KR20180107182A - Process for producing spherical polymethylphenylsilsequioxane particles - Google Patents
Process for producing spherical polymethylphenylsilsequioxane particles Download PDFInfo
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- KR20180107182A KR20180107182A KR1020187024590A KR20187024590A KR20180107182A KR 20180107182 A KR20180107182 A KR 20180107182A KR 1020187024590 A KR1020187024590 A KR 1020187024590A KR 20187024590 A KR20187024590 A KR 20187024590A KR 20180107182 A KR20180107182 A KR 20180107182A
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- Prior art keywords
- methyltrimethoxysilane
- phenyltrimethoxysilane
- aqueous solution
- particles
- stirring
- Prior art date
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- 239000002245 particle Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000007864 aqueous solution Substances 0.000 claims abstract description 52
- 239000000126 substance Substances 0.000 claims abstract description 47
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 64
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 description 42
- 239000011521 glass Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 15
- 238000013019 agitation Methods 0.000 description 15
- 238000006482 condensation reaction Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 230000020169 heat generation Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- -1 acetone Chemical class 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical group O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 description 3
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- ADDKUYIIHFYIMV-UHFFFAOYSA-N methanesulfonic acid;trifluoromethanesulfonic acid Chemical compound CS(O)(=O)=O.OS(=O)(=O)C(F)(F)F ADDKUYIIHFYIMV-UHFFFAOYSA-N 0.000 description 2
- ZJBHFQKJEBGFNL-UHFFFAOYSA-N methylsilanetriol Chemical compound C[Si](O)(O)O ZJBHFQKJEBGFNL-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- FCVNATXRSJMIDT-UHFFFAOYSA-N trihydroxy(phenyl)silane Chemical compound O[Si](O)(O)C1=CC=CC=C1 FCVNATXRSJMIDT-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HDPLNWXZGIQTCJ-UHFFFAOYSA-N [P].C1(=CC=CC=C1)[Si](OC)(OC)OC Chemical compound [P].C1(=CC=CC=C1)[Si](OC)(OC)OC HDPLNWXZGIQTCJ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/32—Post-polymerisation treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
(i) 메틸트라이메톡시실레인을 pH가 4.0∼7.0의 물에 첨가하고, 가수분해 반응을 행하여, 투명한 수용액을 얻는 공정, (ii) 공정 (i)에서 얻어진 수용액에 페닐트라이메톡시실레인을 첨가하고, 가수분해 반응을 행하여, 투명한 실레인 수용액을 얻는 공정, (iii) 공정 (ii)에서 얻어진 수용액을 0∼15℃의 온도로 조절하고, 이것에 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액을 첨가하고, 교반 혼합하여 혼합액을 얻는 공정, 및 (iv) 공정 (iii)에서 얻어진 혼합액을 정치 상태로 히고, 폴리메틸페닐실세스퀴옥세인 입자를 석출시키는 공정을 포함하는, 체적평균 입경이 1∼5㎛의 구상 폴리메틸페닐실세스퀴옥세인 입자의 제조 방법.(i) adding methyltrimethoxysilane to water having a pH of 4.0 to 7.0 to carry out a hydrolysis reaction to obtain a transparent aqueous solution, (ii) adding to the aqueous solution obtained in the step (i) phenyltrimethoxysilane (Iii) an aqueous solution obtained by adjusting the aqueous solution obtained in the step (ii) to a temperature of 0 to 15 占 폚 and dissolving an alkaline substance or an alkaline substance in the aqueous solution; (Iv) a step of bringing the mixed solution obtained in the step (iii) into a stationary state to precipitate the polymethylphenylsilsequioxane particles, and a step of adding a solution having a volume average particle size of 1 to 5 Of the spherical polymethylphenylsilsesquioxane particles.
Description
본 발명은 구상 폴리메틸페닐실세스퀴옥세인 입자의 제조 방법에 관한 것이다.The present invention relates to a process for preparing spherical polymethylphenylsilsequioxane particles.
폴리메틸실세스퀴옥세인 입자는 액정 디스플레이의 백라이트의 광확산용 광확산판, 시트나 LED 조명의 광확산 커버의 광확산제로서 사용되고 있다. 기재 수지와 광확산제 입자에 굴절률차가 있음으로써, 광의 굴절 및 반사가 일어나 광확산성이 발현된다. 굴절률차가 클수록 광확산성은 향상되는 한편, 반사광이 많아지기 때문에, 광의 투과성이 저하된다. 광의 투과성을 중시하는 경우에는, 굴절률차가 작은 편이 바람직하다. 기재 수지에는 폴리메틸메타크릴레이트, 폴리스타이렌, 폴리카보네이트 등이 사용되지만, 폴리메틸실세스퀴옥세인은 이들 수지에 대하여 굴절률은 낮아, 굴절률차를 작게 하기 위해서는, 굴절률을 높게 하게 된다. 폴리메틸실세스퀴옥세인에 페닐실세스퀴옥세인 단위를 도입함으로써 굴절률을 높게 할 수 있다. 메틸실세스퀴옥세인 단위와 페닐실세스퀴옥세인 단위의 조성 비율을 변경함으로써, 굴절률을 1.43∼1.57의 범위에서 변경할 수 있다.The polymethylsilsesquioxane particles are used as a light diffusing agent for a light diffusing plate for a light diffusion of a backlight of a liquid crystal display, a sheet or a light diffusion cover of a LED illumination. Since there is a difference in refractive index between the base resin and the light diffusing agent particle, refraction and reflection of light occur and light diffusibility is expressed. The larger the refractive index difference is, the better the light diffusibility is, while the more the reflected light is, the lower the light transmittance. When the transparency of light is emphasized, it is preferable that the refractive index difference is small. Polymethyl methacrylate, polystyrene, polycarbonate, or the like is used as the base resin. However, the refractive index of polymethylsilsesquioxane is low with respect to these resins and the refractive index is increased in order to reduce the refractive index difference. By introducing phenylsilsesquioxane units into polymethylsilsesquioxane, the refractive index can be increased. The refractive index can be changed within the range of 1.43 to 1.57 by changing the composition ratio of the methylsilsequioxane unit and the phenyl silsesquioxane unit.
이 페닐실세스퀴옥세인 단위를 도입한 구상의 폴리메틸페닐실세스퀴옥세인 입자를 얻는 방법으로서는 일본 특개 평4-202325호 공보(특허문헌 1)에, 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 균일 혼합액을 알칼리성 물질의 수용액에 교반하에 적하하고 가수분해, 축합 반응시키는 방법이 예시되어 있다. 이 방법에서는 교반 날개나 조의 내벽에 겔 형상물이 부착된다고 하는 문제가 있다. 또한 일본 특개 2003-335860호 공보(특허문헌 2)에는, 메틸트라이알콕시실레인과 페닐트라이알콕시실레인의 혼합물을 산성 수용액 중에서 가수분해하고, 이어서 알칼리성 수용액을 첨가, 혼합한 후, 교반을 정지하고, 정치하에서 축합 반응시키는 방법이 제안되어 있다. 여기에서 예시되어 있는 제조법에서는, 겔 형상물은 생성되지 않지만, 모두 체적평균 입경은 5㎛보다 크다.As a method for obtaining spherical polymethylphenylsilsesquioxane particles into which the phenylsilsesquioxane unit is introduced, Japanese Patent Application Laid-open No. 4-202325 (Patent Document 1) discloses a process for producing a polymer comprising methyltrimethoxysilane and phenyltrimethoxysilane Phosphorus-based homogeneous mixed solution is added dropwise to an aqueous solution of an alkaline substance with stirring, followed by hydrolysis and condensation reaction. In this method, there is a problem that the gel material adheres to the stirring blade or the inner wall of the tank. Japanese Patent Application Laid-Open No. 2003-335860 (Patent Document 2) discloses a method in which a mixture of methyltrialkoxysilane and phenyltrialkoxysilane is hydrolyzed in an acidic aqueous solution, and then an alkaline aqueous solution is added and mixed. Thereafter, stirring is stopped , And a condensation reaction is carried out under a pressure. In the manufacturing method exemplified here, no gel material is produced, but all of them have a volume average particle diameter of more than 5 mu m.
광확산제로서는 체적평균 입경이 약 1∼5㎛인 입자가 적합하고, 이 입경의 범위 외에서는, 광확산성이 저하된다. 상기의 일본 특개 2003-335860호 공보에 예시되어 있는 폴리메틸페닐실세스퀴옥세인 입자는 모두 체적평균 입경은 5㎛보다 커, 광확산 용도에는 적합하지 않다. 본 발명은 상기 사정을 감안하여 이루어진 것으로, 겔 형상물이 생성되지 않고, 광확산제로서 적합한 체적평균 입경 1∼5㎛의 구상 폴리메틸페닐실세스퀴옥세인 입자를 제조하는 방법을 제공하는 것을 목적으로 한다.As the light diffusing agent, particles having a volume average particle diameter of about 1 to 5 m are suitable, and out of the range of the particle diameter, the light diffusing properties are lowered. The polymethylphenylsilsesquioxane particles exemplified in the above Japanese Patent Application Laid-Open No. 2003-335860 all have a volume average particle diameter of more than 5 mu m and are not suitable for light diffusion applications. SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing spherical polymethylphenylsilsequioxane particles having a volume average particle diameter of 1 to 5 탆 which is suitable for use as a light diffusing agent, .
본 발명자는 상기 목적을 달성하기 위해 예의 검토한 결과, 메틸트라이메톡시실레인을 pH가 4.0∼7.0의 물에 첨가하여, 투명한 수용액을 얻고, 이것에 페닐트라이메톡시실레인을 첨가하여, 투명한 실레인 수용액을 얻고, 이것에 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액을 첨가하고, 혼합액을 정치 상태로 하여 폴리메틸페닐실세스퀴옥세인 입자를 석출시키고, 물, 메틸트라이메톡시실레인, 페닐트라이메톡시실레인을 적당량으로 함으로써, 겔 형상물이 생성되지 않고, 광확산제로서 적합한 체적평균 입경 1∼5㎛의 구상 폴리메틸페닐실세스퀴옥세인 입자가 얻어지는 것을 발견하고, 본 발명을 이루게 된 것이다.As a result of intensive studies to achieve the above object, the present inventors have found that methyltrimethoxysilane is added to water having a pH of 4.0 to 7.0 to obtain a transparent aqueous solution, phenyltrimethoxysilane is added thereto, A silane aqueous solution is obtained by adding an aqueous solution prepared by dissolving an alkaline substance or an alkaline substance to the aqueous solution, and the mixture is allowed to stand to precipitate the polymethylphenylsilsequioxane particles, and water, methyltrimethoxysilane, phenyltrimethoxy It has been found that spherical polymethylphenylsilsesquioxane particles having a volume average particle diameter of 1 to 5 mu m suitable for use as a light diffusing agent can be obtained without producing a gel-like material by setting an appropriate amount of silane.
따라서, 본 발명은 하기 제조 방법을 제공한다.Accordingly, the present invention provides the following production method.
[1]. (i) 메틸트라이메톡시실레인을 pH 4.0∼7.0의 물에 첨가하고, 가수분해 반응을 행하여, 투명한 수용액을 얻는 공정,[One]. (i) a step of adding methyltrimethoxysilane to water having a pH of 4.0 to 7.0 and performing a hydrolysis reaction to obtain a transparent aqueous solution,
(ii) 공정 (i)에서 얻어진 수용액에 페닐트라이메톡시실레인을 첨가하고, 가수분해 반응을 행하여, 투명한 실레인 수용액을 얻는 공정,(ii) a step of adding phenyltrimethoxysilane to the aqueous solution obtained in the step (i) and performing a hydrolysis reaction to obtain a transparent aqueous silane solution,
(iii) 공정 (ii)에서 얻어진 수용액을 0∼15℃의 온도로 조절하고, 이것에 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액을 첨가하고, 교반 혼합하여 혼합액을 얻는 공정, 및(iii) a step of adjusting the aqueous solution obtained in the step (ii) to a temperature of 0 to 15 캜, adding an aqueous solution in which an alkaline substance or an alkaline substance is dissolved, and stirring to obtain a mixed solution, and
(iv) 공정 (iii)에서 얻어진 혼합액을 정치 상태로 하고, 폴리메틸페닐실세스퀴옥세인 입자를 석출시키는 공정을 포함하고,(iv) a step of bringing the mixed solution obtained in the step (iii) into a standing state to precipitate the polymethylphenylsilsequioxane particles,
상기 공정 (i) 및 (ii)에서, 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 물 100질량부에 대하여 5∼30질량부이며, 메틸트라이메톡시실레인:페닐트라이메톡시실레인으로 표시되는 질량비가 90:10∼20:80인 배합량인, 체적평균 입경이 1∼5㎛의 구상 폴리메틸페닐실세스퀴옥세인 입자의 제조 방법.In the above steps (i) and (ii), the total amount of methyltrimethoxysilane and phenyltrimethoxysilane is 5 to 30 parts by mass based on 100 parts by mass of water, and methyltrimethoxysilane: phenyltrimethoxysilane Wherein the weight ratio of the cyclic polymethylphenylsilsesquioxane particles to the cyclic polymethylphenylsilsesquioxane particles is in the range of 90:10 to 20:80.
[2]. (iv) 공정 후, 교반하, 혼합액을 40∼100℃로 가열하고, 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액을 첨가하는 공정을 포함하는, [1] 기재의 제조 방법.[2]. (iv) a step of heating the mixed solution to 40 to 100 占 폚 with stirring and adding an aqueous solution containing an alkaline substance or an alkaline substance dissolved therein.
본 발명에 의하면, 겔 형상물이 생성되지 않고, 광확산제로서 적합한 체적평균 입경 1∼5㎛의 구상 폴리메틸페닐실세스퀴옥세인 입자를 제조하는 방법을 제공할 수 있다.According to the present invention, it is possible to provide a method for producing a spherical polymethylphenylsilsequioxane particle having a volume average particle diameter of 1 to 5 탆 which is suitable for use as a light diffusing agent, without producing a gel-like material.
(발명을 실시하기 위한 형태)(Mode for carrying out the invention)
이하, 본 발명에 대해 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 제조 방법은,The production method of the present invention,
(i) 메틸트라이메톡시실레인을 pH 4.0∼7.0의 물에 첨가하고, 가수분해 반응을 행하여, 투명한 수용액을 얻는 공정,(i) a step of adding methyltrimethoxysilane to water having a pH of 4.0 to 7.0 and performing a hydrolysis reaction to obtain a transparent aqueous solution,
(ii) 공정 (i)에서 얻어진 수용액에 페닐트라이메톡시실레인을 첨가하고, 가수분해 반응을 행하여, 투명한 수용액을 얻는 공정,(ii) a step of adding phenyltrimethoxysilane to the aqueous solution obtained in the step (i) and conducting a hydrolysis reaction to obtain a transparent aqueous solution,
(iii) 공정 (ii)에서 얻어진 수용액을 0∼15℃의 온도로 조절하고, 이것에 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액을 첨가하고, 교반 혼합하여 혼합액을 얻는 공정, 및(iii) a step of adjusting the aqueous solution obtained in the step (ii) to a temperature of 0 to 15 캜, adding an aqueous solution in which an alkaline substance or an alkaline substance is dissolved, and stirring to obtain a mixed solution, and
(iv) 공정 (iii)에서 얻어진 혼합액을 정치 상태로 하여 폴리메틸페닐실세스퀴옥세인 입자를 석출시키는 공정을 포함하고,(iv) a step of bringing the mixed solution obtained in the step (iii) into a standing state to precipitate the polymethylphenylsilsequioxane particles,
상기 공정 (i) 및 (ii)에서, 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 물 100질량부에 대하여 5∼30질량부이며, 메틸트라이메톡시실레인:페닐트라이메톡시실레인으로 표시되는 질량비가 90:10∼20:80인 배합량인, 체적평균 입경이 1∼5㎛의 구상 폴리메틸페닐실세스퀴옥세인 입자의 제조 방법.In the above steps (i) and (ii), the total amount of methyltrimethoxysilane and phenyltrimethoxysilane is 5 to 30 parts by mass based on 100 parts by mass of water, and methyltrimethoxysilane: phenyltrimethoxysilane Wherein the weight ratio of the cyclic polymethylphenylsilsesquioxane particles to the cyclic polymethylphenylsilsesquioxane particles is in the range of 90:10 to 20:80.
(i) 메틸트라이메톡시실레인을 pH 4.0∼7.0의 물에 첨가하고, 가수분해 반응을 행하여, 투명한 실레인 수용액을 얻는 공정(i) a step of adding methyltrimethoxysilane to water having a pH of 4.0 to 7.0 and performing a hydrolysis reaction to obtain a transparent aqueous silane solution
메틸트라이메톡시실레인은 CH3Si(OCH3)3로 표시된다. 공정 (i)에서 사용되는 물은 메틸트라이메톡시실레인 및 공정 (ii)에서 사용하는 페닐트라이메톡시실레인을 가수분해하기 위해, pH(25℃)를 4.0∼7.0으로 할 필요가 있다. pH가 4.0 미만 또는 7.0보다 높으면, 축합 반응이 진행되어 버려, 겔이 생성된다. 바람직하게는 5.0∼6.8의 범위이다. 예를 들면, 이온교환수이면, 공기 중의 탄산 가스의 용해에 의해 pH가 상기 범위가 되기 때문에, 그대로 사용할 수 있다. 상기 범위의 pH로 하기 위하여 소량의 산성 물질을 첨가해도 된다. 산성 물질은 특별히 한정되지 않고, 예를 들면, 폼산, 아세트산, 옥살산, 말론산, 락트산, 말산 등의 카복실산, 염산; 인산; 황산; 메테인설폰산; 트라이플루오로메테인설폰산 등을 1종 단독으로 또는 2종 이상을 적당하게 조합하여 사용할 수 있다.Methyl trimethoxy silane is represented by CH 3 Si (OCH 3) 3 . The water used in the step (i) needs to have a pH (25 ° C) of 4.0 to 7.0 in order to hydrolyze the methyltrimethoxysilane and the phenyltrimethoxysilane used in the step (ii). If the pH is lower than 4.0 or higher than 7.0, the condensation reaction proceeds and a gel is formed. And preferably in the range of 5.0 to 6.8. For example, in the case of ion-exchanged water, since the pH is in the above range due to the dissolution of carbonic acid gas in the air, it can be used as it is. A small amount of an acidic substance may be added to adjust the pH to the above range. The acidic substance is not particularly limited and includes, for example, carboxylic acids such as formic acid, acetic acid, oxalic acid, malonic acid, lactic acid and malic acid; Phosphoric acid; Sulfuric acid; Methanesulfonic acid; Trifluoromethanesulfonic acid, etc. may be used alone or in combination of two or more.
메틸트라이메톡시실레인의 가수분해 반응 속도 향상이나 폴리메틸페닐실세스퀴옥세인 입자의 입경을 컨트롤할 목적 등으로, 물에 수용성의 유기 용제를 첨가해도 된다. 유기 용제는 특별히 한정되지 않고, 메탄올, 에탄올, 프로판올, 뷰탄올 등의 알코올류나 아세톤 등의 케톤류를 들 수 있고, 1종 단독으로 또는 2종 이상을 적당하게 조합하여 사용할 수 있다.A water-soluble organic solvent may be added to water for the purpose of improving the hydrolysis reaction rate of methyltrimethoxysilane or controlling the particle diameter of the polymethylphenylsilsequioxane particles. The organic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, propanol, and butanol, and ketones such as acetone, and they may be used singly or in combination of two or more.
공정 (i)에서는 물에 메틸트라이메톡시실레인을 첨가하고, 메틸트라이메톡시실레인의 가수분해 반응을 프로펠러 날개, 터빈 날개, 패들 날개 등의 통상의 교반기를 사용하여 교반하에서 행한다. 메틸트라이메톡시실레인은 한번에 첨가해도 되지만, 시간을 들여 서서히 첨가해도 된다. 또한, 반대로 메틸트라이메톡시실레인에 물을 첨가해도 되고, 조에 동시에 첨가 혼합해도 된다. 이때의 온도는 한정되지 않고, 1∼100℃의 범위에서 행하면 되고, 1∼30℃, 18∼30℃의 범위로 해도 된다. 가수분해 반응에 의해, 메틸트라이메톡시실레인은 식 CH3Si(OH)3로 표시되는 메틸실레인트라이올이 되고, 또 메탄올이 부생된다. 그래서, 실레인은 메탄올을 포함하는 물에 대하여 용해성으로 되어, 투명한 수용액이 된다.In step (i), methyltrimethoxysilane is added to water, and the hydrolysis reaction of methyltrimethoxysilane is carried out with stirring using a conventional stirrer such as a propeller blade, a turbine blade, and a paddle blade. Methyltrimethoxysilane may be added at once, but may be added slowly over time. On the contrary, water may be added to methyltrimethoxysilane, or may be added and mixed simultaneously in the tank. The temperature at this time is not limited and may be in the range of 1 to 100 캜, and may be in the range of 1 to 30 캜 and 18 to 30 캜. By the hydrolysis reaction, methyltrimethoxysilane becomes methylsilane triol represented by the formula CH 3 Si (OH) 3 , and methanol is produced as a by-product. Thus, the silane becomes soluble in water containing methanol, and becomes a transparent aqueous solution.
교반은 투명한 수용액으로 될 때까지 계속한다. 그 시간은, 가수분해 반응 속도에 따라, 즉, 물의 pH, 반응온도 및 교반 강도에 따라 다르다. 또한 메틸트라이메톡시실레인의 첨가량에 따라서도 다르다. 또한, 「투명」이란 가시광선에 대하여 흐림이 없이 물질을 통과시켜 맞은 편이 들여다 보이는 상태를 말한다.Stirring is continued until a clear aqueous solution is obtained. The time varies depending on the hydrolysis reaction rate, that is, the pH of the water, the reaction temperature and the stirring strength. It is also different depending on the addition amount of methyltrimethoxysilane. In addition, " transparent " refers to a state in which visible light passes through a material without fogging and is viewed from the opposite side.
(ii) 공정 (i)에서 얻어진 수용액에 페닐트라이메톡시실레인을 첨가하고, 가수분해 반응을 행하여, 투명한 수용액을 얻는 공정(ii) a step of adding phenyltrimethoxysilane to the aqueous solution obtained in the step (i) and conducting a hydrolysis reaction to obtain a transparent aqueous solution
페닐트라이메톡시실레인은 식 C6H5Si(OCH3)3로 표시된다. 또한, 수용액에는, 페닐트라이메톡시실레인의 가수분해 반응 속도 향상 등의 목적으로, 산성 물질을 첨가해도 된다. 산성 물질은 특별히 한정되지 않고, 예를 들면, 폼산, 아세트산, 옥살산, 말론산, 락트산, 말산(능금산) 등의 카복실산, 염산; 인산; 황산; 메테인설폰산; 트라이플루오로메테인설폰산 등을 1종 단독으로 또는 2종 이상을 적당하게 조합하여 사용할 수 있다. 또한, 페닐트라이메톡시실레인의 가수분해 반응 속도 향상이나 폴리메틸페닐실세스퀴옥세인 입자의 입경을 컨트롤할 목적 등으로, 수용액에 수용성의 유기 용제를 첨가해도 된다. 유기 용제는 특별히 한정되지 않고, 메탄올, 에탄올, 프로판올, 뷰탄올 등의 알코올류나 아세톤 등의 케톤류를 들 수 있고, 1종 단독으로 또는 2종 이상을 적당하게 조합하여 사용할 수 있다.Phenyltrimethoxysilane is represented by the formula C 6 H 5 Si (OCH 3 ) 3 . Further, for the purpose of improving the hydrolysis reaction rate of phenyltrimethoxysilane, an acidic substance may be added to the aqueous solution. The acidic substance is not particularly limited and includes, for example, carboxylic acid such as formic acid, acetic acid, oxalic acid, malonic acid, lactic acid, malic acid (malic acid), hydrochloric acid; Phosphoric acid; Sulfuric acid; Methanesulfonic acid; Trifluoromethanesulfonic acid, etc. may be used alone or in combination of two or more. A water-soluble organic solvent may be added to the aqueous solution for the purpose of improving the hydrolysis reaction rate of phenyltrimethoxysilane or controlling the particle diameter of the polymethylphenylsilsequioxane particles. The organic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, propanol, and butanol, and ketones such as acetone, and they may be used singly or in combination of two or more.
공정 (ii)에서는, 공정 (i)에서 얻어진 실레인의 수용액에 페닐트라이메톡시실레인을 첨가하고, 페닐트라이메톡시실레인의 가수분해 반응을 프로펠러 날개, 터빈 날개, 패들 날개 등의 통상의 교반기를 사용하여 교반하에서 행한다. 페닐트라이메톡시실레인은 한번에 첨가해도 되지만, 시간을 들여 서서히 첨가해도 된다. 이때의 온도는 한정되지 않고, 0∼100℃의 범위에서 행하면 된다. 가수분해 반응에 의해, 페닐트라이메톡시실레인은 식 C6H5Si(OH)3로 표시되는 페닐실레인트라이올이 되고, 또한 메탄올이 부생된다. 그래서, 실레인은 메탄올을 포함하는 물에 대하여 용해성으로 되어, 투명한 수용액이 된다.In the step (ii), phenyltrimethoxysilane is added to the aqueous solution of silane obtained in the step (i), and the hydrolysis reaction of the phenyltrimethoxysilane is carried out in a usual manner such as a propeller blade, a turbine blade, This is carried out with stirring using an agitator. The phenyltrimethoxysilane may be added at once, but it may be added slowly over time. The temperature at this time is not limited and may be set in the range of 0 to 100 占 폚. By the hydrolysis reaction, phenyltrimethoxysilane becomes phenylsilane triol represented by the formula C 6 H 5 Si (OH) 3 , and methanol is also produced as a by-product. Thus, the silane becomes soluble in water containing methanol, and becomes a transparent aqueous solution.
교반은 투명한 수용액으로 될 때까지 계속한다. 그 시간은 가수분해 반응 속도에 따라, 즉, 물의 pH, 반응온도 및 교반 강도에 따라 다르다. 또한 페닐트라이메톡시실레인의 첨가량에 따라서도 다르다.Stirring is continued until a clear aqueous solution is obtained. The time varies depending on the hydrolysis reaction rate, that is, the pH of the water, the reaction temperature and the stirring intensity. It is also different depending on the addition amount of phenyltrimethoxysilane.
공정 (i) 및 공정 (ii)에 있어서의, 메틸트라이메톡시실레인 및 페닐트라이메톡시실레인의 배합량은, 물 100질량부에 대하여, 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 5∼30질량부이며, 13∼28질량부가 바람직하다. 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 적으면 생산 효율이 나빠지고, 많으면 폴리메틸페닐실세스퀴옥세인 입자의 체적평균 입경을 5㎛ 이하로 하는 것이 곤란하게 된다.The blending amount of methyltrimethoxysilane and phenyltrimethoxysilane in the step (i) and the step (ii) is preferably in the range of 1 to 50 parts by weight, based on 100 parts by weight of water, of methyltrimethoxysilane and phenyltrimethoxysilane Is preferably 5 to 30 parts by mass, and more preferably 13 to 28 parts by mass. When the total amount of methyltrimethoxysilane and phenyltrimethoxysilane is less, the production efficiency is deteriorated, and when the total amount of methyltrimethoxysilane and phenyltrimethoxysilane is less, it becomes difficult to make the volume average particle diameter of the polymethylphenylsilsesquioxane particles to 5 m or less.
메틸트라이메톡시실레인:페닐트라이메톡시실레인으로 표시되는 질량비는 90:10∼20:80의 범위이며, 85:15∼40:60, 80:20∼50:50이 보다 바람직하고, 80:20∼55:45가 더욱 바람직하다. 트라이메톡시실레인 중의 페닐트라이메톡시실레인의 비율이 적으면 굴절률이 지나치게 낮아지고, 많으면 굴절률이 지나치게 높아질 우려가 있다.The mass ratio of methyltrimethoxysilane to phenyltrimethoxysilane is in the range of 90:10 to 20:80, more preferably 85:15 to 40:60 and 80:20 to 50:50, : 20 to 55: 45 are more preferable. If the proportion of phenyltrimethoxysilane in the trimethoxysilane is small, the refractive index is too low, and if it is large, the refractive index may be excessively high.
메틸트라이메톡시실레인 및 페닐트라이메톡시실레인의 합계 배합량, 및 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 배합 질량비가 상기의 범위에 있는 경우, 물에 메틸트라이메톡시실레인과 페닐트라이메톡시실레인을 동시에 첨가하여 가수분해를 행하면, 투명한 수용액을 얻는 것이 곤란하게 된다. 또한 물에 먼저 페닐트라이메톡시실레인을 첨가해도 투명한 수용액을 얻는 것이 곤란하게 된다. 이것은, 페닐트라이메톡시실레인이 가수분해된 후, 또한 축합 반응이 진행되어 물에 불용으로 되기 때문이다. 이 상태의 액을 사용하여, 앞의 공정으로 진행시키면, 그 불용 성분은 겔이 된다.When the total compounding amount of methyltrimethoxysilane and phenyltrimethoxysilane and the compounding mass ratio of methyltrimethoxysilane and phenyltrimethoxysilane are in the above ranges, methyltrimethoxysilane And phenyltrimethoxysilane are added at the same time and hydrolysis is carried out, it becomes difficult to obtain a transparent aqueous solution. Further, even if phenyltrimethoxysilane is first added to water, it becomes difficult to obtain a transparent aqueous solution. This is because, after the hydrolysis of the phenyltrimethoxysilane, the condensation reaction proceeds and becomes insoluble in water. When the solution in this state is used to proceed to the previous step, the insoluble component becomes a gel.
(iii) 공정 (ii)에서 얻어진 수용액을 0∼15℃의 온도로 조절하고, 이것에 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액을 첨가하고, 교반 혼합하여 혼합액을 얻는 공정(iii) a step of adjusting the aqueous solution obtained in the step (ii) to a temperature of 0 to 15 ° C, adding an aqueous solution in which an alkaline substance or an alkaline substance is dissolved, and stirring the mixture to obtain a mixed solution
알칼리성 물질은 가수분해한 메틸트라이메톡시실레인 및 페닐트라이메톡시실레인, 즉 메틸실레인트라이올 및 페닐실레인트라이올의 축합 반응 촉매로서 작용하고, 그것에 의해 공정 (iv)에서, 폴리메틸페닐실세스퀴옥세인 입자가 생성된다. 알칼리성 물질은 1종 단독으로 사용해도 2종 이상을 병용해도 된다. 알칼리성 물질은 그대로 첨가해도 되지만, 단시간에 물에 균일하게 용해시킬 필요가 있기 때문에, 고체상 및 기체상인 것은 수용액으로 하여 첨가한다. 물에 가용이면, 그 농도는 특별히 한정되지 않는다. 알칼리성 물질의 양은, 적어도, 공정 (iv)에 있어서 축합 반응이 진행되어 폴리메틸페닐실세스퀴옥세인 입자가 생성되는 양이 필요하다. 최저 필요량은 공정 (i)에서의 물의 pH나 알칼리성 물질의 종류나 반응 온도에 따라 다르다. 알칼리성 물질이 지나치게 많으면, 축합 반응 속도가 빨라져, 공정 (iii)에서 폴리메틸페닐실세스퀴옥세인 입자가 생성되기 시작함과 아울러, 응집 알갱이나 겔이 생성된다. 그 때문에 공정 (iii)에서 폴리메틸페닐실세스퀴옥세인 입자가 생성되지 않는 것과 같은 양으로 억제할 필요가 있다. 그 최대량은 메틸트라이메톡시실레인 및 페닐트라이메톡시실레인의 배합량이나 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 배합비나 알칼리성 물질의 종류나 반응온도에 따라 다르다. 예를 들면, 28질량%의 암모니아 수용액의 경우에서, 공정 (i)에서 사용한 물 100질량부에 대하여 0.01∼0.20질량부, 적합하게는 0.03∼0.10질량부의 범위에서 적당하게 선정된다.The alkaline substance acts as a condensation reaction catalyst of the hydrolyzed methyltrimethoxysilane and phenyltrimethoxysilane, i.e. methylsilane triol and phenylsilane triol, whereby in process (iv) the polymethylphenyl Silsesquioxane particles are produced. The alkaline substance may be used singly or in combination of two or more species. The alkaline substance may be added as it is, but it is necessary to dissolve the alkaline substance uniformly in water in a short period of time. If it is soluble in water, its concentration is not particularly limited. The amount of the alkaline substance needs to be such that at least the condensation reaction proceeds in the step (iv) to produce polymethylphenylsilsequioxane particles. The minimum required amount depends on the pH of the water in step (i), the type of alkaline substance, and the reaction temperature. If the amount of the alkaline substance is too large, the rate of the condensation reaction is accelerated so that the polymethylphenylsilsesquioxane particles start to be produced in the step (iii), and aggregated particles or gel are produced. Therefore, it is necessary to suppress the same amount as that in the step (iii) that no polymethylphenylsilsequioxane particles are generated. The maximum amount thereof depends on the blending amount of methyltrimethoxysilane and phenyltrimethoxysilane, the blending ratio of methyltrimethoxysilane and phenyltrimethoxysilane, the type of alkaline substance, and the reaction temperature. For example, in the case of an ammonia aqueous solution of 28 mass%, it is appropriately selected in a range of 0.01 to 0.20 mass parts, preferably 0.03 to 0.10 mass parts, relative to 100 mass parts of the water used in the step (i).
알칼리성 물질은 특별히 한정되지 않고, 예를 들면, 수산화포타슘, 수산화소듐, 수산화리튬 등의 알칼리 금속 수산화물; 수산화칼슘, 수산화바륨 등의 알칼리 토류 금속 수산화물; 탄산포타슘, 탄산소듐 등의 알칼리 금속 탄산염; 암모니아수; 테트라메틸암모늄하이드록사이드, 테트라에틸암모늄하이드록사이드 등의 테트라알킬암모늄하이드록사이드; 모노메틸아민, 모노에틸아민, 모노프로필아민, 모노뷰틸아민, 모노펜틸아민, 다이메틸아민, 다이에틸아민, 트라이메틸아민, 트라이에탄올아민, 에틸렌다이아민 등의 아민류 등을 사용할 수 있다. 그중에서도, 휘발시킴으로써, 얻어지는 폴리메틸페닐실세스퀴옥세인 입자로부터 용이하게 제거할 수 있으므로, 암모니아수가 바람직하다.The alkaline substance is not particularly limited and includes, for example, alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide; Alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; Alkali metal carbonates such as potassium carbonate and sodium carbonate; ammonia; Tetraalkylammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; Amines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, dimethylamine, diethylamine, trimethylamine, triethanolamine and ethylenediamine can be used. Among them, ammonia water is preferable because it can be easily removed from the obtained polymethylphenylsilsequioxane particles by volatilization.
알칼리성 물질 또는 알칼리성 물질을 용해한 수용액을 첨가할 때, 실레인의 수용액의 온도는 0∼15℃이며, 0∼10℃가 바람직하다. 온도가 높으면 축합 반응 속도가 빨라져, 공정 (iii)에서 폴리메틸페닐실세스퀴옥세인 입자가 생성되기 시작함과 아울러 응집 알갱이나 겔이 생성된다.When an aqueous solution in which an alkaline substance or an alkaline substance is dissolved is added, the temperature of the aqueous solution of silane is 0 to 15 占 폚, preferably 0 to 10 占 폚. When the temperature is high, the condensation reaction rate is accelerated, and in step (iii), polymethylphenylsilsesquioxane particles start to be produced and aggregated particles or gel are produced.
(ii)에서 얻어진 수용액에의 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액의 첨가는 프로펠러 날개, 터빈 날개, 패들 날개 등의 통상의 교반기를 사용하여 교반하에서 행한다. 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액은 한번에 첨가하고, 단시간에 물에 균일하게 용해시키는 것이 바람직하다. 균일하게 용해까지 시간이 걸리면, 입도 분포가 넓어지거나, 겔이 생성되거나 할 우려가 있다.The aqueous solution obtained by dissolving the alkaline substance or the alkaline substance in the aqueous solution obtained in the step (ii) is added with stirring using a conventional stirrer such as a propeller blade, a turbine blade or a paddle blade. It is preferable that the aqueous solution in which the alkaline substance or the alkaline substance is dissolved is added at once and dissolved uniformly in water in a short time. If it takes time to dissolve uniformly, the particle size distribution may be widened, or gel may be generated.
교반은 적어도 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액이 실레인의 수용액에 균일하게 용해될 때까지 필요하지만, 폴리메틸페닐실세스퀴옥세인 입자가 생성되기 시작하면 입자의 응집이나 겔을 생기게 하기 때문에, 폴리메틸페닐실세스퀴옥세인 입자가 생성되기 전에 교반을 정지한다. 폴리메틸페닐실세스퀴옥세인 입자가 생성되는 시간은 메틸트라이메톡시실레인 및 페닐트라이메톡시실레인의 배합량, 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 배합비, 알칼리 물질의 종류 및 양, 온도에 따라 다르다. 통상, 5초∼10분, 적합하게는 10초∼5분의 범위에서 적당히 선정된다.Stirring is required at least until an aqueous solution in which an alkaline substance or an alkaline substance is dissolved is uniformly dissolved in an aqueous solution of silane, but when polymethylphenylsilsesquioxane particles start to be produced, aggregation of the particles or gel is caused, Stirring is stopped before the silsesquioxane particles are formed. The time at which the polymethylphenylsilsesquioxane particles are formed is determined by the blending amount of methyltrimethoxysilane and phenyltrimethoxysilane, the blending ratio of methyltrimethoxysilane and phenyltrimethoxysilane, the kind and amount of alkali substance , Depending on temperature. It is appropriately selected in the range of usually 5 seconds to 10 minutes, preferably 10 seconds to 5 minutes.
(iv) 공정 (iii)에서 얻어진 혼합액을 정치 상태로 하고, 폴리메틸페닐실세스퀴옥세인 입자를 석출시키는 공정(iv) a step of bringing the mixed solution obtained in the step (iii) into a stationary state and precipitating polymethylphenylsilsequioxane particles
폴리메틸페닐실세스퀴옥세인 입자가 생성되면, 액은 백탁되어 간다. 백탁되어도 충분히 입자가 고화되지 않았기 때문에, 잠시 동안 그대로 정치해 둔다. 고화되지 않은 상태에서 교반을 행하면 입자가 응집되거나 겔을 생기게 하거나 한다. 필요하게 되는 정치 시간은 축합 반응 속도에 따라, 즉, 알칼리 물질의 종류 및 양, 반응온도에 따라 다르다. 통상, 30분∼24시간, 적합하게는 1시간∼12시간의 범위에서 적당히 선정된다. 이상으로부터, 체적평균 입경이 1∼5㎛의 구상 폴리메틸페닐실세스퀴옥세인 입자를 얻을 수 있다.When polymethylphenylsilsesquioxane particles are produced, the liquid becomes cloudy. Since the particles are not sufficiently solidified even if they are opaque, they are allowed to stand for a while. Stirring without solidification causes the particles to agglomerate or gel. The required standing time differs depending on the condensation reaction rate, that is, the kind and amount of the alkali substance, and the reaction temperature. It is appropriately selected in the range of usually 30 minutes to 24 hours, preferably 1 hour to 12 hours. From the above, spherical polymethylphenylsilsesquioxane particles having a volume average particle diameter of 1 to 5 m can be obtained.
(iv)의 공정 후, 구상 폴리메틸페닐실세스퀴옥세인 입자의 표면을 변성하기 위하여, 교반하, 일반식 R1Si(OR2)3로 표시되는 오가노트라이알콕시실레인이나, 일반식 R3 2Si(OR2)2로 표시되는 다이오가노다이알콕시실레인, 일반식 R3 3SiOR2로 표시되는 트라이오가노알콕시실레인, 일반식 Si(OR2)4로 표시되는 테트라알콕시실레인, 일반식 R2 3SiOH로 표시되는 트라이오가노실란올 및 식 [(CH3)3Si]2NH로 표시되는 헥사메틸다이실라잔의 1종 이상을 첨가하고, 축합 반응시켜도 된다. 식 중, R1은 메틸기 및 페닐기를 제외한 비치환 혹은 치환의 탄소수 1∼20의 1가 탄화수소기, R2는 비치환의 탄소원자수 1∼6의 1가 탄화수소기, R3은 비치환 혹은 치환의 탄소수 1∼20의 1가 탄화수소기이다.(iv), an organotrialkoxysilane represented by the general formula R 1 Si (OR 2 ) 3 and an organotrialkoxysilane represented by the general formula R 3 (OR 2 ) 3 under agitation in order to modify the surface of the spherical polymethylphenylsilsequioxane particles, 2 Si (OR 2 ) 2 , triorganoalkoxysilane represented by the general formula R 3 3 SiOR 2 , tetraalkoxysilane represented by the general formula Si (OR 2 ) 4 , A trioorganosilanol represented by the general formula R 2 3 SiOH and a hexamethyldisilazane represented by the formula [(CH 3 ) 3 Si] 2 NH may be added and condensation reaction may be carried out. Wherein R 1 is an unsubstituted or substituted monovalent hydrocarbon group of 1 to 20 carbon atoms excluding a methyl group and a phenyl group, R 2 is an unsubstituted monovalent hydrocarbon group of 1 to 6 carbon atoms, R 3 is an unsubstituted or substituted And is a monovalent hydrocarbon group of 1 to 20 carbon atoms.
(iv)의 공정 후, 축합 반응을 완결시키기 위하여, 교반하, 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액을 추가하거나, 40∼100℃로 가열하거나 해도 된다. 예를 들면, 교반하, (iv) 공정 후의 혼합액을 40∼100℃로 가열하고, 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액을 첨가해도 된다. 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액으로서는 상기에서 거론된 것을 사용할 수 있다. 교반 시간으로서는 특별히 한정되지 않고, 30분∼12시간에서 적당히 선정된다. (iv)의 공정 후, 필요하면, 교반하, 산성 물질을 투입하여 중화해도 된다.After the step (iv), in order to complete the condensation reaction, an aqueous solution in which an alkaline substance or an alkaline substance is dissolved under stirring may be added or heated to 40 to 100 캜. For example, an aqueous solution obtained by dissolving an alkaline substance or an alkaline substance may be added while heating the mixed solution after the step (iv) under stirring to 40 to 100 占 폚. As the aqueous solution in which the alkaline substance or the alkaline substance is dissolved, those mentioned above may be used. The stirring time is not particularly limited and is appropriately selected from 30 minutes to 12 hours. After the step (iv), if necessary, an acidic substance may be added thereto with stirring to be neutralized.
공정 (iv)에서 얻어진 폴리메틸페닐실세스퀴옥세인 입자의 분산액으로부터 수분 및 가수분해 반응에서 부생된 알코올을 제거함으로써, 구 형상의 폴리메틸페닐실세스퀴옥세인 입자를 얻을 수 있다. 수분의 제거는, 예를 들면, 반응 후의 수분산액을 상압 상태 또는 감압하에 가열함으로써 행할 수 있고, 구체적으로는, 분산액을 가열하에서 정치하여 수분을 제거하는 방법, 분산액을 가열하에서 교반 유동시키면서 수분을 제거하는 방법, 스프레이 드라이어와 같이 열풍기류 중에 분산액을 분무, 분산시키는 방법, 유동 열 매체를 이용하는 방법 등을 들 수 있다. 또한, 이 조작의 사전 처리로서, 가열 탈수, 여과 분리, 원심 분리, 디캔테이션 등의 방법으로 분산액을 농축해도 되고, 필요하면 분산액을 물이나 알코올로 세정해도 된다.By removing water and alcohol generated as a by-product in the hydrolysis reaction from the dispersion of the polymethylphenylsilsesquioxane particles obtained in the step (iv), spherical polymethylphenylsilsesquioxane particles can be obtained. The removal of moisture can be performed, for example, by heating the aqueous dispersion after the reaction under normal pressure or under reduced pressure. Specifically, the dispersion can be removed by standing under heating to remove moisture, A method of spraying and dispersing a dispersion in a hot air stream such as a spray dryer, a method of using a fluidized thermal medium, and the like. As a pretreatment of this operation, the dispersion may be concentrated by methods such as heat dehydration, filtration separation, centrifugation, or decantation, and if necessary, the dispersion may be washed with water or alcohol.
반응 후의 수분산액으로부터 수분을 제거한 후, 체적평균 입경이 1∼5㎛의 구상 폴리메틸페닐실세스퀴옥세인 입자가 응집해 있는 경우에는, 제트밀, 볼밀, 해머밀 등의 분쇄기로 해쇄하면 된다.When water is removed from the aqueous dispersion after the reaction, if the spherical polymethylphenylsilsequioxane particles having a volume average particle diameter of 1 to 5 μm are aggregated, they may be pulverized by a pulverizer such as a jet mill, a ball mill or a hammer mill.
또한, 본 발명에 있어서, 체적평균 입경이란 전기저항법에 의해 구한 체적 기준의 평균 입경을 의미한다. 체적평균 입경은 전위 저항법 입도 분포 측정 장치로 측정할 수 있다. 예를 들면, 베크만 쿨터 가부시키가이샤제의 멀티 사이저에 의해 측정할 수 있다.In the present invention, the volume average particle diameter means the average particle diameter based on volume determined by an electric resistance method. The volume average particle diameter can be measured by a potentiostat method particle size distribution measuring apparatus. For example, it can be measured by a multisizer manufactured by Beckman Coulter, Inc.
실시예Example
이하, 실시예 및 비교예를 제시하여, 본 발명을 구체적으로 설명하지만, 본 발명은 하기의 실시예에 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.
[평균 굴절률의 측정][Measurement of average refractive index]
굴절률이 1.40의 데카메틸사이클로펜테인실록세인과, 굴절률이 1.51의 메틸페닐폴리실록세인을 사용하여, 그 배합비율을 변경하여, 굴절률이 1.46, 1.47, 1.48, 1.49, 1.50의 혼합 용해액을 준비했다. 또한 굴절률이 1.51의 메틸페닐폴리실록세인을 준비했다. 준비한 액 20g을 각각 25ml 유리병에 칭량하여 취하고, 또한 분체를 1g씩 첨가하고, 뚜껑을 닫고 5분간 진탕하여, 액 중에 분체를 균일하게 분산시켰다. 정치 10분 후에 투명성을 관찰하고, 가장 투명성이 높은 액의 굴절률을 분체의 평균 굴절률로 했다.A mixing solution of decamethylcyclopentane siloxane having a refractive index of 1.40 and methylphenyl polysiloxane having a refractive index of 1.51 was used to prepare a mixed solution having refractive indices of 1.46, 1.47, 1.48, 1.49 and 1.50. A methylphenyl polysiloxane having a refractive index of 1.51 was also prepared. Each 20 g of the prepared solution was weighed into a 25 ml glass bottle, and 1 g of the powder was added thereto. The lid was closed and shaken for 5 minutes to disperse the powder uniformly in the liquid. After 10 minutes from the standstill, transparency was observed, and the refractive index of the liquid with the highest transparency was determined as the average refractive index of the powder.
[실시예 1][Example 1]
1리터의 유리 플라스크에 이온교환수 801g을 장입하고, 수온을 20℃로 했다. 이온교환수의 pH를 측정한 바 5.9이었다. 날개 회전수 150rpm의 조건으로 앵커형 교반 날개에 의해 교반을 행하고, 메틸트라이메톡시실레인 95.5g을 투입한 바 발열이 일어나 24℃까지 온도가 상승했다. 3분 후에 투명한 상태로 되었고, 7분 더 교반했다. 이어서, 페닐트라이메톡시실레인 62.5g을 투입하고, 20∼25℃의 온도를 유지하고 교반을 계속한 바, 50분 후에 투명한 상태로 되었고, 5분간 더 교반했다. 25분 걸쳐, 5℃까지 냉각했다. 28질량% 암모니아 수용액 0.53g과 이온교환수 2.65g의 혼합 용해액을 투입하고, 30초간 교반한 후, 교반을 정지했다. 교반 정지 12초 후에 백탁이 일어났다.A 1-liter glass flask was charged with 801 g of ion-exchanged water, and the water temperature was 20 占 폚. The pH of the ion-exchanged water was measured and found to be 5.9. Stirring was carried out with an anchor type stirring blades under the condition of a wing rotation speed of 150 rpm, and 95.5 g of methyltrimethoxysilane was added, and heat generation occurred and the temperature rose to 24 캜. After 3 minutes the mixture became clear and stirred for an additional 7 minutes. Subsequently, 62.5 g of phenyltrimethoxysilane was added, and stirring was continued while maintaining the temperature at 20 to 25 ° C. After 50 minutes, the mixture became transparent and stirred for 5 minutes. It was cooled to 5 캜 over 25 minutes. 0.53 g of a 28% by mass aqueous ammonia solution and 2.65 g of ion-exchanged water were added, stirred for 30 seconds, and then stirred. White stain occurred after 12 seconds of stirring stop.
메틸트라이메톡시실레인 및 페닐트라이메톡시실레인은 물 100질량부에 대한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 19.7질량부이며, 또한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 질량비가 60.4:39.6이 되는 배합량이다.Methyltrimethoxysilane and phenyltrimethoxysilane, the total amount of methyltrimethoxysilane and phenyltrimethoxysilane relative to 100 parts by mass of water is 19.7 parts by mass, and the sum of methyltrimethoxysilane and phenyl And the mass ratio of trimethoxysilane is 60.4: 39.6.
3시간 정치한 후, 날개회전수 150rpm의 조건으로 교반을 개시했다. 75℃까지 가열하고, 28질량% 암모니아 수용액 38g을 첨가하고, 또한 73∼77℃의 온도에서 1시간 교반을 행했다. 30℃ 이하까지 냉각 후, 1리터의 유리 비커에 옮기고, 유리 플라스크의 내벽 및 교반 날개를 관찰한 바, 겔의 부착은 확인되지 않았다. 얻어진 액을 가압 여과기를 사용하여 탈액하여 케이크 형상물로 만들고, 이 케이크 형상물을 열풍 순환 건조기 중에서 105℃의 온도로 건조하고, 건조물을 제트밀로 해쇄하여, 폴리메틸페닐실세스퀴옥세인 입자를 얻었다.After the mixture was allowed to stand for 3 hours, agitation was started under the condition of a blade rotation speed of 150 rpm. The mixture was heated to 75 占 폚, 38 g of a 28 mass% aqueous ammonia solution was added, and the mixture was stirred at a temperature of 73 to 77 占 폚 for 1 hour. After cooling to 30 ° C or lower, the mixture was transferred to a 1-liter glass beaker, and the inner wall of the glass flask and stirring wing were observed. The resulting liquid was dewatered by using a pressure filter to obtain a cake-like material. The cake-like material was dried in a hot-air circulating drier at a temperature of 105 ° C and the dried material was pulverized with a jet mill to obtain polymethylphenylsilsequioxane particles.
이 폴리메틸페닐실세스퀴옥세인 입자의 형상을 전자현미경으로 관찰한 바, 구상이었다. 폴리메틸페닐실세스퀴옥세인 입자의 체적평균 입경을 전기저항법 입도 분포 측정 장치 「멀티 사이저 3」(베크만 쿨터(주)제)을 사용하여 측정한 바, 2.1㎛이었다. 또한 표준편차(S.D.)는 0.29㎛, 변동계수(C.V.)는 13.6%이었다. 상기의 방법으로 평균 굴절률을 측정한 바, 1.49이었다.The shape of the polymethylphenylsilsesquioxane particles was observed by an electron microscope, and it was spherical. The volume average particle diameter of the polymethylphenylsilsesquioxane particles was measured using an electric resistance method particle size distribution analyzer " Multisizer 3 " (manufactured by Beckman Coulter, Inc.), and found to be 2.1 μm. The standard deviation (SD) was 0.29 mu m and the coefficient of variation (CV) was 13.6%. The average refractive index was measured by the above method and was found to be 1.49.
[실시예 2][Example 2]
1리터의 유리 플라스크에 이온교환수 815g을 장입하고, 수온을 20℃로 했다. 이온교환수의 pH를 측정한 바 5.9이었다. 날개 회전수 150rpm의 조건으로 앵커형 교반 날개에 의해 교반을 행하고, 메틸트라이메톡시실레인 77.6g을 투입하자 발열이 일어나 24℃까지 온도가 상승했다. 3분 후에 투명한 상태로 되었고, 7분 더 교반했다. 이어서 페닐트라이메톡시실레인 66.4g을 투입하고, 20∼25℃의 온도를 유지하고 교반을 계속한 바, 55분 후에 투명한 상태로 되었고, 5분간 더 교반했다. 25분 걸쳐, 5℃까지 냉각했다. 28질량% 암모니아 수용액 0.54g과 이온교환수 2.7g의 혼합 용해액을 투입하고, 20초간 교반한 후, 교반을 정지했다. 교반 정지 12초 후에 백탁이 일어났다.A 1-liter glass flask was charged with 815 g of ion-exchanged water, and the water temperature was 20 占 폚. The pH of the ion-exchanged water was measured and found to be 5.9. Agitation was carried out with an anchor type stirring blades under the condition that the number of revolutions of the blade was 150 rpm, and when 77.6 g of methyltrimethoxysilane was added, heat generation occurred and the temperature rose to 24 캜. After 3 minutes the mixture became clear and stirred for an additional 7 minutes. Subsequently, 66.4 g of phenyltrimethoxysilane was added, and stirring was continued while maintaining the temperature at 20 to 25 ° C. After 55 minutes, the mixture became transparent and stirred for 5 minutes. It was cooled to 5 캜 over 25 minutes. 0.54 g of a 28% by mass aqueous ammonia solution and 2.7 g of ion-exchanged water were added, stirred for 20 seconds, and then stirred. White stain occurred after 12 seconds of stirring stop.
메틸트라이메톡시실레인 및 페닐트라이메톡시실레인은 물 100질량부에 대한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 17.7질량부이며, 또한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 질량비가 53.9:46.1이 되는 배합량이다.Methyltrimethoxysilane and phenyltrimethoxysilane, the total amount of methyltrimethoxysilane and phenyltrimethoxysilane relative to 100 parts by mass of water is 17.7 parts by mass, and the sum of methyltrimethoxysilane and phenyl And the mass ratio of trimethoxysilane is 53.9: 46.1.
3시간 정치한 후, 날개 회전수 150rpm의 조건으로 교반을 개시했다. 75℃까지 가열하고, 28질량% 암모니아 수용액 38g을 첨가하고, 73∼77℃의 온도에서 1시간 더 교반을 행했다. 30℃ 이하까지 냉각 후, 1리터의 유리 비커에 옮기고, 유리 플라스크의 내벽 및 교반 날개를 관찰한 바, 겔의 부착은 확인되지 않았다. 얻어진 액을 가압 여과기를 사용하여 탈액하여 케이크 형상물로 만들고, 이 케이크 형상물을 열풍 순환 건조기 중에서 105℃의 온도로 건조하고, 건조물을 제트밀로 해쇄하여, 폴리메틸페닐실세스퀴옥세인 입자를 얻었다.After the mixture was allowed to stand for 3 hours, agitation was started under the condition of a blade rotation speed of 150 rpm. The mixture was heated to 75 캜, 38 g of a 28% by mass aqueous ammonia solution was added, and stirring was further performed at a temperature of 73 to 77 캜 for one hour. After cooling to 30 ° C or lower, the mixture was transferred to a 1-liter glass beaker, and the inner wall of the glass flask and stirring wing were observed. The resulting liquid was dewatered by using a pressure filter to obtain a cake-like material. The cake-like material was dried in a hot-air circulating drier at a temperature of 105 ° C and the dried material was pulverized with a jet mill to obtain polymethylphenylsilsequioxane particles.
이 폴리메틸페닐실세스퀴옥세인 입자의 형상을 전자현미경으로 관찰한 바, 구상이었다. 폴리메틸페닐실세스퀴옥세인 입자의 체적평균 입경을 전기저항법 입도 분포 측정 장치 「멀티 사이저 3」(베크만 쿨터(주)제)을 사용하여 측정한 바, 2.1㎛이었다. 또한 표준편차(S.D.)는 0.19㎛, 변동계수(C.V.)는 8.6%이었다. 상기의 방법으로 평균 굴절률을 측정한 바, 1.50이었다.The shape of the polymethylphenylsilsesquioxane particles was observed by an electron microscope, and it was spherical. The volume average particle diameter of the polymethylphenylsilsesquioxane particles was measured using an electric resistance method particle size distribution analyzer " Multisizer 3 " (manufactured by Beckman Coulter, Inc.), and found to be 2.1 μm. The standard deviation (SD) was 0.19 mu m and the coefficient of variation (CV) was 8.6%. The average refractive index was measured by the above method and was found to be 1.50.
[실시예 3][Example 3]
1리터의 유리 플라스크에 이온교환수 789g을 장입하고, 수온을 20℃로 했다. 이온교환수의 pH를 측정한 바 5.8이었다. 날개회전수 150rpm의 조건으로 앵커형 교반 날개에 의해 교반을 행하고, 메틸트라이메톡시실레인 110.5g을 투입한 바 발열이 일어나 24℃까지 온도가 상승했다. 4분 후에 투명한 상태로 되었고, 6분 더 교반했다. 이어서 페닐트라이메톡시실레인 59.5g을 투입하고, 20∼25℃의 온도를 유지하고 교반을 계속한 바, 45분 후에 투명한 상태로 되었고, 5분간 더 교반했다. 25분 걸쳐, 5℃까지 냉각했다. 28질량% 암모니아 수용액 0.52g과 이온교환수 2.6g의 혼합 용해액을 투입하고, 30초간 교반한 후, 교반을 정지했다. 교반 정지 30초 후에 백탁이 일어났다.A 1-liter glass flask was charged with 789 g of ion-exchanged water, and the water temperature was 20 占 폚. The pH of the ion-exchanged water was measured to be 5.8. Stirring was carried out with an anchor type stirring wing under the condition of a wing rotation speed of 150 rpm, and 110.5 g of methyltrimethoxysilane was added, and heat generation occurred and the temperature rose to 24 캜. After 4 minutes the mixture became clear and stirred for an additional 6 minutes. Subsequently, 59.5 g of phenyltrimethoxysilane was added, and stirring was continued at a temperature of 20 to 25 ° C. After 45 minutes, the mixture became transparent and stirred for 5 minutes. It was cooled to 5 캜 over 25 minutes. 0.52 g of 28% by mass aqueous ammonia solution and 2.6 g of ion-exchanged water were added, stirred for 30 seconds, and then stirred. Whitening occurred after 30 seconds of stirring stop.
메틸트라이메톡시실레인 및 페닐트라이메톡시실레인은 물 100질량부에 대한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 21.5질량부이며, 또한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 질량비가 65.0:35.0이 되는 배합량이다.Methyltrimethoxysilane and phenyltrimethoxysilane, the total amount of methyltrimethoxysilane and phenyltrimethoxysilane relative to 100 parts by mass of water is 21.5 parts by mass, and the sum of methyltrimethoxysilane and phenyl And the mass ratio of trimethoxysilane is 65.0: 35.0.
3시간 정치한 후, 날개 회전수 150rpm의 조건으로 교반을 개시했다. 75℃까지 가열하고, 28질량% 암모니아 수용액 38g을 첨가하고, 또한 73∼77℃의 온도에서 1시간 교반을 행했다. 30℃ 이하까지 냉각 후, 1리터의 유리 비커에 옮기고, 유리 플라스크의 내벽 및 교반 날개를 관찰한 바, 겔의 부착은 확인되지 않았다. 얻어진 액을 가압 여과기를 사용하여 탈액하여 케이크 형상물로 만들고, 이 케이크 형상물을 열풍 순환 건조기 중에서 105℃의 온도로 건조하고, 건조물을 제트밀로 해쇄하여, 폴리메틸페닐실세스퀴옥세인 입자를 얻었다.After the mixture was allowed to stand for 3 hours, agitation was started under the condition of a blade rotation speed of 150 rpm. The mixture was heated to 75 占 폚, 38 g of a 28 mass% aqueous ammonia solution was added, and the mixture was stirred at a temperature of 73 to 77 占 폚 for 1 hour. After cooling to 30 ° C or lower, the mixture was transferred to a 1-liter glass beaker, and the inner wall of the glass flask and stirring wing were observed. The resulting liquid was dewatered by using a pressure filter to obtain a cake-like material. The cake-like material was dried in a hot-air circulating drier at a temperature of 105 ° C and the dried material was pulverized with a jet mill to obtain polymethylphenylsilsequioxane particles.
이 폴리메틸페닐실세스퀴옥세인 입자의 형상을 전자현미경으로 관찰한 바, 구상이었다. 폴리메틸페닐실세스퀴옥세인 입자의 체적평균 입경을 전기저항법 입도 분포 측정 장치「멀티 사이저 3」(베크만 쿨터(주)제)를 사용하여 측정한 바, 2.2㎛이었다. 또한 표준편차(S.D.)는 0.27㎛, 변동계수(C.V.)는 12.0%이었다. 상기의 방법에서 평균 굴절률을 측정한 바, 1.48이었다.The shape of the polymethylphenylsilsesquioxane particles was observed by an electron microscope, and it was spherical. The volume average particle diameter of the polymethylphenylsilsesquioxane particles was measured using an electric resistance method particle size distribution analyzer " Multisizer 3 " (manufactured by Beckman Coulter, Inc.) and found to be 2.2 μm. The standard deviation (SD) was 0.27 mu m and the coefficient of variation (CV) was 12.0%. In the above method, the average refractive index was measured to be 1.48.
[실시예 4][Example 4]
1리터의 유리 플라스크에 이온교환수 754g을 장입하고, 수온을 20℃로 했다. 이온교환수의 pH를 측정한 바 5.9이었다. 날개 회전수 150rpm의 조건으로 앵커형 교반 날개에 의해 교반을 행하고, 메틸트라이메톡시실레인 142.9g을 투입한 바 발열이 일어나 24℃까지 온도가 상승했다. 7분 후에 투명한 상태로 되었고, 8분 더 교반했다. 이어서 페닐트라이메톡시실레인 62.1g을 투입하고, 20∼25℃의 온도를 유지하고 교반을 계속한 바, 35분 후에 투명한 상태로 되었고, 5분간 더 교반했다. 25분 걸쳐, 5℃까지 냉각했다. 28질량% 암모니아 수용액 0.50g과 이온교환수 2.5g의 혼합 용해액을 투입하고, 30초간 교반한 후, 교반을 정지했다. 교반 정지 1분 15초 후에 백탁이 일어났다.One liter glass flask was charged with 754 g of ion-exchanged water, and the water temperature was 20 占 폚. The pH of the ion-exchanged water was measured and found to be 5.9. Stirring was carried out with an anchor type stirring wing under the condition of a wing rotation speed of 150 rpm, and 142.9 g of methyltrimethoxysilane was added, and heat generation occurred and the temperature rose to 24 캜. After 7 minutes, it became clear and stirred for an additional 8 minutes. Subsequently, 62.1 g of phenyltrimethoxysilane was added, and stirring was continued while maintaining the temperature at 20 to 25 ° C. After 35 minutes, the mixture became transparent and stirred for 5 minutes. It was cooled to 5 캜 over 25 minutes. 0.50 g of a 28% by mass aqueous ammonia solution and 2.5 g of ion-exchanged water were added, stirred for 30 seconds, and then stirred. After 1 minute and 15 seconds of agitation, clouding occurred.
메틸트라이메톡시실레인 및 페닐트라이메톡시실레인은 물 100질량부에 대한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 27.2질량부이며, 또한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 질량비가 69.7:30.3이 되는 배합량이다.Methyltrimethoxysilane and phenyltrimethoxysilane, the total amount of methyltrimethoxysilane and phenyltrimethoxysilane relative to 100 parts by mass of water is 27.2 parts by mass, and the sum of methyltrimethoxysilane and phenyl And the mass ratio of trimethoxysilane is 69.7: 30.3.
3시간 정치한 후, 날개 회전수 150rpm의 조건으로 교반을 개시했다. 75℃까지 가열하고, 28질량% 암모니아 수용액 38g을 첨가하고, 73∼77℃의 온도에서 1시간 더 교반을 행했다. 30℃ 이하까지 냉각 후, 1리터의 유리 비커에 옮기고, 유리 플라스크의 내벽 및 교반 날개를 관찰한 바, 겔의 부착은 확인되지 않았다. 얻어진 액을 가압 여과기를 사용하여 탈액하여 케이크 형상물로 만들고, 이 케이크 형상물을 열풍 순환 건조기 중에서 105℃의 온도로 건조하고, 건조물을 제트밀로 해쇄하여, 폴리메틸페닐실세스퀴옥세인 입자를 얻었다.After the mixture was allowed to stand for 3 hours, agitation was started under the condition of a blade rotation speed of 150 rpm. The mixture was heated to 75 캜, 38 g of a 28% by mass aqueous ammonia solution was added, and stirring was further performed at a temperature of 73 to 77 캜 for one hour. After cooling to 30 ° C or lower, the mixture was transferred to a 1-liter glass beaker, and the inner wall of the glass flask and stirring wing were observed. The resulting liquid was dewatered by using a pressure filter to obtain a cake-like material. The cake-like material was dried in a hot-air circulating drier at a temperature of 105 ° C and the dried material was pulverized with a jet mill to obtain polymethylphenylsilsequioxane particles.
이 폴리메틸페닐실세스퀴옥세인 입자의 형상을 전자현미경으로 관찰한 바, 구상이었다. 폴리메틸페닐실세스퀴옥세인 입자의 체적평균 입경을 전기저항법 입도 분포 측정 장치 「멀티 사이저 3」(베크만 쿨터(주)제)을 사용하여 측정한 바, 2.8㎛이었다. 또한 표준편차(S.D.)는 0.37㎛, 변동계수(C.V.)는 13.4%이었다. 상기의 방법으로 평균 굴절률을 측정한 바, 1.47이었다.The shape of the polymethylphenylsilsesquioxane particles was observed by an electron microscope, and it was spherical. The volume average particle diameter of the polymethylphenylsilsesquioxane particles was measured using an electric resistance method particle size distribution analyzer " Multisizer 3 " (manufactured by Beckman Coulter, Inc.), and found to be 2.8 μm. The standard deviation (SD) was 0.37 mu m and the coefficient of variation (CV) was 13.4%. The average refractive index was measured by the above method and found to be 1.47.
[실시예 5][Example 5]
1리터의 유리 플라스크에 이온교환수 759g을 장입하고, 수온을 20℃로 했다. 이온교환수의 pH를 측정한 바 6.0이었다. 날개회전수 150rpm의 조건으로 앵커형 교반 날개에 의해 교반을 행하고, 메틸트라이메톡시실레인 151.6g을 투입한 바 발열이 일어나 24℃까지 온도가 상승했다. 8분 후에 투명한 상태로 되었고, 7분 더 교반했다. 이어서 페닐트라이메톡시실레인 48.4g을 투입하고, 20∼25℃의 온도를 유지하고 교반을 계속한 바, 30분 후에 투명한 상태로 되었고, 5분간 더 교반했다. 25분 걸쳐, 5℃까지 냉각했다. 28질량% 암모니아 수용액 0.50g과 이온교환수 2.5g의 혼합 용해액을 투입하고, 30초간 교반한 후, 교반을 정지했다. 교반 정지 1분 40초 후에 백탁이 일어났다.A 1-liter glass flask was charged with 759 g of ion-exchanged water, and the water temperature was 20 占 폚. The pH of the ion-exchanged water was measured to be 6.0. Stirring was carried out with an anchor type stirring blades under the condition of a wing rotation speed of 150 rpm, and 151.6 g of methyltrimethoxysilane was added, and heat generation occurred and the temperature rose to 24 캜. After 8 minutes the mixture became clear and stirred for an additional 7 minutes. Subsequently, 48.4 g of phenyltrimethoxysilane was added, and stirring was continued while maintaining the temperature at 20 to 25 ° C. After 30 minutes, the mixture became transparent and stirred for 5 minutes. It was cooled to 5 캜 over 25 minutes. 0.50 g of a 28% by mass aqueous ammonia solution and 2.5 g of ion-exchanged water were added, stirred for 30 seconds, and then stirred. Agitation stopped After 1 minute and 40 seconds, cloudiness occurred.
메틸트라이메톡시실레인 및 페닐트라이메톡시실레인은 물 100질량부에 대한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 26.3질량부이며, 또한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 질량비가 75.8:24.2이 되는 배합량이다.Methyltrimethoxysilane and phenyltrimethoxysilane, the total amount of methyltrimethoxysilane and phenyltrimethoxysilane relative to 100 parts by mass of water is 26.3 parts by mass, and the sum of methyltrimethoxysilane and phenyl And the mass ratio of trimethoxysilane is 75.8: 24.2.
3시간 정치한 후, 날개회전수 150rpm의 조건으로 교반을 개시했다. 75℃까지 가열하고, 28질량% 암모니아 수용액 38g 첨가하고, 또한 73∼77℃의 온도에서 1시간 교반을 행했다. 30℃ 이하까지 냉각 후, 1리터의 유리 비커에 옮기고, 유리 플라스크의 내벽 및 교반 날개를 관찰한 바, 겔의 부착은 확인되지 않았다. 얻어진 액을 가압 여과기를 사용하여 탈액하여 케이크 형상물로 만들고, 이 케이크 형상물을 열풍 순환 건조기 중에서 105℃의 온도로 건조하고, 건조물을 제트밀로 해쇄하여, 폴리메틸페닐실세스퀴옥세인 입자를 얻었다.After the mixture was allowed to stand for 3 hours, agitation was started under the condition of a blade rotation speed of 150 rpm. The mixture was heated to 75 DEG C, 38 g of a 28 mass% ammonia aqueous solution was added, and stirring was performed at 73 to 77 DEG C for 1 hour. After cooling to 30 ° C or lower, the mixture was transferred to a 1-liter glass beaker, and the inner wall of the glass flask and stirring wing were observed. The resulting liquid was dewatered by using a pressure filter to obtain a cake-like material. The cake-like material was dried in a hot-air circulating drier at a temperature of 105 ° C and the dried material was pulverized with a jet mill to obtain polymethylphenylsilsequioxane particles.
이 폴리메틸페닐실세스퀴옥세인 입자의 형상을 전자현미경으로 관찰한 바, 구상이었다. 폴리메틸페닐실세스퀴옥세인 입자의 체적평균 입경을 전기저항법 입도 분포 측정 장치 「멀티 사이저 3」(베크만 쿨터(주)제)을 사용하여 측정한 바, 3.2㎛이었다. 또한 표준편차(S.D.)는 0.52㎛, 변동계수(C.V.)는 16.3%이었다. 상기의 방법으로 평균 굴절률을 측정한 바, 1.46이었다.The shape of the polymethylphenylsilsesquioxane particles was observed by an electron microscope, and it was spherical. The volume average particle diameter of the polymethylphenylsilsesquioxane particles was measured using an electric resistance method particle size distribution analyzer " Multisizer 3 " (manufactured by Beckman Coulter, Inc.), and found to be 3.2 탆. The standard deviation (SD) was 0.52 탆 and the coefficient of variation (CV) was 16.3%. The average refractive index was measured by the above method and found to be 1.46.
[비교예 1][Comparative Example 1]
1리터의 유리 플라스크에 이온교환수 801g을 장입하고, 수온을 20℃로 했다. 이온교환수의 pH를 측정한 바 5.9이었다. 날개 회전수 150rpm의 조건으로 앵커형 교반 날개에 의해 교반을 행하고, 메틸트라이메톡시실레인 95.5g 및 페닐트라이메톡시실레인 62.5g의 혼합 용해액을 투입하자 발열이 일어나 24℃까지 온도가 상승했다. 20∼25℃의 온도를 유지하고 300분간 교반을 계속했지만, 회색으로 흐려진 상태로 투명으로 되지 않았다.A 1-liter glass flask was charged with 801 g of ion-exchanged water, and the water temperature was 20 占 폚. The pH of the ion-exchanged water was measured and found to be 5.9. Agitation was carried out with an anchor type stirring blade under the condition of a wing rotation speed of 150 rpm and a mixed solution of 95.5 g of methyltrimethoxysilane and 62.5 g of phenyltrimethoxysilane was put into a heating solution to raise the temperature to 24 캜 did. The stirring was continued for 300 minutes while maintaining the temperature at 20 to 25 占 폚, but it did not become transparent in a gray-blurred state.
메틸트라이메톡시실레인 및 페닐트라이메톡시실레인은 물 100질량부에 대한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 19.7질량부이며, 또한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 질량비가 60.4:39.6이 되는 배합량이다.Methyltrimethoxysilane and phenyltrimethoxysilane, the total amount of methyltrimethoxysilane and phenyltrimethoxysilane relative to 100 parts by mass of water is 19.7 parts by mass, and the sum of methyltrimethoxysilane and phenyl And the mass ratio of trimethoxysilane is 60.4: 39.6.
25분 걸쳐서, 5℃까지 냉각했다. 28질량% 암모니아 수용액 0.54g과 이온교환수 2.7g의 혼합 용해액을 투입하고, 20초간 교반한 후, 교반을 정지했다. 교반 정지 10초 후에 백탁이 일어났다. 3시간 정치한 후, 날개 회전수 150rpm의 조건으로 교반을 개시했다. 75℃까지 가열하고, 28질량% 암모니아 수용액 38g을 첨가하고, 또한 73∼77℃의 온도에서 1시간 교반을 행했다. 30℃ 이하까지 냉각 후, 1리터의 유리 비커에 옮기고, 유리 플라스크의 내벽 및 교반 날개를 관찰한 바, 유리 플라스크의 바닥부 및 교반 날개에 단단한 겔의 부착이 확인되었다.Over a period of 25 minutes, to 5 占 폚. 0.54 g of a 28% by mass aqueous ammonia solution and 2.7 g of ion-exchanged water were added, stirred for 20 seconds, and then stirred. Clouding occurred after 10 seconds of stoppage of stirring. After the mixture was allowed to stand for 3 hours, agitation was started under the condition of a blade rotation speed of 150 rpm. The mixture was heated to 75 占 폚, 38 g of a 28 mass% aqueous ammonia solution was added, and the mixture was stirred at a temperature of 73 to 77 占 폚 for 1 hour. After cooling to 30 DEG C or lower, the mixture was transferred to a 1 liter glass beaker, and the inner wall of the glass flask and the stirring blades were observed. As a result, the adhesion of the solid gel to the bottom of the glass flask and the stirring blades was confirmed.
[비교예 2][Comparative Example 2]
1리터의 유리 플라스크에 이온교환수 801g을 장입하고, 수온을 20℃로 했다. 이온교환수의 pH를 측정한 바 5.9이었다. 날개 회전수 150rpm의 조건으로 앵커형 교반 날개에 의해 교반을 행하고, 페닐트라이메톡시실레인 62.5g을 투입하고 20∼25℃의 온도를 유지하고 300분간 교반을 계속했지만, 회색으로 흐려진 상태로 투명으로 되지 않았다. 이어서 메틸트라이메톡시실레인 95.5g을 투입한 바 발열이 일어나 26℃까지 온도가 상승했다. 20∼25℃의 온도를 유지하여 60분간 교반을 계속했지만, 회색으로 흐려진 상태로 투명으로 되지 않았다.A 1-liter glass flask was charged with 801 g of ion-exchanged water, and the water temperature was 20 占 폚. The pH of the ion-exchanged water was measured and found to be 5.9. Agitation was carried out with an anchor type stirring blade under the conditions of a blade rotation speed of 150 rpm, 62.5 g of phenyltrimethoxysilane was added, and the stirring was continued for 300 minutes while maintaining the temperature at 20 to 25 캜. However, Respectively. Subsequently, 95.5 g of methyltrimethoxysilane was added, and heat generation occurred, and the temperature rose to 26 캜. Stirring was continued for 60 minutes while maintaining the temperature at 20 to 25 ° C, but it did not become transparent in a gray blurred state.
메틸트라이메톡시실레인 및 페닐트라이메톡시실레인은 물 100질량부에 대한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 19.7질량부이며, 또한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 질량비가 60.4:39.6이 되는 배합량이다.Methyltrimethoxysilane and phenyltrimethoxysilane, the total amount of methyltrimethoxysilane and phenyltrimethoxysilane relative to 100 parts by mass of water is 19.7 parts by mass, and the sum of methyltrimethoxysilane and phenyl And the mass ratio of trimethoxysilane is 60.4: 39.6.
25분 걸쳐, 5℃까지 냉각했다. 28질량% 암모니아 수용액 0.54g과 이온교환수 2.7g의 혼합 용해액을 투입하고, 20초간 교반한 후, 교반을 정지했다. 교반 정지 9초 후에 백탁이 일어났다. 3시간 정치한 후, 날개 회전수 150rpm의 조건으로 교반을 개시했다. 75℃까지 가열하고, 28질량% 암모니아 수용액 38g을 첨가하고, 또한 73∼77℃의 온도에서 1시간 교반을 행했다. 30℃ 이하까지 냉각 후, 1리터의 유리 비커에 옮기고, 유리 플라스크의 내벽 및 교반 날개를 관찰한 바, 유리 플라스크의 바닥부 및 교반 날개에 단단한 겔의 부착이 확인되었다.It was cooled to 5 캜 over 25 minutes. 0.54 g of a 28% by mass aqueous ammonia solution and 2.7 g of ion-exchanged water were added, stirred for 20 seconds, and then stirred. White stain occurred after 9 seconds of stirring stop. After the mixture was allowed to stand for 3 hours, agitation was started under the condition of a blade rotation speed of 150 rpm. The mixture was heated to 75 占 폚, 38 g of a 28 mass% aqueous ammonia solution was added, and the mixture was stirred at a temperature of 73 to 77 占 폚 for 1 hour. After cooling to 30 DEG C or lower, the mixture was transferred to a 1 liter glass beaker, and the inner wall of the glass flask and the stirring blades were observed. As a result, the adhesion of the solid gel to the bottom of the glass flask and the stirring blades was confirmed.
[비교예 3][Comparative Example 3]
1리터의 유리 플라스크에 이온교환수 722g을 장입하고, 수온을 25℃로 했다. 이온교환수의 pH를 측정한 바 5.9이었다. 날개 회전수 150rpm의 조건으로 앵커형 교반 날개에 의해 교반을 행하고, 페닐트라이메톡시실레인 47.9g을 투입하고 20∼25℃의 온도를 유지하여 60분간 교반을 계속했지만, 회색으로 흐려진 상태로 투명으로 되지 않았다. 이어서 메틸트라이메톡시실레인 191.7g을 투입한 바, 발열이 일어나 32℃까지 온도가 상승했다. 38분 후에 투명한 상태로 되었고, 5분간 더 교반했다. 25분 걸쳐, 20℃까지 냉각했다. 28질량% 암모니아 수용액 0.064g과 이온교환수 0.32g의 혼합 용해액을 투입하고, 30초간 교반한 후, 교반을 정지했다. 교반 정지 9분 후에 백탁이 일어났다.A 1-liter glass flask was charged with 722 g of ion-exchanged water, and the water temperature was 25 占 폚. The pH of the ion-exchanged water was measured and found to be 5.9. Agitation was carried out with an anchor type stirring blade under the condition of the number of revolutions of the blade of 150 rpm, 47.9 g of phenyltrimethoxysilane was added, and the stirring was continued for 60 minutes while keeping the temperature at 20 to 25 캜. However, Respectively. Subsequently, 191.7 g of methyltrimethoxysilane was added, and heat generation occurred, and the temperature rose to 32 캜. After 38 minutes, it became clear and stirred for another 5 minutes. It was cooled to 20 DEG C over 25 minutes. 0.064 g of a 28% by mass aqueous ammonia solution and 0.32 g of ion-exchanged water were mixed and stirred for 30 seconds, and stirring was stopped. After 9 minutes of stirring stoppage, clouding occurred.
메틸트라이메톡시실레인 및 페닐트라이메톡시실레인은 물 100질량부에 대한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 33.1질량부이며, 또한 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 질량비가 80:20이 되는 배합량이다. 12시간 정치한 후, 날개 회전수 150rpm의 조건으로 교반을 개시했다. 75℃까지 가열하고, 28질량% 암모니아 수용액 38g을 첨가하고, 또한 73∼77℃의 온도에서 1시간 교반을 행했다.Methyltrimethoxysilane and phenyltrimethoxysilane, the total amount of methyltrimethoxysilane and phenyltrimethoxysilane relative to 100 parts by mass of water is 33.1 parts by mass, and the sum of methyltrimethoxysilane and phenyl And the mass ratio of trimethoxysilane is 80:20. After the mixture was allowed to stand for 12 hours, agitation was started under the condition of a wing rotation speed of 150 rpm. The mixture was heated to 75 占 폚, 38 g of a 28 mass% aqueous ammonia solution was added, and the mixture was stirred at a temperature of 73 to 77 占 폚 for 1 hour.
30℃ 이하까지 냉각 후, 1리터의 유리 비커에 옮기고, 유리 플라스크의 내벽 및 교반 날개를 관찰한 바, 겔의 부착은 확인되지 않았다. 얻어진 액을, 가압 여과기를 사용하여 탈액하여 케이크 형상물로 만들고, 이 케이크 형상물을 열풍 순환 건조기 중에서 105℃의 온도로 건조하고, 건조물을 제트밀로 해쇄하여, 폴리메틸페닐실세스퀴옥세인 입자를 얻었다. 이 폴리메틸페닐실세스퀴옥세인 입자의 형상을 전자현미경으로 관찰한 바, 구상이었다.After cooling to 30 ° C or lower, the mixture was transferred to a 1-liter glass beaker, and the inner wall of the glass flask and stirring wing were observed. The resulting liquid was dewatered by using a pressure filter to obtain a cake-like material. The cake-like material was dried in a hot air circulating drier at a temperature of 105 ° C, and the dried material was pulverized with a jet mill to obtain polymethylphenylsilsequioxane particles. The shape of the polymethylphenylsilsesquioxane particles was observed by an electron microscope, and it was spherical.
폴리메틸페닐실세스퀴옥세인 입자의 체적평균 입경을 전기저항법 입도 분포 측정 장치 「멀티 사이저 3」(베크만 쿨터(주)제)을 사용하여 측정한 바, 8.4㎛이었다. 또한 표준편차(S.D.)는 1.13㎛, 변동계수(C.V.)는 13.4%이었다. 상기의 방법에서 평균 굴절률을 측정한 바, 1.45이었다.The volume average particle diameter of the polymethylphenylsilsesquioxane particles was measured using an electric resistance method particle size distribution analyzer " Multisizer 3 " (manufactured by Beckman Coulter, Inc.), and found to be 8.4 탆. The standard deviation (SD) was 1.13 mu m and the coefficient of variation (CV) was 13.4%. In the above method, the average refractive index was measured to be 1.45.
Claims (2)
(ii) 공정 (i)에서 얻어진 수용액에 페닐트라이메톡시실레인을 첨가하고, 가수분해 반응을 행하여, 투명한 실레인 수용액을 얻는 공정,
(iii) 공정 (ii)에서 얻어진 수용액을 0∼15℃의 온도로 조절하고, 이것에 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액을 첨가하고, 교반 혼합하여 혼합액을 얻는 공정, 및
(iv) 공정 (iii)에서 얻어진 혼합액을 정치 상태로 하고, 폴리메틸페닐실세스퀴옥세인 입자를 석출시키는 공정을 포함하고,
상기 공정 (i) 및 (ii)에서, 메틸트라이메톡시실레인과 페닐트라이메톡시실레인의 합계량이 물 100질량부에 대하여 5∼30질량부이며, 메틸트라이메톡시실레인:페닐트라이메톡시실레인으로 표시되는 질량비가 90:10∼20:80인 배합량인, 체적평균 입경이 1∼5㎛의 구상 폴리메틸페닐실세스퀴옥세인 입자의 제조 방법.(i) a step of adding methyltrimethoxysilane to water having a pH of 4.0 to 7.0 and performing a hydrolysis reaction to obtain a transparent aqueous solution,
(ii) a step of adding phenyltrimethoxysilane to the aqueous solution obtained in the step (i) and performing a hydrolysis reaction to obtain a transparent aqueous silane solution,
(iii) a step of adjusting the aqueous solution obtained in the step (ii) to a temperature of 0 to 15 캜, adding an aqueous solution in which an alkaline substance or an alkaline substance is dissolved, and stirring to obtain a mixed solution, and
(iv) a step of bringing the mixed solution obtained in the step (iii) into a standing state to precipitate the polymethylphenylsilsequioxane particles,
In the above steps (i) and (ii), the total amount of methyltrimethoxysilane and phenyltrimethoxysilane is 5 to 30 parts by mass based on 100 parts by mass of water, and methyltrimethoxysilane: phenyltrimethoxysilane Wherein the weight ratio of the cyclic polymethylphenylsilsesquioxane particles to the cyclic polymethylphenylsilsesquioxane particles is in the range of 90:10 to 20:80.
(iv) 공정 후, 교반하, 혼합액을 40∼100℃로 가열하고, 알칼리성 물질 또는 알칼리성 물질을 용해한 수용액을 첨가하는 공정을 포함하는 것을 특징으로 하는 제조 방법.The method according to claim 1,
(iv) heating the mixed solution to 40 to 100 캜 under stirring, and adding an aqueous solution containing an alkaline substance or an alkaline substance dissolved therein.
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| JP2016016829A JP6439712B2 (en) | 2016-02-01 | 2016-02-01 | Method for producing spherical polymethylphenylsilsesquioxane particles |
| JPJP-P-2016-016829 | 2016-02-01 | ||
| PCT/JP2017/001700 WO2017135045A1 (en) | 2016-02-01 | 2017-01-19 | Method for producing spherical polymethylphenylsilsesquioxane particles |
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| WO2020111359A1 (en) * | 2018-11-28 | 2020-06-04 | 이영철 | Method for preparing wrinkle-shaped polymethylsilsesquioxane particles, and polymethylsilsesquioxane powder comprising polymethylsilsesquioxane particles prepared thereby |
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| KR102114059B1 (en) * | 2018-08-17 | 2020-05-25 | 주식회사 케이씨씨 | Curable organopolysiloxane composition and reflective materials for opical semiconductor comprising the same |
| KR20210096637A (en) * | 2018-12-10 | 2021-08-05 | 와커 헤미 아게 | Method for producing spherical silicone resin particles |
| JP7490325B2 (en) | 2020-11-27 | 2024-05-27 | 信越化学工業株式会社 | Thermosetting resin composition |
| CN116041706A (en) * | 2022-12-30 | 2023-05-02 | 中国科学院广州能源研究所 | Microsphere hydrate inhibitor and application thereof |
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| JPS63295637A (en) * | 1987-05-28 | 1988-12-02 | Toshiba Silicone Co Ltd | Spherical polymethylsilsequioxane powder and its production |
| JPH04202325A (en) * | 1990-11-29 | 1992-07-23 | Toray Ind Inc | Spherical fine particle of silicone |
| JP3189979B2 (en) * | 1991-07-24 | 2001-07-16 | ポーラ化成工業株式会社 | Method for producing spherical or fibrous organic silicon oxide powder |
| JP3932155B2 (en) * | 1999-06-03 | 2007-06-20 | 信越化学工業株式会社 | Spherical silicone resin fine particles |
| JP4040362B2 (en) * | 2002-05-20 | 2008-01-30 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Method for producing spherical polymethylphenylsilsesquioxane fine particles |
| JP2004262981A (en) * | 2003-02-27 | 2004-09-24 | Ube Nitto Kasei Co Ltd | Preparation process for polyorganosiloxane particle and preparation process for silica particle |
| JP4397037B2 (en) * | 2004-09-21 | 2010-01-13 | 竹本油脂株式会社 | Method for producing spherical silsesquioxane fine particles |
| JP5117145B2 (en) * | 2006-09-08 | 2013-01-09 | 宇部日東化成株式会社 | Method for producing polyorganosiloxane particles and method for producing silica particles |
| JPWO2008047654A1 (en) * | 2006-10-12 | 2010-02-25 | 積水化学工業株式会社 | Film forming composition, pattern film manufacturing method using the same, and electronic device insulating film |
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