMSHFZKHQOOIX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- AHQDZKRRVNGIQL-UHFFFAOYSA-N methyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(OC(C)(C)C)OC(C)(C)C AHQDZKRRVNGIQL-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OQTSOKXAWXRIAC-UHFFFAOYSA-N tetrabutan-2-yl silicate Chemical compound CCC(C)O[Si](OC(C)CC)(OC(C)CC)OC(C)CC OQTSOKXAWXRIAC-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- AXXDFXLLUOVTEU-UHFFFAOYSA-N tri(butan-2-yl)-methoxysilane Chemical compound CCC(C)[Si](OC)(C(C)CC)C(C)CC AXXDFXLLUOVTEU-UHFFFAOYSA-N 0.000 description 1
- RJNDDRZGJNVASH-UHFFFAOYSA-N tri(butan-2-yloxy)-methylsilane Chemical compound CCC(C)O[Si](C)(OC(C)CC)OC(C)CC RJNDDRZGJNVASH-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- NZINNJYWGLAHPB-UHFFFAOYSA-N tributyl(methoxy)silane Chemical compound CCCC[Si](CCCC)(CCCC)OC NZINNJYWGLAHPB-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-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
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- PGZGBYCKAOEPQZ-UHFFFAOYSA-N trimethyl-[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(C)C PGZGBYCKAOEPQZ-UHFFFAOYSA-N 0.000 description 1
- IEVQSSVQJPNPJB-UHFFFAOYSA-N tritert-butyl(methoxy)silane Chemical compound CO[Si](C(C)(C)C)(C(C)(C)C)C(C)(C)C IEVQSSVQJPNPJB-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Abstract
【課題】有機樹脂粒子をポリオルガノシロキサンで被覆してなる複合粒子の粒子表面にポリオルガノシロキサンの突起が形成された金平糖状の複合粒子を得る。
【解決手段】水３００重量部を仕込んだ反応容器に平均粒子径２μｍのポリメチルメタクリレート樹脂粒子を３０重量部投入し超音波で１分間照射して粒子分散液を得る。次に、上記分散液にメチルトリメトキシシラン１５重量部を添加して粒子分散液中でメチルトリメトキシシランの加水分解物を得る。その後、１重量％のアンモニア水１０重量部を添加して１分後に撹拌を停止し、静置下で１０時間熟成した後、ろ過、乾燥することにより粒子表面にポリオルガノシロキサンの突起を有する金平糖状粒子が得られる。
【選択図】図２An object of the present invention is to obtain confetti-like composite particles in which polyorganosiloxane protrusions are formed on the surface of composite particles obtained by coating organic resin particles with polyorganosiloxane.
A reaction vessel charged with 300 parts by weight of water is charged with 30 parts by weight of polymethyl methacrylate resin particles having an average particle diameter of 2 μm and irradiated with ultrasonic waves for 1 minute to obtain a particle dispersion. Next, 15 parts by weight of methyltrimethoxysilane is added to the dispersion to obtain a hydrolyzate of methyltrimethoxysilane in the particle dispersion. Thereafter, 10 parts by weight of 1% by weight of ammonia water was added, and stirring was stopped after 1 minute. After aging for 10 hours, the confetti having polyorganosiloxane protrusions on the particle surface was obtained by filtration and drying. Shaped particles are obtained.
[Selection] Figure 2
Description
本発明は、有機樹脂粒子を主としてポリオルガノシロキサンで被覆してなる複合粒子の製造方法に関するものであり、特に、該複合粒子の表面に主としてポリオルガノシロキサンの突起を有する金平糖状粒子の製造方法に関するものである。
本発明による金平糖状粒子は、各種プラスティック、各種ゴムおよび化粧品等の、滑り性、耐摩耗性、ブロッキング防止性、撥水性、光拡散性等付与剤として利用される。The present invention relates to a method for producing composite particles formed by coating organic resin particles mainly with polyorganosiloxane, and more particularly, to a method for producing gold flat sugar particles having polyorganosiloxane protrusions mainly on the surface of the composite particles. Is.
The gold flat sugar particles according to the present invention are used as an imparting agent such as slipperiness, abrasion resistance, antiblocking property, water repellency, and light diffusibility for various plastics, various rubbers and cosmetics.
ポリオルガノシロキサン粒子は、各種プラスティック、ゴム等の耐磨耗性、滑り性、光拡散性、ブロッキング防止性等の目的として幅広く利用されている。特に粒子形状が球状で平均粒子径が０．１μｍ〜１０μｍのものが好適とされている。
また機能性向上のため、ポリオルガノシロキサンを含有する複合粒子についても、その製造方法が提案されている。例えば、シリカ、アルミナ等をコア粒子とし分散した系内に、アルコキシシランを添加してポリオルガノシロキサン被覆を形成させた複合粒子を得る方法が開示されている（特許文献１参照）。
また、有機樹脂粒子をポリオルガノシロキサンで被覆してなる複合粒子についても、その製法が開示されている（特許文献２参照）。
In order to improve functionality, a method for producing composite particles containing polyorganosiloxane has also been proposed. For example, a method for obtaining composite particles in which a polyorganosiloxane coating is formed by adding alkoxysilane in a system in which silica, alumina or the like is dispersed as core particles is disclosed (see Patent Document 1).
Moreover, the manufacturing method is disclosed also about the composite particle formed by coat | covering an organic resin particle with polyorganosiloxane (refer patent document 2).
アクリル樹脂粒子、ポリウレタン樹脂粒子、ポリスチレン樹脂粒子、ポリアミド樹脂粒子等各種有機樹脂粒子は、各種プラスティック、ゴム等の添加剤や化粧品原料として利用されている。
しかしながらこれら有機樹脂粒子は、耐熱性に乏しく温度による粒子同士の融着凝集が発生するため、使用環境が限定されていた。また一般に流動性に乏しく取り扱いが困難であり、各種プラスティック、ゴム等への均一な分散が困難であった。
特に特許文献２のものでは、各種有機樹脂粒子にポリオルガノシロキサンを被覆してなる複合粒子が公開されており、流動性向上に一定の効果をあげているが十分とはいえない。しかも特許文献２のもので合成される複合粒子は、ポリオルガノシロキサンが粒子表面に均一に被覆された球状の粒子であるため、光拡散性等光学特性においても十分とはいえなかった。Various organic resin particles such as acrylic resin particles, polyurethane resin particles, polystyrene resin particles, and polyamide resin particles are used as additives such as various plastics and rubbers and cosmetic raw materials.
However, these organic resin particles have poor heat resistance and cause fusion aggregation between particles due to temperature, so that the use environment is limited. In general, it is difficult to handle due to poor fluidity, and uniform dispersion to various plastics, rubbers and the like is difficult.
In particular, in
本発明者らは、各種有機樹脂粒子をコア粒子とし、これをポリオルガノシロキサンで被覆してなる平均粒子径が０．１〜５０μｍの複合粒子において、該複合粒子の表面に突起を有した形状として金平糖状とすることにより、球形状被覆粒子と比べ流動性が飛躍的に向上するとともに、光学特性においても他素材と比べ大幅に向上することを見出し、本発明を完成するに至った。
本発明はポリオルガノシロキサンで被覆してなる複合粒子であって、該複合粒子の粒子表面にポリオルガノシロキサンの突起を有する金平糖状粒子およびその製造方法に係る以下記載の発明である。In the composite particles having an average particle diameter of 0.1 to 50 μm formed by coating various organic resin particles as core particles with polyorganosiloxane, the present inventors have a shape having protrusions on the surface of the composite particles As a result, the present inventors have found that the flowability is dramatically improved compared to the spherical coated particles, and that the optical characteristics are greatly improved compared to other materials, and the present invention has been completed.
The present invention is a composite particle formed by coating with a polyorganosiloxane, and the invention described below relates to a confetti particle having a polyorganosiloxane protrusion on the particle surface of the composite particle and a method for producing the same.
まず請求項１の発明は、オルガノトリアルコキシシランおよび／またはオルガノトリアルコキシシラン加水分解物を主成分化合物とし、該主成分化合物と、分散された有機樹脂粒子と、アルカリ性物質またはアルカリ性水溶液とを、前記主成分化合物が脱水縮合反応する前までに反応系内に添加して前記主成分化合物の脱水縮合反応を行うことで、該有機樹脂粒子表面にポリオルガノシロキサンを突起状に析出させることを特徴とする金平糖状粒子の製造方法である。
請求項２の発明は、トリオルガノモノアルコキシシラン、ジオルガノジアルコキシシラン、テトラアルコキシシラン、オルガノハロシランから選択される少なくとも１種類が副成分化合物として添加してもよいことを特徴とする請求項１記載の金平糖状粒子の製造方法である。
請求項３の発明は、分散された有機樹脂粒子と少なくとも主成分化合物との混合液に、アルカリ性物質またはアルカリ性水溶液を添加することを特徴とする請求項１または２記載の金平糖状粒子の製造方法である。
請求項４の発明は、分散された有機樹脂粒子とアルカリ性物質またはアルカリ性水溶液との混合液に、少なくとも主成分化合物を添加することを特徴とする請求項１または２記載の金平糖状粒子の製造方法である。
請求項５の発明は、少なくとも主成分化合物が非水溶性である場合、反応液は分離した２層の界面で加水分解反応が進行し、該進行により水溶性となった加水分解物が分散液側に溶解して脱水縮合反応をすることを特徴とする請求項４記載の金平糖状粒子の製造方法である。
請求項６の発明は、有機樹脂粒子とポリオルガノシロキサンの比率が、有機樹脂粒子１００重量部に対してポリオルガノシロキサンが１０〜１００重量部であり、且つ脱水縮合反応時の反応液のｐＨが８．０〜１０．５であることを特徴とする請求項１乃至５の何れか一つに記載の金平糖状粒子の製造方法である。
請求項７の発明は、有機樹脂粒子がアクリル樹脂粒子、ポリウレタン樹脂粒子、ポリスチレン樹脂粒子、ポリアミド樹脂粒子および／またはこれら有機樹脂の共重合粒子や複合粒子であることを特徴とする請求項１乃至６の何れか一つに記載の金平糖状粒子の製造方法である。
First, the invention of
The invention of
The invention according to claim 3 is characterized in that an alkaline substance or an alkaline aqueous solution is added to a mixed liquid of dispersed organic resin particles and at least a main component compound. It is.
The invention according to claim 4 is characterized in that at least a main component compound is added to a mixed liquid of dispersed organic resin particles and an alkaline substance or an alkaline aqueous solution. It is.
In the invention of
The invention of claim 6, the ratio of the organic resin particles and the polyorganosiloxane is a polyorganosiloxane 10-100 parts by weight per 100 by weight parts of the organic resin particles, and the pH of the reaction solution at the time of dehydration condensation reaction Is from 8.0 to 10.5. The method for producing confetti particles according to any one of
The invention according to claim 7 is characterized in that the organic resin particles are acrylic resin particles, polyurethane resin particles, polystyrene resin particles, polyamide resin particles and / or copolymer particles or composite particles of these organic resins. 6. The method for producing confetti particles according to any one of 6.
本発明によれば、有機樹脂粒子をポリオルガノシロキサンで被覆してなる複合粒子であって、該複合粒子の粒子表面にポリオルガノシロキサンの突起を有する金平糖状の複合粒子を工業的に有利な方法で効率よく製造することが出来る。 According to the present invention, a composite particle obtained by coating organic resin particles with a polyorganosiloxane, which is an industrially advantageous method for producing confetti-like composite particles having polyorganosiloxane protrusions on the particle surface of the composite particles. Can be manufactured efficiently.
以下に本発明について詳しく説明する。
本発明の金平糖状粒子は、主成分化合物としてオルガノトリアルコキシシランを加水分解、脱水縮合させる工程において、有機樹脂粒子を該主成分化合物が脱水縮合する前までに反応系内に添加して、該有機樹脂粒子表面にポリオルガノシロキサンを析出させることにより得られる。The present invention is described in detail below.
In the process of hydrolyzing and dehydrating and condensing organotrialkoxysilane as the main component compound, the konpeito sugar particles of the present invention are added to the reaction system before the main component compound is dehydrated and condensed, It can be obtained by depositing polyorganosiloxane on the surface of the organic resin particles.
有機樹脂粒子は具体的には、アクリル樹脂、ポリウレタン樹脂、ポリスチレン樹脂、ポリアミド樹脂、フェノール樹脂、メラミン樹脂またはこれらを含有する複合樹脂粒子および／または共重合樹脂粒子からなる。 Specifically, the organic resin particles include acrylic resin, polyurethane resin, polystyrene resin, polyamide resin, phenol resin, melamine resin, or composite resin particles and / or copolymer resin particles containing these.
本発明に使用される有機樹脂粒子は一般的な製造方法で得られるものでよく、その平均粒子径および粒度分布についても特に限定されるものではなく、使用目的、用途により適宜選定される。
また、各種有機樹脂粒子の架橋の有無についても特に限定されない。
さらにまた、該有機樹脂粒子の形状は、真球状、じゃがいも状、微粒子凝集体状等、外観が略球状となっていれば特に限定されない。The organic resin particles used in the present invention may be obtained by a general production method, and the average particle size and particle size distribution are not particularly limited, and are appropriately selected depending on the purpose of use and application.
In addition, the presence or absence of crosslinking of various organic resin particles is not particularly limited.
Furthermore, the shape of the organic resin particles is not particularly limited as long as the appearance is substantially spherical, such as a true spherical shape, a potato shape, or a fine particle aggregate shape.
本発明に用いる球状樹脂粒子は、乾燥した樹脂粒子または予め溶媒分散した樹脂粒子をいう。 The spherical resin particles used in the present invention are dry resin particles or resin particles dispersed in advance in a solvent.
本発明に用いる球状樹脂粒子の添加量は、反応液１００重量部に対し、１〜５０重量部であり、１重量部以下では単位容積当りの収量が悪くなり、また５０重量部以上では粒子同士の凝集が発生して金平糖状粒子として取り出せなくなる。
The addition amount of the spherical resin particles used in the present invention, compared
本発明で使用される反応初液および有機樹脂粒子用分散媒は、電気伝導度５００μＳ／ｃｍ以下の水または該水と水溶性有機溶剤との混合物である。 The reaction initial solution and the dispersion medium for organic resin particles used in the present invention are water having an electric conductivity of 500 μS / cm or less or a mixture of the water and a water-soluble organic solvent.
上記水溶性有機溶剤とは水溶性で主成分化合物であるオルガノトリアルコキシシラン、副成分化合物であるトリオルガノモノアルコキシシラン、ジオルガノジアルコキシシラン、テトラアルコキシシラン、オルガノハロシランおよび各種球状樹脂粒子に対して不活性であれば特に限定されないが、入手が容易であることから低級アルコールが好ましい。
水と水溶性有機溶媒との混合比率は、水１重量部に対し水溶性有機溶媒１重量部以下が好ましい。
The above water-soluble organic solvents are water-soluble, organotrialkoxysilane, which is a main component compound, triorganomonoalkoxysilane, diorganodialkoxysilane, tetraalkoxysilane, organohalosilane, and various spherical resin particles, which are accessory components. Although it will not specifically limit if it is inert with respect to it, A lower alcohol is preferable from availability.
The mixing ratio of water and a water-soluble organic solvent is preferably less than 1 by weight part water-soluble organic solvent to 1 part by weight of water.
球状樹脂粒子の分散方法は、球状樹脂粒子が分散すればよく、分散方法はとくに限定されないが、超音波分散が好適に用いられる。
また、疎水性樹脂粒子の場合は水溶性有機溶剤に予め分散させることが有効である。The spherical resin particles may be dispersed by any method as long as the spherical resin particles are dispersed. The dispersion method is not particularly limited, but ultrasonic dispersion is preferably used.
In the case of hydrophobic resin particles, it is effective to disperse in a water-soluble organic solvent in advance.
本発明で使用される主成分化合物であるオルガノトリアルコキシシランは、一般式
Ｒ１Ｓｉ（ＯＲ２）３
で示される。
該一般式において、Ｒ１はメチル基、エチル基、プロピル基、ブチル基などの炭素数１〜６の直鎖状あるいは分枝状のアルキル基、フェニル基、アミノ基、エポキシ基、あるいはビニル基を少なくとも１個有する１価の有機基であり、またＲ２はＲ１と同様の炭素数１〜６の直鎖状あるいは分枝状のアルキル基である。Organotrialkoxysilane, which is a main component compound used in the present invention, has a general formula R 1 Si (OR 2 ) 3.
Indicated by
In the general formula, R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a phenyl group, an amino group, an epoxy group, or a vinyl group. And R 2 is a linear or branched alkyl group having 1 to 6 carbon atoms similar to R 1 .
さらに具体的には、オルガノトリアルコキシシランとしては、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−ｎ−プロポキシシラン、メチルトリ−ｉ−プロポキシシラン、メチルトリ−ｎ−ブトキシシラン、メチルトリ−ｉ−ブトキシシラン、メチルトリ−ｓ−ブトキシシラン、メチルトリ−ｔ−ブトキシシラン、エチルトリメトキシシラン、ｎ−プロピルトリメトキシシラン、ｉ−プロピルトリメトキシシラン、ｎ−ブチルトリメトキシシラン、ｓ−ブチルトリメトキシシラン、ｔ−ブチ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、ビニルトリメトキシシラン、フェニルトリメトキシシランなどが例示される。 More specifically, as the organotrialkoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-i-butoxysilane , Methyltri-s-butoxysilane, methyltri-t-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, i-propyltrimethoxysilane, n-butyltrimethoxysilane, s-butyltrimethoxysilane, t- Examples include butyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, and phenyltrimethoxysilane.
これらのオルガノトリアルコキシシランは単独、あるいは二種以上の混合物で用いても良いが、これらオルガノトリアルコキシシランのうち、入手が容易なメチルトリメトキシシラン、フェニルトリメトキシシランが好適に用いられる。 These organotrialkoxysilanes may be used alone or in a mixture of two or more. Among these organotrialkoxysilanes, methyltrimethoxysilane and phenyltrimethoxysilane, which are easily available, are preferably used.
本発明で用いられるオルガノトリアルコキシシランの添加量は、有機樹脂粒子１００重量部に対してポリオルガノシロキサンとして１０〜１００重量部が好ましく、１０重量部以下では突起が形成し難くなり、１００重量部を越えるとポリオルガノシロキサン単独粒子が発生し易くなる。 The addition amount of the organotrialkoxysilane used in the present invention, 10 to 100 parts by weight polyorganosiloxane preferably per 100 by weight parts of the organic resin particles, it is difficult to form projections in the following 10 by weight part, 100 polyorganosiloxane alone particles easily occurs exceeds weight unit.
本発明における合成方法としては、前述した主成分化合物と、有機樹脂粒子と、アルカリ性物質またはアルカリ性水溶液とを、前記主成分化合物が脱水縮合反応する前までに反応系内に添加して前記主成分化合物の脱水縮合反応を行うことで、該有機樹脂粒子表面にポリオルガノシロキサンを突起状に析出させるものであればどのような方法であっても良く、そのようなものにおいて、具体的な第一の合成方法としては、分散された有機樹脂粒子と少なくとも主成分化合物との混合液に、アルカリ性物質またはアルカリ性水溶液を添加する金平糖状粒子の製造方法である。さらに具体的には、
Ａ）球状樹脂粒子を水または水と水溶性有機溶剤との混合液に分散させた系内に、撹拌下で少なくとも主成分化合物を添加して、少なくとも主成分化合物の加水分解物を得る工程、
Ｂ）これにアルカリ性物質またはアルカリ性水溶液を添加して、少なくとも主成分化合物の加水分解物を脱水縮合させ、該球状樹脂粒子表面にポリオルガノシロキサンとして析出させる工程からなる。As a synthesis method in the present invention, the main component compound, the organic resin particles, and an alkaline substance or an alkaline aqueous solution are added to the reaction system before the main component compound undergoes a dehydration condensation reaction. Any method may be used as long as the polyorganosiloxane is precipitated in the shape of protrusions on the surface of the organic resin particles by performing a dehydration condensation reaction of the compound. This synthesis method is a method for producing gold flat sugar particles in which an alkaline substance or an alkaline aqueous solution is added to a mixed liquid of dispersed organic resin particles and at least a main component compound. More specifically,
A) A step of adding at least a main component compound under stirring to a system in which spherical resin particles are dispersed in water or a mixed solution of water and a water-soluble organic solvent to obtain a hydrolyzate of at least the main component compound,
B) It comprises a step of adding an alkaline substance or an alkaline aqueous solution to dehydrate and condense at least the hydrolyzate of the main component compound and depositing it on the surface of the spherical resin particles as polyorganosiloxane.
また、本発明の具体的な第二の合成方法としては、有機樹脂粒子分散液とアルカリ性物質またはアルカリ性水溶液との混合液に、少なくとも主成分化合物を添加する金平糖状粒子の製造方法である。この合成方法の中には、少なくとも主成分化合物が非水溶性である場合、反応液は分離した２層の界面で加水分解反応が進行し、該進行により水溶性となった加水分解物が分散液側に溶解して脱水縮合反応をするものも含むものとする。
さらに本発明の第三の合成方法としては、有機樹脂粒子分散液に、アルカリ性物質またはアルカリ性水溶液との混合液と、少なくとも主成分化合物とを同時的に添加する金平糖状粒子の製造方法である。そしてこれらを実施する場合に、前記第一の方法において具体的に記載した手法を採用することができる。A specific second synthesis method of the present invention is a method for producing gold flat sugar particles in which at least a main component compound is added to a mixed liquid of an organic resin particle dispersion and an alkaline substance or an aqueous alkaline solution. In this synthesis method, when at least the main component compound is water-insoluble, the reaction solution undergoes a hydrolysis reaction at the interface between the two separated layers, and the hydrolyzate that has become water-soluble due to the progress is dispersed. Including those that dissolve on the liquid side and undergo a dehydration condensation reaction.
Furthermore, the third synthesis method of the present invention is a method for producing confetti sugar particles in which a mixed liquid of an alkaline substance or an alkaline aqueous solution and at least a main component compound are simultaneously added to an organic resin particle dispersion. And when implementing these, the method concretely described in said 1st method is employable.
少なくとも主成分化合物の添加方法は特に限定されず、短時間で投入しても良く、また連続滴下しても構わない。 The method for adding at least the main component compound is not particularly limited, and it may be added in a short time or may be continuously dropped.
アルカリ性物質とは、一般に周期律表Ｉａ属、ＩＩａ属の金属の水酸化物、酸化物、炭酸塩または有機窒素化合物、アンモニアなどが挙げられ、アルカリ性水溶液とは前記したアルカリ性物質の水溶液であるが、反応後除去しやすいことから、特にアンモニアが好ましい。これらアルカリ性物質および／またはその水溶液は単独でも、あるいは２種類以上を混合して用いても良い。また、該アルカリ水溶液に水溶性有機溶剤、界面活性剤などが含まれていても使用することが出来る。 Alkaline substances generally include hydroxides, oxides, carbonates or organic nitrogen compounds, ammonia, etc. of metals of Group Ia and Group IIa of the periodic table. Alkaline aqueous solutions are aqueous solutions of the aforementioned alkaline substances. Ammonia is particularly preferred because it is easy to remove after the reaction. These alkaline substances and / or aqueous solutions thereof may be used alone or in combination of two or more. The aqueous alkali solution can be used even if it contains a water-soluble organic solvent, a surfactant or the like.
アルカリ性物質またはアルカリ性水溶液の添加量は、主成分化合物の脱水縮合反応時の反応液のｐＨが８．０〜１０．５の範囲となるように添加することが望ましく、ｐＨが８．０以下では粒子同士の融着が発生し易く、ｐＨが１０．５を超えると脱水縮合反応が早すぎて有機樹脂粒子の表面に突起が形成し難くなり、均一にポリオルガノシロキサンが被覆した単純な球状複合粒子となり易い。 The addition amount of the alkaline substance or the aqueous alkaline solution is desirably added so that the pH of the reaction solution during the dehydration condensation reaction of the main component compound is in the range of 8.0 to 10.5. A simple spherical composite in which polyorganosiloxane is uniformly coated because particles are likely to be fused, and when the pH exceeds 10.5, the dehydration condensation reaction is too early to form protrusions on the surface of the organic resin particles. Easy to become particles.
アルカリ性物質またはアルカリ性水溶液を添加することで主成分化合物の加水分解物を脱水縮合させるときの反応液温度としては、１０〜６０℃が好ましい。 The reaction solution temperature when dehydrating and condensing the hydrolyzate of the main component compound by adding an alkaline substance or an aqueous alkaline solution is preferably 10 to 60 ° C.
アルカリ性物質またはアルカリ性水溶液の添加方法は、反応液撹拌下で、速やかに添加することが望ましい。また、アルカリ性物質またはアルカリ性水溶液を添加する際の反応液の撹拌は特に限定されないが、強い撹拌とすると粒子同士の融着、あるいは不定形粒子が生成する場合があるので、通常、液が混合されている程度の、穏やかな撹拌であることが好ましい。 As for the method of adding the alkaline substance or the alkaline aqueous solution, it is desirable to add it quickly while stirring the reaction solution. In addition, the stirring of the reaction liquid when adding an alkaline substance or an aqueous alkaline solution is not particularly limited, but if the stirring is strong, the particles may be fused together, or amorphous particles may be formed. It is preferable that the stirring be gentle.
本発明を実施するにあたり、主成分化合物である前述したオルガノトリアルコキシシランに、副成分化合物としてトリオルガノモノアルコキシシラン、ジオルガノジアルコキシシラン、テトラアルコキシシラン、オルガノハロシランから選択される少なくとも１種類を副成分化合物として添加してもよい。 In carrying out the present invention, at least one selected from triorganomonoalkoxysilanes, diorganodialkoxysilanes, tetraalkoxysilanes, and organohalosilanes as accessory component compounds to the aforementioned organotrialkoxysilanes that are the main component compounds. May be added as an accessory component compound.
トリオルガノモノアルコキシシランとしては、トリメチルモノメトキシシラン、トリメチルモノエトキシシラン、トリメチルモノ−ｎ−プロポキシシラン、トリメチルモノ−ｉ−プロポキシシラン、トリメチルモノ−ｎ−ブトキシシラン、トリメチルモノ−ｉ−ブトキシシラン、トリメチルモノ−ｓ−ブトキシシラン、トリメチルモノ−ｔ−ブトキシシラン、トリエチルモノメトキシシラン、トリ−ｎ−プロピルモノメトキシシラン、トリ−ｉ−プロピルモノメトキシシラン、トリ−ｎ−ブチルモノメトキシシラン、トリ−ｓ−ブチルモノメトキシシラン、トリ−ｔ−ブチルモノメトキシシラン、トリ−Ｎ−β（アミノエチル）γ−アミノプロピルモノメトキシシラン、トリ−γ−グリシドキシプロピルモノメトキシシラン、トリビニルモノメトキシシラン、トリフェニルモノメトキシシランなどが例示される。 Examples of the triorganomonoalkoxysilane include trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmono-n-propoxysilane, trimethylmono-i-propoxysilane, trimethylmono-n-butoxysilane, trimethylmono-i-butoxysilane, Trimethylmono-s-butoxysilane, trimethylmono-t-butoxysilane, triethylmonomethoxysilane, tri-n-propylmonomethoxysilane, tri-i-propylmonomethoxysilane, tri-n-butylmonomethoxysilane, tri- s-butylmonomethoxysilane, tri-t-butylmonomethoxysilane, tri-N-β (aminoethyl) γ-aminopropylmonomethoxysilane, tri-γ-glycidoxypropylmonomethoxysilane, trivinylmonomethyl Kishishiran, triphenyl monomethoxy silane is exemplified.
ジオルガノジアルコキシしランとしては、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジ−ｎ−プロポキシシラン、ジメチルジ−ｉ−プロポキシシラン、ジメチルジ−ｎ−ブトキシシラン、ジメチルジ−ｉ−ブトキシシラン、ジメチルジ−ｓ−ブトキシシラン、ジメチルジ−ｔ−ブトキシシラン、ジエチルジメトキシシラン、ジ−ｎ−プロピルジメトキシシラン、ジ−ｉ−プロピルジメトキシシラン、ジ−ｎ−ブチルジメトキシシラン、ジ−ｓ−ブチルジメトキシシラン、ジ−ｔ−ブチルジメトキシシラン、ジ−Ｎ−β（アミノエチル）γ−アミノプロピルジメトキシシラン、ジ−γ−グリシドキシプロピルジメトキシシラン、ジビニルジメトキシシラン、ジフェニルジメトキシシランなどが例示される。 Diorganodialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-i-butoxysilane, dimethyldi-s- Butoxysilane, dimethyldi-t-butoxysilane, diethyldimethoxysilane, di-n-propyldimethoxysilane, di-i-propyldimethoxysilane, di-n-butyldimethoxysilane, di-s-butyldimethoxysilane, di-t- Examples include butyldimethoxysilane, di-N-β (aminoethyl) γ-aminopropyldimethoxysilane, di-γ-glycidoxypropyldimethoxysilane, divinyldimethoxysilane, and diphenyldimethoxysilane.
テトラアルコキシシランとしては、テトラメトキシシラン、テトラエトキシシラン、テトラ−ｎ−プロポキシシラン、テトラ−ｉ−プロポキシシラン、テトラ−ｎ−ブトキシシラン、テトラ−ｉ−ブトキシシラン、テトラ−ｓ−ブトキシシラン、テトラ−ｔ−ブトキシシランなどが例示される。 Examples of tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-s-butoxysilane, tetra -T-butoxysilane and the like are exemplified.
オルガノハロシランとしては、メチルトリクロロシラン、ジメチルジクロロシラン、トリメチルモノクロロシラン、エチルトリクロロシラン、ジエチルジクロロシラン、トリエチルモノクロロシランなどが例示される。 Examples of the organohalosilane include methyltrichlorosilane, dimethyldichlorosilane, trimethylmonochlorosilane, ethyltrichlorosilane, diethyldichlorosilane, and triethylmonochlorosilane.
本発明では、アルカリ性物質またはアルカリ性水溶液の存在下において、主成分化合物であるオルガノトリアルコキシシランおよび／またはオルガノトリアルコキシシランの加水分解物を脱水縮合反応させることになるが、この場合に、脱水縮合させた反応液スラリーに、さらにオルガノトリアルコキシシランおよび／またはオルガノトリアルコキシシランの加水分解物が脱水縮合することにより、先に合成した金平糖状粒子のポリオルガノシロキサン層を成長させることができる。 In the present invention, the main component compound organotrialkoxysilane and / or hydrolyzate of organotrialkoxysilane is subjected to a dehydration condensation reaction in the presence of an alkaline substance or an alkaline aqueous solution. The organotrialkoxysilane and / or organotrialkoxysilane hydrolyzate is further subjected to dehydration condensation on the reaction liquid slurry thus prepared, so that the polyorganosiloxane layer of the synthesizer confetti particles previously synthesized can be grown.
この場合、主成分化合物の添加速度は、速すぎるとポリオルガノシロキサン単独粒子が発生し易くなるので、時間をかけて滴下するほうが望ましい。 In this case, if the addition rate of the main component compound is too high, polyorganosiloxane single particles are likely to be generated.
このようにして合成した粒子は、その後、ろ過分離・水洗浄あるいは有機溶剤洗浄をした後、乾燥し、場合によっては解砕して微粒子を得る。
得られた粒子は、粒子表面にポリオルガノシロキサンの突起を有する金平糖状粒子であり、該金平糖状粒子の突起の大きさが、母体粒子からの高さ方向および幅方向ともに母体粒子径の１／５０〜１／２であり、該突起が母体粒子表面全体の１／２以上に形成される。
また、前述したように金平糖状のポリオルガノシロキサンを脱水縮合反応して合成した後、反応系内に各種のシランカップリング剤等を添加することで表面処理をすることもできる。
以下に実施例を比較例と共に記載するが、本発明は以下に記載される実施例に限定されないものであることはいうまでもない。The particles thus synthesized are then filtered, washed with water, or washed with an organic solvent, and then dried and, if necessary, crushed to obtain fine particles.
The obtained particles are gold flat sugar particles having polyorganosiloxane protrusions on the particle surface, and the size of the protrusions of the gold flat sugar particles is 1 / of the base particle diameter in the height direction and the width direction from the base particles. 50 to 1/2, and the protrusions are formed on half or more of the entire surface of the base particle.
Further, as described above, after synthesizing a confetti polyorganosiloxane by dehydration condensation reaction, surface treatment can be performed by adding various silane coupling agents and the like in the reaction system.
Although an example is described below with a comparative example, it cannot be overemphasized that this invention is not limited to an example described below.
＜実施例１＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径７μｍである球状ポリウレタン樹脂粒子（根上工業株式会社製アートパールＣ−８００（透明））を２２．５重量部投入し、超音波を１分間照射して、ポリウレタン樹脂粒子分散液を得た。
次に、上記分散液を液温３０℃として、メチルトリメトキシシラン１５重量部を添加して、ポリウレタン樹脂粒子分散液中でメチルトリメトキシシランの加水分解物を得た。
引き続き液温を３０℃に維持して３０分間撹拌した後、１重量％のアンモニア水１０重量部を速やかに添加して、１分後に撹拌を停止した。このときの反応液のｐＨは９．７であった。
静置下で２時間熟成した後、ろ過、乾燥して白色粉末を得た。得られた白色粉末の重量は２８．８ｇであった。原料の仕込み比率から、ポリウレタン樹脂粒子１００重量部に対しポリメチルシルセスキオキサンは３３重量部となる。
得られた粉末を電子顕微鏡観察したところ、図１に示す写真図のように粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。
得られた粒子の突起物の大きさを突起物１００個について測定した平均は、母体粒子からの高さが０．２μｍ、幅が０．３μｍであった。
コア粒子である根上工業製アートパールＣ−８００（透明）を差動型示差熱天秤（以下「ＴＧ−ＤＴＡ」と称する：理学電機株式会社製ＴＧ８１２０）で測定をしたところ２００℃から４４５℃の重量減量率が７６．７重量％であったが、実施例１で得られた複合粒子の２００℃から４４５℃の重量減量率は６９．８重量％であった。
根上工業製アートパールＣ−８００（透明）と実施例１で得られた金平糖状粒子を１５０℃で熱処理したところ、アートパールＣ−８００（透明）は粒子同士の融着により流動性が損なわれていたが、実施例１で得られた金平糖状粒子は粒子同士の融着は確認されず、処理前と同様な流動性を維持していた。続いて２００℃で熱処理したが実施例１の金平糖状粒子の粒子同士の融着は確認されず、処理前と同様な流動性を維持していた。これらはポリオルガノシルセスキオキサンを被覆したことで耐熱性が向上したと考えられる。<Example 1>
Into a reaction vessel equipped with a thermometer, a reflux device, and a stirring device, 300 parts by weight of water was charged, and spherical polyurethane resin particles having an average particle diameter of 7 μm (Art Pearl C-800 (transparent) manufactured by Negami Kogyo Co., Ltd.) 22 .5 parts by weight was added and irradiated with ultrasonic waves for 1 minute to obtain a polyurethane resin particle dispersion.
Next, 15 parts by weight of methyltrimethoxysilane was added at a liquid temperature of 30 ° C. to obtain a hydrolyzate of methyltrimethoxysilane in the polyurethane resin particle dispersion.
Subsequently, after stirring for 30 minutes while maintaining the liquid temperature at 30 ° C., 10 parts by weight of 1 wt% aqueous ammonia was quickly added, and stirring was stopped after 1 minute. The pH of the reaction solution at this time was 9.7.
The mixture was aged for 2 hours and then filtered and dried to obtain a white powder. The weight of the obtained white powder was 28.8 g. From the raw material charge ratio, polymethylsilsesquioxane is 33 parts by weight per 100 parts by weight of the polyurethane resin particles.
When the obtained powder was observed with an electron microscope, as shown in the photograph shown in FIG. 1, confetti particles having protrusions on the particle surface were observed, but almost no polymethylsilsesquioxane single particles could be confirmed.
The average of the protrusions of the obtained particles measured for 100 protrusions was 0.2 μm in height from the base particle and 0.3 μm in width.
The core particle Art Pearl C-800 (transparent), which is a core particle, was measured with a differential type differential thermal balance (hereinafter referred to as “TG-DTA”: TG8120 manufactured by Rigaku Corporation). Although the weight loss rate was 76.7% by weight, the weight loss rate from 200 ° C. to 445 ° C. of the composite particles obtained in Example 1 was 69.8% by weight.
When the Nepal Industrial Art Pearl C-800 (transparent) and the gold flat sugar particles obtained in Example 1 were heat-treated at 150 ° C., the fluidity of Art Pearl C-800 (transparent) was impaired by the fusion of the particles. However, the gold flat sugar particles obtained in Example 1 were not confirmed to be fused with each other, and maintained the same fluidity as before the treatment. Subsequently, heat treatment was performed at 200 ° C., but fusion of the particles of the confetti particles of Example 1 was not confirmed, and the same fluidity as before the treatment was maintained. These are considered to have improved heat resistance by coating with polyorganosilsesquioxane.
＜実施例２〜７＞
実施例２および３は、反応温度を表１のようにした以外は実施例１と同様にして金平糖状粒子を得た。
実施例４および５は仕込み量を表１のようにした以外は実施例１と同様にして金平糖状粒子を得た。
実施例６および７は球状ポリウレタン粒子の平均粒子径を表１に示したものを用いて、仕込み量を表１のようにした以外は実施例１と同様にして金平糖状粒子を得た。<Examples 2 to 7>
In Examples 2 and 3, confetti particles were obtained in the same manner as in Example 1 except that the reaction temperature was as shown in Table 1.
In Examples 4 and 5, gold flat sugar-like particles were obtained in the same manner as in Example 1 except that the amounts charged were as shown in Table 1.
Examples 6 and 7 were obtained by using the average particle diameter of spherical polyurethane particles shown in Table 1, except that the amount charged was as shown in Table 1, and obtained confetti particles as in Example 1.
＜実施例８＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径２μｍであるポリメチルメタクリレート樹脂粒子（根上工業製アートパールＪ−４Ｐ）を３０重量部投入し、超音波を１分間照射して、ポリメチルメタクリレート樹脂粒子分散液を得た。
次に、上記分散液を液温３０℃として、メチルトリメトキシシラン１５重量部を添加して、ポリメチルメタクリレート樹脂粒子分散液中でメチルトリメトキシシランの加水分解物を得た。
引き続き液温を３０℃に維持して３０分間撹拌した後、１重量％のアンモニア水１０重量部を速やかに添加して、１分後に撹拌を停止した。このときの反応液ｐＨは９．６であった。
静置下で１０時間熟成した後、ろ過、乾燥して白色粉末を得た。原料の仕込み比率から、ポリメチルメタクリレート樹脂粒子１００重量部に対しポリメチルシルセスキオキサンは２５重量部となる。
得られた白色粉末の重量は２９．１ｇであった。得られた粉末を電子顕微鏡観察したところ、図２に示す写真図のように粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。
得られた粒子の突起物の大きさを突起物１００個について測定した平均値は、母体粒子からの高さが０．３μｍ、幅が０．５μｍであった。
コア粒子である根上工業製アートパールＪ−４ＰをＴＧ−ＤＴＡで測定をしたところ、２００℃から４４５℃の重量減量率が１００重量％であったが、実施例８で得られた複合粒子の重量減量率は９２重量％となった。
根上工業製アートパールＪ−４Ｐと実施例８で得られた金平糖状粒子を１５０℃で熱処理したところ、アートパールＪ−４Ｐは粒子同士の融着により流動性が損なわれていたが、実施例８で得られた金平糖状粒子は粒子同士の融着は確認されず、処理前と同様な流動性を維持していた。続いて２００℃で熱処理したが実施例８の金平糖状粒子の粒子同士の融着は確認されず、処理前と同様な流動性を維持していた。これらはポリオルガノシルセスキオキサンを被覆したことで耐熱性が向上したと考えられる。<Example 8>
A reaction vessel equipped with a thermometer, a reflux device and a stirrer was charged with 300 parts by weight of water, and 30 parts by weight of polymethyl methacrylate resin particles (Negami Kogyo Art Pearl J-4P) having an average particle diameter of 2 μm were added thereto. Then, an ultrasonic wave was irradiated for 1 minute to obtain a polymethyl methacrylate resin particle dispersion.
Next, 15 parts by weight of methyltrimethoxysilane was added at a liquid temperature of 30 ° C. to obtain a hydrolyzate of methyltrimethoxysilane in the polymethyl methacrylate resin particle dispersion.
Subsequently, after stirring for 30 minutes while maintaining the liquid temperature at 30 ° C., 10 parts by weight of 1 wt% aqueous ammonia was quickly added, and stirring was stopped after 1 minute. The reaction solution pH at this time was 9.6.
The mixture was aged for 10 hours and then filtered and dried to obtain a white powder. From the raw material charge ratio, polymethylsilsesquioxane is 25 parts by weight per 100 parts by weight of the polymethyl methacrylate resin particles.
The weight of the obtained white powder was 29.1 g. When the obtained powder was observed with an electron microscope, confetti particles having protrusions on the particle surface were observed as shown in the photograph of FIG. 2, but almost no polymethylsilsesquioxane single particles could be confirmed.
The average value obtained by measuring the size of the protrusions of the obtained particles with respect to 100 protrusions was 0.3 μm in height from the base particles and 0.5 μm in width.
The core particle Art Pearl J-4P manufactured by Negami Kogyo was measured with TG-DTA. The weight loss rate from 200 ° C. to 445 ° C. was 100% by weight. The composite particles obtained in Example 8 The weight loss rate was 92% by weight.
Nepal Kogyo Art Pearl J-4P and the gold flat sugar particles obtained in Example 8 were heat-treated at 150 ° C., and Art Pearl J-4P was impaired in fluidity by fusion of the particles. The confetti particles obtained in No. 8 were not confirmed to be fused with each other, and maintained the same fluidity as before the treatment. Subsequently, heat treatment was performed at 200 ° C., but the fusion of the confetti particles of Example 8 was not confirmed, and the same fluidity as before the treatment was maintained. These are considered to have improved heat resistance by coating with polyorganosilsesquioxane.
＜実施例９〜１６＞
実施例９は、反応温度を表２のようにした以外は実施例１と同様にして金平糖状粒子を得た。
実施例１０〜１２は仕込み量を表２のようにした以外は実施例１と同様にして金平糖状粒子を得た。
実施例１３および１４はコア粒子の平均粒子径を表２に示したものを用いて、仕込み量を表２のようにした以外は実施例１と同様にして金平糖状粒子を得た。
実施例１５および１６はコア粒子種を表２のようにした以外は実施例１と同様にして金平糖状粒子を得た。<Examples 9 to 16>
In Example 9, confetti particles were obtained in the same manner as in Example 1 except that the reaction temperature was as shown in Table 2.
In Examples 10 to 12, gold flat sugar-like particles were obtained in the same manner as in Example 1 except that the amounts charged were as shown in Table 2.
Examples 13 and 14 were obtained in the same manner as in Example 1 except that the average particle diameter of the core particles shown in Table 2 was used, and the charged amount was as shown in Table 2.
In Examples 15 and 16, confetti particles were obtained in the same manner as in Example 1 except that the core particle types were as shown in Table 2.
＜実施例１７＞
温度計、還流装置および撹拌装置を備えた反応容器にメタノール５０重量部を仕込み、これに平均粒子径５μｍである球状ポリアミド樹脂粒子を２２．５重量部投入し、超音波を１分間照射して、ポリアミド微粒子分散液を得た後、水を２５０重量部仕込み、球状ポリアミド樹脂粒子分散液を得た。
次に、上記分散液を液温３０℃として、メチルトリメトキシシラン１５重量部を添加して、メチルトリメトキシシランの加水分解物を得た。
引き続き液温を３０℃に維持して３０分間撹拌した後、１重量％のアンモニア水１０重量部を速やかに添加して、１分後に撹拌を停止した。このときの反応液ｐＨは９．５であった。
静置下で１０時間熟成した後、ろ過、乾燥して白色粉末を得た。原料の仕込み比率から、ポリアミド樹脂粒子１００重量部に対しポリメチルシルセスキオキサンは３３重量部となる。
得られた白色粉末の重量は２９．２ｇであった。得られた粉末を電子顕微鏡観察したところ、図３に示す写真図のように粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。
コア粒子である球状ポリアミド樹脂粒子をＴＧ−ＤＴＡで測定をしたところ、２００℃から４４５℃の重量減量率が７６．７重量％であったが、実施例１７で得られた複合粒子の重量減量率は６９．８重量％となった。
<Example 17>
A thermometer, was charged with
Next, 15 parts by weight of methyltrimethoxysilane was added at a liquid temperature of 30 ° C. to obtain a hydrolyzate of methyltrimethoxysilane.
Subsequently, after stirring for 30 minutes while maintaining the liquid temperature at 30 ° C., 10 parts by weight of 1 wt% aqueous ammonia was quickly added, and stirring was stopped after 1 minute. The reaction solution pH at this time was 9.5.
The mixture was aged for 10 hours and then filtered and dried to obtain a white powder. From the raw material charge ratio, polymethylsilsesquioxane is 33 parts by weight per 100 parts by weight of the polyamide resin particles.
The weight of the obtained white powder was 29.2 g. When the obtained powder was observed with an electron microscope, confetti particles having protrusions on the particle surface were observed as shown in the photograph of FIG. 3, but almost no polymethylsilsesquioxane single particles could be confirmed.
When the spherical polyamide resin particles as the core particles were measured by TG-DTA, the weight loss rate from 200 ° C. to 445 ° C. was 76.7% by weight, but the weight loss of the composite particles obtained in Example 17 was The rate was 69.8% by weight.
＜実施例１８＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径１μｍである球状ポリスチレン樹脂粒子を２５重量部投入し、超音波を１分間照射して、球状ポリスチレン樹脂粒子分散液を得た。
次に、上記分散液を液温３０℃として、メチルトリメトキシシラン２０重量部を添加して、メチルトリメトキシシランの加水分解物を得た。
引き続き液温を３０℃に維持して３０分間撹拌した後、１重量％のアンモニア水１０重量部を速やかに添加して、１分後に撹拌を停止した。このときの反応液ｐＨは９．８であった。
静置下で１０時間熟成した後、ろ過、乾燥して淡白色粉末を得た。原料の仕込み比率から、ポリスチレン樹脂粒子１００重量部に対しポリメチルシルセスキオキサンは３９重量部となる。
得られた白色粉末の重量は３３．９ｇであった。得られた粉末を電子顕微鏡観察したところ、図４に示す写真図のように粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。<Example 18>
A reaction vessel equipped with a thermometer, a reflux device and a stirrer was charged with 300 parts by weight of water, and 25 parts by weight of spherical polystyrene resin particles having an average particle diameter of 1 μm were added thereto, irradiated with ultrasonic waves for 1 minute, and spherical A polystyrene resin particle dispersion was obtained.
Next, 20 parts by weight of methyltrimethoxysilane was added at a liquid temperature of 30 ° C. to obtain a hydrolyzate of methyltrimethoxysilane.
Subsequently, after stirring for 30 minutes while maintaining the liquid temperature at 30 ° C., 10 parts by weight of 1 wt% aqueous ammonia was quickly added, and stirring was stopped after 1 minute. The reaction solution pH at this time was 9.8.
After aging for 10 hours, the mixture was filtered and dried to obtain a pale white powder. From the raw material charge ratio, polymethylsilsesquioxane is 39 parts by weight per 100 parts by weight of polystyrene resin particles.
The weight of the obtained white powder was 33.9 g. When the obtained powder was observed with an electron microscope, as shown in the photograph shown in FIG. 4, confetti particles having protrusions on the particle surface were observed, but almost no polymethylsilsesquioxane single particles could be confirmed.
＜実施例１９＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径１μｍであるポリスチレンとポリメチルメタクリレートの共重合樹脂粒子（ポリスチレン：ポリメタクリレート＝４０：６０）を２２．５重量部投入し、超音波を１分間照射して、樹脂粒子分散液を得た。
次に、上記分散液を液温３０℃として、メチルトリメトキシシラン１５重量部を添加して、メチルトリメトキシシランの加水分解物を得た。
引き続き液温を３０℃に維持して３０分間撹拌した後、１重量％のアンモニア水１０重量部を速やかに添加して、１分後に撹拌を停止した。このときの反応液ｐＨは９．７であった。
静置下で１０時間熟成した後、ろ過、乾燥して淡白色粉末を得た。得られた白色粉末の重量は２９．０ｇであった。得られた粉末を電子顕微鏡観察したところ、図５に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。
このように共重合樹脂粒子を使用することにより、コア粒子の屈折率を任意に設定できる利点があることから、光学関係用途への利用が期待される。<Example 19>
Into a reaction vessel equipped with a thermometer, a reflux device, and a stirring device, 300 parts by weight of water was charged, and copolymer resin particles of polystyrene and polymethyl methacrylate (polystyrene: polymethacrylate = 40: 60) having an average particle diameter of 1 μm were added thereto. 22.5 parts by weight were charged and irradiated with ultrasonic waves for 1 minute to obtain a resin particle dispersion.
Next, 15 parts by weight of methyltrimethoxysilane was added at a liquid temperature of 30 ° C. to obtain a hydrolyzate of methyltrimethoxysilane.
Subsequently, after stirring for 30 minutes while maintaining the liquid temperature at 30 ° C., 10 parts by weight of 1 wt% aqueous ammonia was quickly added, and stirring was stopped after 1 minute. The reaction solution pH at this time was 9.7.
After aging for 10 hours, the mixture was filtered and dried to obtain a pale white powder. The weight of the obtained white powder was 29.0 g. When the obtained powder was observed with an electron microscope, as shown in the photograph shown in FIG. 5, confetti particles having protrusions on the particle surface were observed, but polymethylsilsesquioxane single particles were hardly confirmed. .
By using the copolymer resin particles in this way, there is an advantage that the refractive index of the core particles can be arbitrarily set, so that it is expected to be used for optical applications.
＜実施例２０＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径２μｍであるポリメチルメタクリレート樹脂粒子（根上工業製アートパールＪ−４Ｐ）を２５重量部投入し、超音波を１分間照射して、ポリメチルメタクリレート樹脂粒子分散液を得た。
次に、１重量％のアンモニア水１０重量部を速やかに添加してよく撹拌した後、穏やかな撹拌とした。
上記分散液の温度を３０℃として、メチルトリメトキシシラン１０重量部を１５分で滴下し、３０分間撹拌継続した後、静置下で１０時間熟成した後、ろ過、乾燥して白色粉末を得た。このときの反応液ｐHは９．７であった。原料の仕込み比率から、ポリメチルメタクリレート樹脂粒子１００重量部に対しポリメチルシルセスキオキサンは２０重量部となる。
得られた白色粉末の重量は２９．１ｇであった。得られた粉末を電子顕微鏡観察したところ、図６に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。
<Example 20>
A reaction vessel equipped with a thermometer, a reflux device and a stirrer was charged with 300 parts by weight of water, and 25 parts by weight of polymethyl methacrylate resin particles having an average particle diameter of 2 μm (Art Pearl J-4P manufactured by Negami Kogyo Co., Ltd.) were added thereto. Then, an ultrasonic wave was irradiated for 1 minute to obtain a polymethyl methacrylate resin particle dispersion.
Next, 10 parts by weight of 1% by weight aqueous ammonia was quickly added and stirred well, followed by gentle stirring.
The temperature of the dispersion was set to 30 ° C., 10 parts by weight of methyltrimethoxysilane was added dropwise over 15 minutes, and stirring was continued for 30 minutes. After aging for 10 hours, the mixture was filtered and dried to obtain a white powder. It was. The reaction solution pH at this time was 9.7. From charging ratio of the raw materials, polymethylsilsesquioxane per 100 by weight of poly (methyl methacrylate) resin particles is 20 by weight part.
The weight of the obtained white powder was 29.1 g. When the obtained powder was observed with an electron microscope, as shown in the photograph shown in FIG. 6, gold flat sugar particles having protrusions on the particle surface were observed, but polymethylsilsesquioxane single particles were hardly confirmed. .
＜比較例１＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径２μｍであるポリメチルメタクリレート樹脂粒子（根上工業製アートパールＪ−４Ｐ）を２５重量部投入し、超音波を１分間照射して、ポリメチルメタクリレート樹脂粒子分散液を得た。
次に、上記分散液を液温３０℃として、メチルトリメトキシシラン４重量部を添加して、ポリメチルメタクリレート樹脂粒子分散液中でメチルトリメトキシシランの加水分解物を得た。
引き続き液温を３０℃に維持して３０分間撹拌した後、１重量％のアンモニア水１０重量部を速やかに添加して、１分後に撹拌を停止した。このときの反応液ｐＨは９．８であった。
静置下で１０時間熟成した後、ろ過、乾燥して白色粉末を得た。得られた白色粉末の重量は２６．３ｇであった。原料の仕込み比率から、ポリメチルメタクリレート樹脂粒子１００重量部に対しポリメチルシルセスキオキサンは８重量部となる。
得られた粉末を電子顕微鏡観察したところ、図７に示す写真図のように、粒子表面の突起は確認できず、ポリメチルシルセスキオキサンで粒子表面を均一に被覆した球状粒子であった。
<Comparative Example 1>
A reaction vessel equipped with a thermometer, a reflux device and a stirrer was charged with 300 parts by weight of water, and 25 parts by weight of polymethyl methacrylate resin particles having an average particle diameter of 2 μm (Art Pearl J-4P manufactured by Negami Kogyo Co., Ltd.) were added thereto. Then, an ultrasonic wave was irradiated for 1 minute to obtain a polymethyl methacrylate resin particle dispersion.
Next, the dispersion was heated to 30 ° C. and 4 parts by weight of methyltrimethoxysilane was added to obtain a hydrolyzate of methyltrimethoxysilane in the polymethylmethacrylate resin particle dispersion.
Subsequently, after stirring for 30 minutes while maintaining the liquid temperature at 30 ° C., 10 parts by weight of 1 wt% aqueous ammonia was quickly added, and stirring was stopped after 1 minute. The reaction solution pH at this time was 9.8.
The mixture was aged for 10 hours and then filtered and dried to obtain a white powder. The weight of the obtained white powder was 26.3 g. From charging ratio of the raw materials, polymethylsilsesquioxane per 100 by weight of poly (methyl methacrylate) resin particles is 8 by weight section.
When the obtained powder was observed with an electron microscope, as shown in the photograph of FIG. 7, no protrusions on the particle surface could be confirmed, and the particles were spherical particles with the particle surface uniformly coated with polymethylsilsesquioxane.
＜比較例２＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径２μｍであるポリメチルメタクリレート樹脂粒子（根上工業製アートパールＪ−４Ｐ）を２５重量部投入し、超音波を１分間照射して、ポリメチルメタクリレート樹脂粒子分散液を得た。
次に、２８重量％のアンモニア水７重量部を速やかに添加してよく撹拌した後、穏やかな撹拌とした。
上記分散液の温度を３０℃として、メチルトリメトキシシラン１０重量部を１５分で滴下し、３０分間撹拌継続した。このときの反応液ｐHは１０．８であった。静置下で１０時間熟成した後、ろ過、乾燥して白色粉末を得た。原料の仕込み比率から、ポリメチルメタクリレート樹脂粒子１００重量部に対しポリメチルシルセスキオキサンは２０重量部となる。
得られた白色粉末の重量は２９．０ｇであった。得られた粉末を電子顕微鏡観察したところ、図８に示す写真図のように、粒子表面の突起は確認できず、ポリメチルシルセスキオキサンで粒子表面を均一に被覆した球状粒子であった。
<Comparative example 2>
A reaction vessel equipped with a thermometer, a reflux device and a stirrer was charged with 300 parts by weight of water, and 25 parts by weight of polymethyl methacrylate resin particles having an average particle diameter of 2 μm (Art Pearl J-4P manufactured by Negami Kogyo Co., Ltd.) were added thereto. Then, an ultrasonic wave was irradiated for 1 minute to obtain a polymethyl methacrylate resin particle dispersion.
Next, 7 parts by weight of 28% by weight aqueous ammonia was quickly added and stirred well, followed by gentle stirring.
The temperature of the dispersion was 30 ° C., 10 parts by weight of methyltrimethoxysilane was added dropwise over 15 minutes, and stirring was continued for 30 minutes. The reaction solution pH at this time was 10.8. The mixture was aged for 10 hours and then filtered and dried to obtain a white powder. From charging ratio of the raw materials, polymethylsilsesquioxane per 100 by weight of poly (methyl methacrylate) resin particles is 20 by weight part.
The weight of the obtained white powder was 29.0 g. When the obtained powder was observed with an electron microscope, projections on the particle surface could not be confirmed as shown in the photographic diagram in FIG. 8, and the particles were spherical particles whose surface was uniformly coated with polymethylsilsesquioxane.
実施例８と比較例２で得られた粉末を用いて、手の甲に粉末を少量乗せ指先で伸ばした際のすべり性、伸展性をパネラー１０人により評価した結果、１０人中１０人が実施例８で得られた粉末のほうがすべり性および伸展性に優れているという結果であった。 Using the powders obtained in Example 8 and Comparative Example 2, a small amount of powder was placed on the back of the hand, and the slipperiness and extensibility when stretched with fingertips were evaluated by 10 panelists. The result was that the powder obtained in No. 8 was superior in slipperiness and extensibility.
実施例８と比較例２で得られた粉末を用いて、反射光分布測定装置（株式会社村上色彩技術研究所製ＧＰ−２００）により入射角−４５°における−９０〜９０°の反射光分布測定を実施した。その結果を図９のグラフ図に示す。これによると、実施例８で得られた粒子のほうが比較例２で得られた粒子より光拡散性に優れていることが確認された。金平糖状粒子としたことにより、光拡散性が向上したと考えられる。 Using the powder obtained in Example 8 and Comparative Example 2, the reflected light distribution of −90 to 90 ° at an incident angle of −45 ° by a reflected light distribution measuring device (GP-200 manufactured by Murakami Color Research Laboratory Co., Ltd.). Measurements were performed. The result is shown in the graph of FIG. According to this, it was confirmed that the particles obtained in Example 8 were more excellent in light diffusibility than the particles obtained in Comparative Example 2. It is considered that the light diffusibility was improved by using the confetti particles.
ポリスチレン樹脂に、実施例８で得られた粉末を０．２ｗｔ％および０．５ｗｔ％の２水準で添加して板厚２ｍｍ、３ｍｍの拡散板を調製した。比較例２で得られた粉末についても同様に拡散板を調製した。
これらの光透過率と光拡散率を測定したところ、図１０に示すグラフ図のようになった。これによると、実施例８で得られた金平糖状粒子は比較例２で得られた球状粒子に比べ高透過率、高拡散率であることが確認できた。To the polystyrene resin, the powder obtained in Example 8 was added at two levels of 0.2 wt% and 0.5 wt% to prepare a diffusion plate having a plate thickness of 2 mm and 3 mm. A diffusion plate was similarly prepared for the powder obtained in Comparative Example 2.
When these light transmittance and light diffusivity were measured, it became like the graph shown in FIG. According to this, it was confirmed that the gold flat sugar-like particles obtained in Example 8 had higher transmittance and higher diffusivity than the spherical particles obtained in Comparative Example 2.
＜実施例２１＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径２μｍであるポリメチルメタクリレート樹脂粒子（根上工業製アートパールJ−４P）を２５重量部投入し、超音波を1分間照射して、ポリメチルメタクリレート樹脂粒子分散液を得た。
次に、１重量％のアンモニア水１０重量部を速やかに添加してよく撹拌した後、穏やかな撹拌とした。
上記分散液の温度を３０℃として、メチルトリメトキシシラン１０重量部を１５分で滴下し、３０分間撹拌継続した後、静置下で１０時間熟成した後、ろ過、乾燥して白色粉末を得た。このときの反応液ｐHは９．７であった。原料の仕込み比率から、ポリメチルメタクリレート樹脂粒子１００重量部に対しポリメチルシルセスキオキサンは２０重量部となる。
得られた白色粉末の重量は２９．１ｇであった。得られた粉末を電子顕微鏡観察したところ、図１１に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。
<Example 21>
A reaction vessel equipped with a thermometer, a reflux device and a stirrer was charged with 300 parts by weight of water, and 25 parts by weight of polymethyl methacrylate resin particles having an average particle diameter of 2 μm (Art Pearl J-4P manufactured by Negami Kogyo Co., Ltd.) were added thereto. Then, an ultrasonic wave was irradiated for 1 minute to obtain a polymethyl methacrylate resin particle dispersion.
Next, 10 parts by weight of 1% by weight aqueous ammonia was quickly added and stirred well, followed by gentle stirring.
The temperature of the dispersion was set to 30 ° C., 10 parts by weight of methyltrimethoxysilane was added dropwise over 15 minutes, and stirring was continued for 30 minutes. After aging for 10 hours, the mixture was filtered and dried to obtain a white powder. It was. The reaction solution pH at this time was 9.7. From charging ratio of the raw materials, polymethylsilsesquioxane per 100 by weight of poly (methyl methacrylate) resin particles is 20 by weight part.
The weight of the obtained white powder was 29.1 g. When the obtained powder was observed with an electron microscope, as shown in the photographic diagram shown in FIG. 11, confetti particles having protrusions on the particle surface were observed, but polymethylsilsesquioxane single particles were hardly confirmed. .
＜実施例２２〜２８＞
実施例２２は、反応温度を表３のようにした以外は実施例２１と同様にして金平糖状粒子を得た。
実施例２３〜２５は仕込み量を表３のようにした以外は実施例２１と同様にして金平糖状粒子を得た。
実施例２６〜２８は球状アクリル樹脂粒子の平均粒子径を表３に示したものを用いて、仕込み量を表３のようにした以外は実施例２１と同様にして金平糖状粒子を得た。<Examples 22 to 28>
In Example 22, confetti particles were obtained in the same manner as in Example 21 except that the reaction temperature was as shown in Table 3.
In Examples 23 to 25, gold flat sugar-like particles were obtained in the same manner as in Example 21 except that the amounts charged were as shown in Table 3.
In Examples 26 to 28, the average particle size of the spherical acrylic resin particles shown in Table 3 was used, and the amount of the charged particles was changed as shown in Table 3 to obtain gold flat sugar particles.
＜実施例２９＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径３μｍであるポリスチレン樹脂粒子を２２重量部投入し、超音波を1分間照射して、ポリスチレン樹脂粒子分散液を得た。
次に、１重量％のアンモニア水１０重量部を速やかに添加してよく撹拌した後、穏やかな撹拌とした。
上記分散液の温度を３０℃として、メチルトリメトキシシラン９重量部を５分で滴下し、２０分間撹拌継続した後、静置下で２時間熟成した後、ろ過、乾燥して白色粉末を得た。このときの反応液ｐHは９．６であった。原料の仕込み比率から、ポリスチレン樹脂粒子１００重量部に対しポリメチルシルセスキオキサンは２０重量部となる。
得られた白色粉末の重量は２５．９ｇであった。得られた粉末を電子顕微鏡観察したところ、図１２に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。
<Example 29>
A reaction vessel equipped with a thermometer, a reflux device, and a stirring device was charged with 300 parts by weight of water, and 22 parts by weight of polystyrene resin particles having an average particle diameter of 3 μm were added thereto, irradiated with ultrasonic waves for 1 minute, and polystyrene resin A particle dispersion was obtained.
Next, 10 parts by weight of 1% by weight aqueous ammonia was quickly added and stirred well, followed by gentle stirring.
The temperature of the dispersion was 30 ° C., 9 parts by weight of methyltrimethoxysilane was added dropwise over 5 minutes, and stirring was continued for 20 minutes. After aging for 2 hours, the solution was filtered and dried to obtain a white powder. It was. The reaction solution pH at this time was 9.6. From charging ratio of the raw materials, polymethylsilsesquioxane per 100 by weight parts polystyrene resin particles is 20 by weight part.
The weight of the obtained white powder was 25.9 g. When the obtained powder was observed with an electron microscope, as shown in the photographic diagram shown in FIG. 12, confetti grains having protrusions on the particle surface were observed, but polymethylsilsesquioxane single particles were hardly confirmed. .
＜実施例３０＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径７μｍであるポリウレタン樹脂粒子（根上工業製アートパールＣ−８００（透明））を２２．５重量部投入し、超音波を1分間照射して、ポリウレタン樹脂粒子分散液を得た。
次に、１重量％のアンモニア水１０重量部を速やかに添加してよく撹拌した後、穏やかな撹拌とした。
上記分散液の温度を３０℃として、メチルトリメトキシシラン１５重量部を５分で滴下し、２０分間撹拌継続した後、静置下で２時間熟成した後、ろ過、乾燥して白色粉末を得た。このときの反応液ｐHは９．６であった。原料の仕込み比率から、ポリウレタン樹脂粒子１００重量部に対しポリメチルシルセスキオキサンは３３重量部となる。
得られた白色粉末の重量は２８．９ｇであった。得られた粉末を電子顕微鏡観察したところ、図１３に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。
<Example 30>
A reaction vessel equipped with a thermometer, a reflux device and a stirrer was charged with 300 parts by weight of water, and 22.5 wt% of polyurethane resin particles having an average particle diameter of 7 μm (Art Pearl C-800 (transparent) manufactured by Negami Kogyo Co., Ltd.). A polyurethane resin particle dispersion was obtained by irradiating with ultrasonic waves for 1 minute.
Next, 10 parts by weight of 1% by weight aqueous ammonia was quickly added and stirred well, followed by gentle stirring.
The temperature of the dispersion was 30 ° C., 15 parts by weight of methyltrimethoxysilane was added dropwise over 5 minutes, and stirring was continued for 20 minutes. After aging for 2 hours, the mixture was filtered and dried to obtain a white powder. It was. The reaction solution pH at this time was 9.6. From charging ratio of the raw materials, polymethylsilsesquioxane per 100 by weight of the polyurethane resin particles becomes 33 by weight part.
The weight of the obtained white powder was 28.9 g. When the obtained powder was observed with an electron microscope, as shown in the photographic diagram shown in FIG. 13, confetti particles having protrusions on the particle surface were observed, but polymethylsilsesquioxane single particles were hardly confirmed. .
＜実施例３１＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに１重量％のアンモニア水１０重量部を添加して、アンモニア水溶液を調製した。アンモニア水溶液に球状アクリル樹脂粒子である根上工業株式会社製アートパールＪ−５Ｐを２５重量部投入し、超音波を１分間照射して、アクリル樹脂粒子分散液を得た。
次に、上記分散液を液温３０℃として、穏やかな撹拌下でメチルトリメトキシシラン１０重量部を１分間で添加して、引き続き液温を３０℃に維持して２０分間撹拌した後、撹拌を停止した。
静置下で２時間熟成した後、ろ過、乾燥して白色粉末を得た。得られた白色粉末の重量は２８．９ｇであった。得られた粉末を電子顕微鏡観察したところ、図１４に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。<Example 31>
A reaction vessel equipped with a thermometer, a reflux device and a stirring device was charged with 300 parts by weight of water, and 10 parts by weight of 1% by weight ammonia water was added thereto to prepare an aqueous ammonia solution. 25 parts by weight of Nepal Kogyo Co., Ltd. Art Pearl J-5P, which is spherical acrylic resin particles, was added to an aqueous ammonia solution and irradiated with ultrasonic waves for 1 minute to obtain an acrylic resin particle dispersion.
Next, the dispersion was brought to a liquid temperature of 30 ° C., 10 parts by weight of methyltrimethoxysilane was added over 1 minute with gentle stirring, and then the liquid temperature was maintained at 30 ° C. and stirred for 20 minutes. Stopped.
The mixture was aged for 2 hours and then filtered and dried to obtain a white powder. The weight of the obtained white powder was 28.9 g. When the obtained powder was observed with an electron microscope, as shown in the photographic diagram shown in FIG. 14, confetti particles having protrusions on the particle surface were observed, but polymethylsilsesquioxane single particles were hardly confirmed. .
＜実施例３２〜３８＞
実施例３２は、反応温度を表４のようにした以外は実施例２１と同様にして金平糖状粒子を得た。
実施例３３〜３４は仕込み量を表４のようにした以外は実施例２１と同様にして金平糖状粒子を得た。
実施例３５〜３６は球状アクリル樹脂粒子の平均粒子径を表４に示したものを用いて、仕込み量を表４のようにした以外は実施例２１と同様にして金平糖状粒子を得た。
実施例３７〜３８は、有機樹脂粒子を表４のようにした以外は実施例２１と同様にして金平糖状粒子を得た。<Examples 32-38>
In Example 32, confetti particles were obtained in the same manner as in Example 21 except that the reaction temperature was as shown in Table 4.
In Examples 33 to 34, gold flat sugar-like particles were obtained in the same manner as in Example 21 except that the amounts charged were as shown in Table 4.
In Examples 35 to 36, the average particle diameter of the spherical acrylic resin particles shown in Table 4 was used, and the amount of the charged particles was changed as shown in Table 4 to obtain gold flat sugar particles.
In Examples 37 to 38, gold flat sugar-like particles were obtained in the same manner as in Example 21 except that the organic resin particles were changed as shown in Table 4.
＜実施例３９＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径２μｍであるポリメチルメタクリレート樹脂粒子（根上工業製アートパールＪ−４Ｐ）を２５重量部投入し、超音波を１分間照射して、ポリメチルメタクリレート樹脂粒子分散液を得た。
次に、上記分散液の温度を３０℃として、メチルトリメトキシシラン８重量部およびジメチルジメトキシシラン２重量部を添加して、ポリメチルメタクリレート樹脂粒子分散液中でメチルトリメトキシシランおよびジメチルジメトキシシランの加水分解物を得た。引き続き液温を３０℃に維持して３０分間撹拌した後、１重量％のアンモニア水５重量部を速やかに添加して、１分後に撹拌を停止した。このときの反応液ｐＨは９．１であった。静置下で５時間熟成した後、ろ過、乾燥して白色粉末を得た。
得られた粉末を電子顕微鏡観察したところ、図１５に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシロキサン単独粒子は殆ど確認できなかった。<Example 39>
A reaction vessel equipped with a thermometer, a reflux device and a stirrer was charged with 300 parts by weight of water, and 25 parts by weight of polymethyl methacrylate resin particles having an average particle diameter of 2 μm (Art Pearl J-4P manufactured by Negami Kogyo Co., Ltd.) were added thereto. Then, an ultrasonic wave was irradiated for 1 minute to obtain a polymethyl methacrylate resin particle dispersion.
Next, the temperature of the dispersion is 30 ° C., 8 parts by weight of methyltrimethoxysilane and 2 parts by weight of dimethyldimethoxysilane are added, and methyltrimethoxysilane and dimethyldimethoxysilane in the polymethylmethacrylate resin particle dispersion are added. A hydrolyzate was obtained. Subsequently, after stirring for 30 minutes while maintaining the liquid temperature at 30 ° C., 5 parts by weight of 1 wt% aqueous ammonia was quickly added, and stirring was stopped after 1 minute. The reaction solution pH at this time was 9.1. After aging for 5 hours, the mixture was filtered and dried to obtain a white powder.
When the obtained powder was observed with an electron microscope, as shown in the photographic diagram of FIG. 15, confetti particles having protrusions on the particle surface were observed, but polymethylsiloxane single particles were hardly confirmed.
＜実施例４０＞
オルガノアルコキシシランとして、メチルトリメトキシシラン６重量部およびトリメチルモノメトキシシラン４重量部に変更した以外は、実施例３９と同じ条件で白色粉末を得た。
得られた粉末を電子顕微鏡観察したところ、図１６に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシロキサン単独粒子は殆ど確認できなかった。<Example 40>
A white powder was obtained under the same conditions as in Example 39 except that the organoalkoxysilane was changed to 6 parts by weight of methyltrimethoxysilane and 4 parts by weight of trimethylmonomethoxysilane.
When the obtained powder was observed with an electron microscope, as shown in the photograph shown in FIG. 16, confetti particles having protrusions on the particle surface were observed, but polymethylsiloxane single particles were hardly confirmed.
＜実施例４１＞
オルガノアルコキシシランとして、メチルトリメトキシシラン９重量部およびテトラメトシキシシラン１重量部に変更した以外は、実施例３９と同じ条件で白色粉末を得た。
得られた粉末を電子顕微鏡観察したところ、図１７に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシロキサン単独粒子は殆ど確認できなかった。<Example 41>
A white powder was obtained under the same conditions as in Example 39, except that the organoalkoxysilane was changed to 9 parts by weight of methyltrimethoxysilane and 1 part by weight of tetramethoxysilane.
When the obtained powder was observed with an electron microscope, as shown in a photograph shown in FIG. 17, confetti particles having protrusions on the particle surface were observed, but polymethylsiloxane single particles were hardly confirmed.
＜実施例４２＞
オルガノアルコキシシランとして、メチルトリメトキシシラン７重量部、ジメチルジメトキシシラン１重量部、トリメチルモノメトキシシラン２重量部とした以外は、実施例３９と同じ条件で白色粉末を得た。
得られた粉末を電子顕微鏡観察したところ、図１８に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシロキサン単独粒子は殆ど確認できなかった。<Example 42>
A white powder was obtained under the same conditions as in Example 39 except that 7 parts by weight of methyltrimethoxysilane, 1 part by weight of dimethyldimethoxysilane, and 2 parts by weight of trimethylmonomethoxysilane were used as the organoalkoxysilane.
When the obtained powder was observed with an electron microscope, as shown in the photograph shown in FIG. 18, confetti particles having protrusions on the particle surface were observed, but polymethylsiloxane single particles were hardly confirmed.
＜実施例４３＞
オルガノアルコキシシランとして、メチルトリメトキシシラン９．５重量部、オルガノハロシランとしてメチルトリクロルシラン０．５重量部とした以外は、実施例３９と同じ条件で白色粉末を得た。
得られた粉末を電子顕微鏡観察したところ、図１９に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。<Example 43>
A white powder was obtained under the same conditions as in Example 39 except that 9.5 parts by weight of methyltrimethoxysilane was used as the organoalkoxysilane and 0.5 parts by weight of methyltrichlorosilane was used as the organohalosilane.
When the obtained powder was observed with an electron microscope, as shown in the photograph shown in FIG. 19, confetti particles having protrusions on the particle surface were observed, but polymethylsilsesquioxane single particles were hardly confirmed. .
＜実施例４４＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これに平均粒子径２μｍであるポリメチルメタクリレート樹脂粒子（根上工業製アートパールＪ−４Ｐ）を２５重量部投入し、超音波を１分間照射して、ポリメチルメタクリレート樹脂粒子分散液を得た。次に、１重量％のアンモニア水５重量部を速やかに添加してよく撹拌した後、穏やかな撹拌とした。
上記分散液の温度を３０℃として、メチルトリメトキシシラン１５重量部を添加して、分散液とメチルトリメトキシシランが２層に分離された状態で穏やかな撹拌を継続した。メチルトリメトキシシラン添加６分後にはメチルトリメトキシシラン層がほぼ消失していた。さらに１０分間撹拌継続した後、静置下で２時間熟成した後、ろ過、乾燥して白色粉末を得た。
得られた粉末を電子顕微鏡観察したところ、図２０に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。
因みに、メチルトリメトキシシランは非水溶性なため、上記分散液とは２層に分離するが、界面でメチルトリメトキシシランの加水分解反応を進行させることで、水溶性となった加水分解物が分散液側に分散し、さらに脱水縮合反応することにより金平糖状粒子の合成が可能となる。<Example 44>
A reaction vessel equipped with a thermometer, a reflux device and a stirrer was charged with 300 parts by weight of water, and 25 parts by weight of polymethyl methacrylate resin particles having an average particle diameter of 2 μm (Art Pearl J-4P manufactured by Negami Kogyo Co., Ltd.) were added thereto. Then, an ultrasonic wave was irradiated for 1 minute to obtain a polymethyl methacrylate resin particle dispersion. Next, 5 parts by weight of 1% by weight aqueous ammonia was quickly added and stirred well, followed by gentle stirring.
The temperature of the dispersion was 30 ° C., 15 parts by weight of methyltrimethoxysilane was added, and gentle stirring was continued in a state where the dispersion and methyltrimethoxysilane were separated into two layers. The methyltrimethoxysilane layer almost disappeared 6 minutes after the addition of methyltrimethoxysilane. After further stirring for 10 minutes, the mixture was aged for 2 hours and then filtered and dried to obtain a white powder.
When the obtained powder was observed with an electron microscope, as shown in the photograph shown in FIG. 20, confetti particles having protrusions on the particle surface were observed, but polymethylsilsesquioxane single particles were hardly confirmed. .
Incidentally, since methyltrimethoxysilane is insoluble in water, it is separated into two layers from the above dispersion, but the hydrolyzate that has become water-soluble can be obtained by advancing the hydrolysis reaction of methyltrimethoxysilane at the interface. Dispersion on the dispersion side and further dehydration condensation reaction enable synthesis of confetti particles.
＜実施例４５＞
温度計、還流装置および撹拌装置を備えた反応容器に水３００重量部を仕込み、これにメチルトリメトキシシラン１２重量部を添加して３０℃で１時間撹拌してメチルトリメトキシシランの加水分解液を調製した。
次に、上記加水分解液に平均粒子径３μｍであるポリメチルメタクリレート樹脂粒子（根上工業製アートパールＪ−５Ｐ）を２５重量部投入し、超音波を１分間照射して、アクリル樹脂粒子分散液を得た。上記分散液を液温３０℃として撹拌下で１重量％のアンモニア水溶液５重量部を添加して１分間撹拌継続した後に静置下で２時間熟成させた後、ろ過、乾燥して白色粉末を得た。
得られた粉末を電子顕微鏡観察したところ、図２１に示す写真図のように、粒子表面に突起を有する金平糖状粒子が観察されたが、ポリメチルシルセスキオキサン単独粒子は殆ど確認できなかった。<Example 45>
A reaction vessel equipped with a thermometer, a reflux device and a stirrer was charged with 300 parts by weight of water, 12 parts by weight of methyltrimethoxysilane was added thereto, and stirred at 30 ° C. for 1 hour to hydrolyze methyltrimethoxysilane. Was prepared.
Next, 25 parts by weight of polymethylmethacrylate resin particles having an average particle diameter of 3 μm (Art Pearl J-5P, manufactured by Negami Kogyo Co., Ltd.) are added to the hydrolyzed liquid, and ultrasonic waves are irradiated for 1 minute, whereby acrylic resin particle dispersion liquid is used. Got. The dispersion was heated to 30 ° C., 5 parts by weight of a 1 wt% aqueous ammonia solution was added with stirring, and stirring was continued for 1 minute, followed by aging for 2 hours, followed by filtration and drying to obtain a white powder. Obtained.
When the obtained powder was observed with an electron microscope, as shown in the photographic diagram shown in FIG. 21, confetti particles having protrusions on the particle surface were observed, but polymethylsilsesquioxane single particles were hardly confirmed. .
本発明は、核となる有機樹脂粒子の表面にポリオルガノシロキサンの突起を有する金平糖状粒子の製造方法に関するもので、斯かる製造方法によって製造された表面金平糖状の複合粒子は、各種プラスティック、各種ゴムおよび化粧品等の製品の滑り性、耐摩耗性、ブロッキング防止性、撥水性、光拡散性等付与剤として産業上の利用可能性がある。 The present invention relates to a method for producing confetti particles having polyorganosiloxane protrusions on the surface of organic resin particles as a core, and the surface confectionary composite particles produced by such a production method include various plastics, It has industrial applicability as an imparting agent such as slipperiness, abrasion resistance, antiblocking property, water repellency and light diffusibility of products such as rubber and cosmetics.
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