WO2017135045A1 - Procédé de production de particules sphériques de polyméthylphénylsilsesquioxane - Google Patents

Procédé de production de particules sphériques de polyméthylphénylsilsesquioxane Download PDF

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WO2017135045A1
WO2017135045A1 PCT/JP2017/001700 JP2017001700W WO2017135045A1 WO 2017135045 A1 WO2017135045 A1 WO 2017135045A1 JP 2017001700 W JP2017001700 W JP 2017001700W WO 2017135045 A1 WO2017135045 A1 WO 2017135045A1
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Prior art keywords
aqueous solution
stirring
phenyltrimethoxysilane
methyltrimethoxysilane
water
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PCT/JP2017/001700
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English (en)
Japanese (ja)
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良範 井口
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信越化学工業株式会社
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Priority to KR1020187024590A priority Critical patent/KR20180107182A/ko
Priority to CN201780009073.9A priority patent/CN108602957B/zh
Publication of WO2017135045A1 publication Critical patent/WO2017135045A1/fr

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    • 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

Definitions

  • the present invention relates to a method for producing spherical polymethylphenylsilsesquioxane particles.
  • Polymethylsilsesquioxane particles are used as a light diffusing agent for light diffusing plates for backlights of liquid crystal displays, light diffusing covers for sheets and LED lighting. Due to the difference in refractive index between the base resin and the light diffusing agent particles, light is refracted and reflected, and light diffusibility is exhibited. The greater the difference in refractive index, the better the light diffusibility, while the more reflected light, the lower the light transmission. When importance is attached to light transmittance, it is desirable that the difference in refractive index is small. Polymethylmethacrylate, polystyrene, polycarbonate, etc.
  • the refractive index can be increased by introducing phenylsilsesquioxane units into polymethylsilsesquioxane. By changing the composition ratio of the methyl silsesquioxane unit and the phenyl silsesquioxane unit, the refractive index can be changed in the range of 1.43 to 1.57.
  • JP-A-4-202325 discloses methyltrimethoxysilane and phenyltrimethoxysilane.
  • An example is a method in which a homogeneous mixed solution is dropped into an aqueous solution of an alkaline substance with stirring to cause hydrolysis and condensation. This method has a problem that gel-like substances adhere to the stirring blade and the inner wall of the tank.
  • Patent Document 2 discloses that a mixture of methyltrialkoxysilane and phenyltrialkoxysilane is hydrolyzed in an acidic aqueous solution, and then an alkaline aqueous solution is added and mixed, followed by stirring. A method of stopping and allowing the condensation reaction to stand still has been proposed. In the production method exemplified here, no gel-like material is produced, but in all cases, the volume average particle diameter is larger than 5 ⁇ m.
  • the light diffusing agent particles having a volume average particle diameter of about 1 to 5 ⁇ m are suitable, and the light diffusibility decreases outside this particle diameter range.
  • All of the polymethylphenylsilsesquioxane particles exemplified in the aforementioned Japanese Patent Application Laid-Open No. 2003-335860 have a volume average particle size larger than 5 ⁇ m and are not suitable for light diffusion applications.
  • the present invention has been made in view of the above circumstances, and provides a method for producing spherical polymethylphenylsilsesquioxane particles having a volume average particle diameter of 1 to 5 ⁇ m suitable as a light diffusing agent without forming a gel. The purpose is to do.
  • the present inventor added methyltrimethoxysilane to water having a pH of 4.0 to 7.0 to obtain a transparent aqueous solution, and phenyltrimethoxysilane was added thereto.
  • the present invention provides the following production method. [1].
  • (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) adding phenyltrimethoxysilane to the aqueous solution obtained in step (i), performing a hydrolysis reaction, and obtaining a transparent silane aqueous solution;
  • iv) including the step of allowing the liquid mixture obtained in step (iii) to stand and precipitating polymethylphenylsilsesquioxane particles;
  • the present invention it is possible to provide a method for producing spherical polymethylphenylsilsesquioxane particles having a volume average particle diameter of 1 to 5 ⁇ m suitable as a light diffusing agent without producing a gel-like material.
  • the production method of the present invention comprises: (I) 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) adding phenyltrimethoxysilane to the aqueous solution obtained in step (i), performing a hydrolysis reaction, and obtaining a transparent aqueous solution; (Iii) adjusting the temperature of the aqueous solution obtained in step (ii) to a temperature of 0 to 15 ° C., adding an alkaline substance or an aqueous solution in which the alkaline substance is dissolved thereto, stirring and mixing to obtain a mixed liquid; iv) including the step of allowing the liquid mixture obtained in step (iii) to stand and precipitating polymethylphenylsilsesquioxane particles; In the above steps (i) and (ii), the total amount of methyltrimethoxysilane and phen
  • step (I) Step of adding methyltrimethoxysilane to water having a pH of 4.0 to 7.0 and performing a hydrolysis reaction to obtain a transparent silane aqueous solution
  • Methyltrimethoxysilane is represented by CH 3 Si (OCH 3 ) 3 . It is.
  • the water used in step (i) must have a pH (25 ° C.) of 4.0 to 7.0 in order to hydrolyze methyltrimethoxysilane and phenyltrimethoxysilane used in step (ii). There is. If the pH is less than 4.0 or higher than 7.0, the condensation reaction proceeds and a gel is generated. Preferably, it is in the range of 5.0 to 6.8.
  • ion-exchanged water can be used as it is because the pH falls within the above range due to dissolution of carbon dioxide in the air.
  • a small amount of an acidic substance may be added to adjust the pH within the above range.
  • the acidic substance is not particularly limited.
  • carboxylic acid such as formic acid, acetic acid, oxalic acid, malonic acid, lactic acid, malic acid, hydrochloric acid; phosphoric acid; sulfuric acid; methanesulfonic acid; trifluoromethanesulfonic acid, etc. Or two or more can be used in appropriate combination.
  • 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 size of polymethylphenylsilsesquioxane 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, which can be used alone or in combination of two or more.
  • step (i) methyltrimethoxysilane is added to water, and the hydrolysis reaction of methyltrimethoxysilane is carried out with stirring using a normal stirrer such as a propeller blade, a turbine blade, or a paddle blade.
  • Methyltrimethoxysilane may be added at once, but may be gradually added over time.
  • water may be added to methyltrimethoxysilane, or it may be added and mixed in the tank at the same time.
  • the temperature at this time is not limited and may be in the range of 1 to 100 ° C., and may be in the range of 1 to 30 ° C. or 18 to 30 ° C.
  • methyltrimethoxysilane becomes methylsilanetriol represented by the formula CH 3 Si (OH) 3 and methanol is by-produced.
  • silane becomes soluble in water containing methanol and becomes a transparent aqueous solution.
  • Phenyltrimethoxysilane has the formula C 6 H 5 Si (OCH 3 ) 3 Indicated by An acidic substance may be added to the aqueous solution for the purpose of improving the hydrolysis reaction rate of phenyltrimethoxysilane.
  • the acidic substance is not particularly limited.
  • carboxylic acid such as formic acid, acetic acid, oxalic acid, malonic acid, lactic acid, malic acid, hydrochloric acid; phosphoric acid; sulfuric acid; methanesulfonic acid; trifluoromethanesulfonic acid, etc. Or two or more can be used in appropriate combination.
  • 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 size of the polymethylphenylsilsesquioxane 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, which can be used alone or in combination of two or more.
  • step (ii) phenyltrimethoxysilane is added to the aqueous solution of silane obtained in step (i), and the hydrolysis reaction of phenyltrimethoxysilane is carried out by using an ordinary agitator such as a propeller blade, a turbine blade, or a paddle blade. With stirring. Phenyltrimethoxysilane may be added at once, but may be gradually added over time. The temperature at this time is not limited and may be in the range of 0 to 100 ° C.
  • phenyltrimethoxysilane becomes phenylsilanetriol represented by the formula C 6 H 5 Si (OH) 3 , and methanol is by-produced.
  • silane becomes soluble in water containing methanol and becomes a transparent aqueous solution.
  • the blending amount of methyltrimethoxysilane and phenyltrimethoxysilane in step (i) and step (ii) is 5 to 30 parts by mass of the total amount of methyltrimethoxysilane and phenyltrimethoxysilane with respect to 100 parts by mass of water. It is preferably 13 to 28 parts by mass.
  • the total amount of methyltrimethoxysilane and phenyltrimethoxysilane is small, the production efficiency is deteriorated, and when it is large, it is difficult to make the volume average particle diameter of the polymethylphenylsilsesquioxane particles 5 ⁇ m or less.
  • the mass ratio represented by methyltrimethoxysilane: phenyltrimethoxysilane is in the range of 90:10 to 20:80, more preferably 85:15 to 40:60, and 80:20 to 50:50, and 80: 20 to 55:45 is more preferable. If the proportion of phenyltrimethoxysilane in trimethoxysilane is small, the refractive index will be too low, and if it is too high, the refractive index may be too high. .
  • methyltrimethoxysilane and phenyltrimethoxysilane are simultaneously added to water. If hydrolysis is performed, it becomes difficult to obtain a transparent aqueous solution. Moreover, even if phenyltrimethoxysilane is added to water first, it becomes difficult to obtain a transparent aqueous solution. This is because after the phenyltrimethoxysilane is hydrolyzed, the condensation reaction further proceeds and becomes insoluble in water. When the liquid in this state is used to proceed to the previous step, the insoluble matter becomes a gel.
  • step (Iii) A step of adjusting the aqueous solution obtained in step (ii) to a temperature of 0 to 15 ° C., adding an alkaline substance or an aqueous solution in which an alkaline substance is dissolved thereto, and stirring and mixing to obtain a mixed solution. It acts as a condensation reaction catalyst for hydrolyzed methyltrimethoxysilane and phenyltrimethoxysilane, ie, methylsilanetriol and phenylsilanetriol, thereby producing polymethylphenylsilsesquioxane particles in step (iv).
  • An alkaline substance may be used individually by 1 type, or may use 2 or more types together.
  • the alkaline substance may be added as it is, but since it is necessary to uniformly dissolve in water in a short time, the solid and gaseous substances are added as an aqueous solution.
  • the concentration is not particularly limited as long as it is soluble in water.
  • the amount of the alkaline substance is required to be at least an amount by which the condensation reaction proceeds in the step (iv) to produce polymethylphenylsilsesquioxane particles.
  • the minimum required amount varies depending on the pH of water in step (i), the type of alkaline substance, and the reaction temperature. When there is too much alkaline substance, the condensation reaction rate increases, and in the step (iii), polymethylphenylsilsesquioxane particles begin to be produced, and aggregated particles and gels are produced.
  • the maximum amount varies depending on the blending amount of methyltrimethoxysilane and phenyltrimethoxysilane, the blending ratio of methyltrimethoxysilane and phenyltrimethoxysilane, the type of alkaline substance, and the reaction temperature.
  • a 28% by mass aqueous ammonia solution in the range of 0.01 to 0.20 parts by mass, preferably 0.03 to 0.10 parts by mass with respect to 100 parts by mass of water used in step (i). It is selected appropriately.
  • the alkaline substance is not particularly limited, and examples thereof include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; potassium carbonate and carbonate Alkali metal carbonates such as sodium; ammonia water; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, dimethylamine, diethylamine Further, amines such as trimethylamine, triethanolamine and ethylenediamine can be used. Among these, ammonia water is preferred because it can be easily removed from the resulting polymethylphenylsilsesquioxane particles by volatilization.
  • the temperature of the aqueous silane solution is 0 to 15 ° C., preferably 0 to 10 ° C.
  • the condensation reaction rate is increased, and in the step (iii), polymethylphenylsilsesquioxane particles start to be generated and aggregated particles and gel are generated.
  • the addition of the alkaline substance or the aqueous solution in which the alkaline substance is dissolved to the aqueous solution obtained in (ii) is performed with stirring using a normal agitator such as a propeller blade, a turbine blade, or a paddle blade. It is desirable that an alkaline substance or an aqueous solution in which an alkaline substance is dissolved is added at once and is uniformly dissolved in water in a short time. If it takes time to dissolve uniformly, the particle size distribution may be widened or a gel may be formed.
  • step (Iv) The step of allowing the liquid mixture obtained in step (iii) to stand still and precipitating polymethylphenylsilsesquioxane particles
  • the liquid becomes cloudy. Even if it becomes cloudy, the particles are not sufficiently solidified.
  • stirring is performed in a state where the solidification is not performed, the particles are aggregated or a gel is formed.
  • the required standing time depends on the condensation reaction rate, that is, the type and amount of the alkaline substance and the reaction temperature. Usually, it is appropriately selected in the range of 30 minutes to 24 hours, preferably 1 hour to 12 hours.
  • spherical polymethylphenylsilsesquioxane particles having a volume average particle diameter of 1 to 5 ⁇ m can be obtained.
  • the organotrialkoxysilane represented by the general formula R 1 Si (OR 2 ) 3 or the general formula R 3 is used with stirring.
  • Diorganodialkoxysilane represented by Si (OR 2 ) 2 Diorganodialkoxysilane represented by Si (OR 2 ) 2 , triorganoalkoxysilane represented by general formula R 3 3 SiOR 2 , tetraalkoxysilane represented by general formula Si (OR 2 ) 4 , general formula R 2 3
  • One or more of triorganosilanol represented by SiOH and hexamethyldisilazane represented by the formula [(CH 3 ) 3 Si] 2 NH may be added to cause a condensation reaction.
  • R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms excluding a methyl group and a phenyl group
  • R 2 is an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms
  • R 3 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • an alkaline substance or an aqueous solution in which an alkaline substance is dissolved may be added or heated at 40 to 100 ° C. with stirring.
  • the mixture after step (iv) may be heated to 40 to 100 ° C. with stirring, and an alkaline substance or an aqueous solution in which an alkaline substance is dissolved may be added.
  • the stirring time is not particularly limited, and is appropriately selected from 30 minutes to 12 hours.
  • the removal of water can be performed, for example, by heating the aqueous dispersion after the reaction under normal pressure or reduced pressure, specifically, a method of removing the water by leaving the dispersion still under heating, Examples thereof include a method of removing moisture while stirring and flowing the dispersion liquid, a method of spraying and dispersing the dispersion liquid in a hot air stream like a spray dryer, and a method of using a fluidized heat medium.
  • the dispersion liquid may be concentrated by a method such as heat dehydration, filtration separation, centrifugation, decantation or the like, and the dispersion liquid may be washed with water or alcohol if necessary.
  • the volume average particle diameter means a volume-based average particle diameter determined by an electric resistance method.
  • the volume average particle diameter can be measured with a potential resistance method particle size distribution measuring apparatus. For example, it can be measured by a multisizer manufactured by Beckman Coulter, Inc.
  • Example 1 801 g of ion-exchanged water was charged into a 1 liter glass flask, and the water temperature was 20 ° C. The pH of ion-exchanged water was measured and found to be 5.9. Stirring was performed with a vertical stirring blade under a blade rotation speed of 150 rpm, and when 95.5 g of methyltrimethoxysilane was added, heat generation occurred and the temperature rose to 24 ° C. After 3 minutes, it became transparent and stirred for another 7 minutes. Next, 62.5 g of phenyltrimethoxysilane was added and stirring was continued while maintaining a temperature of 20 to 25 ° C. After 50 minutes, the solution became transparent and further stirred for 5 minutes. Cooled to 5 ° C. over 25 minutes. A mixed solution of 0.53 g of 28 mass% ammonia aqueous solution and 2.65 g of ion-exchanged water was added and stirred for 30 seconds, and then stirring was stopped. Cloudiness occurred 12 seconds after stirring was stopped.
  • methyltrimethoxysilane and phenyltrimethoxysilane the total amount of methyltrimethoxysilane and phenyltrimethoxysilane with respect to 100 parts by mass of water is 19.7 parts by mass, and the mass ratio of methyltrimethoxysilane and phenyltrimethoxysilane Is a blending amount of 60.4: 39.6.
  • the volume average particle size 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 ⁇ m.
  • the standard deviation (SD) was 0.29 ⁇ m, and the coefficient of variation (CV) was 13.6%.
  • the average refractive index measured by the above method was 1.49.
  • Example 2 815 g of ion-exchanged water was charged into a 1 liter glass flask, and the water temperature was set to 20 ° C. The pH of ion-exchanged water was measured and found to be 5.9. Stirring was performed with a vertical stirring blade under a blade rotation speed of 150 rpm, and when 77.6 g of methyltrimethoxysilane was added, heat generation occurred and the temperature rose to 24 ° C. After 3 minutes, it became transparent and stirred for another 7 minutes. Subsequently, 66.4 g of phenyltrimethoxysilane was added and stirring was continued while maintaining a temperature of 20 to 25 ° C. After 55 minutes, the solution became transparent and further stirred for 5 minutes.
  • methyltrimethoxysilane and phenyltrimethoxysilane In methyltrimethoxysilane and phenyltrimethoxysilane, the total amount of methyltrimethoxysilane and phenyltrimethoxysilane with respect to 100 parts by mass of water is 17.7 parts by mass, and the mass ratio of methyltrimethoxysilane and phenyltrimethoxysilane Is a blending amount of 53.9: 46.1.
  • the volume average particle size 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 ⁇ m.
  • the standard deviation (SD) was 0.19 ⁇ m, and the coefficient of variation (CV) was 8.6%.
  • SD standard deviation
  • CV coefficient of variation
  • Example 3 789 g of ion-exchanged water was charged into a 1 liter glass flask, and the water temperature was 20 ° C. It was 5.8 when pH of ion-exchange water was measured. Stirring was performed with a vertical stirring blade at a blade rotation speed of 150 rpm, and when 110.5 g of methyltrimethoxysilane was added, heat generation occurred and the temperature rose to 24 ° C. After 4 minutes, it became transparent and stirred for another 6 minutes. Subsequently, 59.5 g of phenyltrimethoxysilane was added and stirring was continued while maintaining a temperature of 20 to 25 ° C. After 45 minutes, the solution became transparent and further stirred for 5 minutes.
  • methyltrimethoxysilane and phenyltrimethoxysilane the total amount of methyltrimethoxysilane and phenyltrimethoxysilane with respect to 100 parts by mass of water is 21.5 parts by mass, and the mass ratio of methyltrimethoxysilane and phenyltrimethoxysilane Is 65.0: 35.0.
  • the volume average particle size 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 ⁇ m.
  • the standard deviation (SD) was 0.27 ⁇ m and the coefficient of variation (CV) was 12.0%.
  • the average refractive index measured by the above method was 1.48.
  • Example 4 754 g of ion-exchanged water was charged into a 1 liter glass flask, and the water temperature was 20 ° C. The pH of ion-exchanged water was measured and found to be 5.9. Stirring was performed with a vertical stirring blade under a blade rotation speed of 150 rpm, and when 142.9 g of methyltrimethoxysilane was added, heat generation occurred and the temperature rose to 24 ° C. After 7 minutes, it became transparent and stirred for another 8 minutes. Subsequently, 62.1 g of phenyltrimethoxysilane was added and stirring was continued while maintaining a temperature of 20 to 25 ° C., and after 35 minutes it became transparent and further stirred for 5 minutes.
  • methyltrimethoxysilane and phenyltrimethoxysilane the total amount of methyltrimethoxysilane and phenyltrimethoxysilane with respect to 100 parts by mass of water is 27.2 parts by mass, and the mass ratio of methyltrimethoxysilane and phenyltrimethoxysilane Is a blending amount of 69.7: 30.3.
  • the volume average particle size 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 ⁇ m.
  • the standard deviation (SD) was 0.37 ⁇ m, and the coefficient of variation (CV) was 13.4%.
  • the average refractive index measured by the above method was 1.47.
  • Example 5 759 g of ion-exchanged water was charged into a 1 liter glass flask, and the water temperature was 20 ° C. The pH of the ion exchange water was measured and found to be 6.0. Stirring was performed with a vertical stirring blade under a blade rotation speed of 150 rpm, and when 151.6 g of methyltrimethoxysilane was added, heat generation occurred and the temperature rose to 24 ° C. After 8 minutes, it became transparent and stirred for an additional 7 minutes. Subsequently, 48.4 g of phenyltrimethoxysilane was added and stirring was continued while maintaining a temperature of 20 to 25 ° C. After 30 minutes, the solution became transparent and further stirred for 5 minutes.
  • methyltrimethoxysilane and phenyltrimethoxysilane the total amount of methyltrimethoxysilane and phenyltrimethoxysilane with respect to 100 parts by mass of water is 26.3 parts by mass, and the mass ratio of methyltrimethoxysilane and phenyltrimethoxysilane Is a blending amount of 75.8: 24.2.
  • the volume average particle size 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 ⁇ m.
  • the standard deviation (SD) was 0.52 ⁇ m, and the coefficient of variation (CV) was 16.3%.
  • the average refractive index measured by the above method was 1.46.
  • methyltrimethoxysilane and phenyltrimethoxysilane the total amount of methyltrimethoxysilane and phenyltrimethoxysilane with respect to 100 parts by mass of water is 19.7 parts by mass, and the mass ratio of methyltrimethoxysilane and phenyltrimethoxysilane Is a blending amount of 60.4: 39.6.
  • methyltrimethoxysilane and phenyltrimethoxysilane the total amount of methyltrimethoxysilane and phenyltrimethoxysilane with respect to 100 parts by mass of water is 19.7 parts by mass, and the mass ratio of methyltrimethoxysilane and phenyltrimethoxysilane Is a blending amount of 60.4: 39.6.
  • methyltrimethoxysilane and phenyltrimethoxysilane the total amount of methyltrimethoxysilane and phenyltrimethoxysilane with respect to 100 parts by mass of water is 33.1 parts by mass, and the mass ratio of methyltrimethoxysilane and phenyltrimethoxysilane Is a blending amount of 80:20.
  • stirring was started under conditions of blade rotation speed of 150 rpm. The mixture was heated to 75 ° C., 38 g of a 28% by mass aqueous ammonia solution was added, and the mixture was further stirred at a temperature of 73 to 77 ° C. for 1 hour.
  • the sample was transferred to a 1 liter glass beaker, and when the inner wall of the glass flask and the stirring blade were observed, no adhesion of gel was observed.
  • the obtained liquid is drained using a pressure filter to form a cake, and the cake is dried in a hot air circulating dryer at a temperature of 105 ° C., and the dried product is crushed with a jet mill.
  • Polymethylphenylsilsesquioxane particles were obtained. When the shape of the polymethylphenylsilsesquioxane particles was observed with an electron microscope, it was spherical.
  • the volume average particle size of the polymethylphenylsilsesquioxane particles was measured using an electric resistance method particle size distribution measuring device “Multisizer 3” (manufactured by Beckman Coulter, Inc.), and found to be 8.4 ⁇ m.
  • the standard deviation (SD) was 1.13 ⁇ m, and the coefficient of variation (CV) was 13.4%.
  • the average refractive index measured by the above method was 1.45.

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  • Health & Medical Sciences (AREA)
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Abstract

La présente invention concerne un procédé de production de particules sphériques de polyméthylphénylsilsesquioxane présentant une taille de particule moyenne en volume de 1 à 5 µm, comprenant : (i) une étape d'addition de méthyltriméthoxysilane à de l'eau présentant un pH de 4,0 à 7,0, et permettant à la solution de subir une réaction d'hydrolyse, pour obtenir une solution aqueuse transparente ; (ii) une étape d'addition de phényltriméthoxysilane à la solution aqueuse obtenue dans l'étape (i), et le fait de laisser la solution subir une réaction d'hydrolyse, pour obtenir une solution de silane aqueuse transparente ; (iii) une étape de réglage de la température de la solution aqueuse obtenue dans l'étape (ii) à 0 à 15 °C, l'addition, à la solution aqueuse, d'une substance alcaline ou d'une solution aqueuse dans laquelle la substance alcaline est dissoute, et l'agitation et le mélange de la solution, pour obtenir une solution de mélange ; et (iv) une étape permettant de laisser la solution de mélange obtenue dans l'étape (iii) reposer jusqu'à ce que les particules de polyméthylphénylsilsesquioxane précipitent.
PCT/JP2017/001700 2016-02-01 2017-01-19 Procédé de production de particules sphériques de polyméthylphénylsilsesquioxane WO2017135045A1 (fr)

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KR1020187024590A KR20180107182A (ko) 2016-02-01 2017-01-19 구상 폴리메틸페닐실세스퀴옥세인 입자의 제조 방법
CN201780009073.9A CN108602957B (zh) 2016-02-01 2017-01-19 球状聚甲基苯基硅倍半氧烷粒子的制造方法

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JP2016-016829 2016-02-01
JP2016016829A JP6439712B2 (ja) 2016-02-01 2016-02-01 球状ポリメチルフェニルシルセスキオキサン粒子の製造方法

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JP2020523425A (ja) * 2017-10-30 2020-08-06 ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ 球状ポリシルセスキオキサン粒子の製造方法
CN112533994A (zh) * 2018-08-17 2021-03-19 Kcc有机硅株式会社 可固化的有机聚硅氧烷组合物及包含所述可固化的有机聚硅氧烷组合物的光学半导体反射材料
US20220056217A1 (en) * 2018-12-10 2022-02-24 Wacker Chemie Ag Process for preparing spherical silicone resin particles
CN116041706A (zh) * 2022-12-30 2023-05-02 中国科学院广州能源研究所 一种微球型水合物抑制剂及其应用
JP7490325B2 (ja) 2020-11-27 2024-05-27 信越化学工業株式会社 熱硬化性樹脂組成物

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KR102212703B1 (ko) * 2018-11-28 2021-02-05 이영철 주름 모양 폴리메틸실세스퀴옥세인 입자의 제조방법 및 이를 통해 제조된 폴리메틸실세스퀴옥세인 입자를 포함하는 폴리메틸실세스퀴옥세인 파우더

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JP2020523425A (ja) * 2017-10-30 2020-08-06 ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ 球状ポリシルセスキオキサン粒子の製造方法
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US20220056217A1 (en) * 2018-12-10 2022-02-24 Wacker Chemie Ag Process for preparing spherical silicone resin particles
JP7490325B2 (ja) 2020-11-27 2024-05-27 信越化学工業株式会社 熱硬化性樹脂組成物
CN116041706A (zh) * 2022-12-30 2023-05-02 中国科学院广州能源研究所 一种微球型水合物抑制剂及其应用

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