JP5582734B2 - Method for producing polyorganosiloxane particles - Google Patents

Description

The present invention relates to a method for producing polyorganosiloxane particles, and more specifically, a hydrolyzable organosilicon compound phase is disposed in an upper layer, and a water / alcohol mixed solvent phase of a hydrolysis catalyst is disposed in a lower layer. The present invention relates to a method for producing polyorganosiloxane particles in which a silicon compound and a catalyst for hydrolysis are brought into contact.

  In a liquid crystal display device, a spacer is interposed between a pair of electrodes provided in a liquid crystal cell for a liquid crystal display device, and a liquid crystal substance is sealed to form a liquid crystal layer. If the thickness of the liquid crystal layer is not uniform, the image displayed on the liquid crystal cell may cause color unevenness or a decrease in contrast at the time of lighting. For this reason, the liquid crystal layer is desired to have a uniform thickness. In addition, when the display image is switched at high speed, it is desired that the thickness of the liquid crystal layer inside the liquid crystal cell is uniform even when an image with a wide viewing angle is displayed.

In addition, regarding the seal portion located at the peripheral edge of the liquid crystal layer, if the distance between the substrates is not uniform, this may cause problems such as uneven image display and a decrease in contrast. It is also required to be uniform.
In particular, in a large screen liquid crystal display device of STN mode, the thickness of the liquid crystal layer inside the liquid crystal cell is made more uniform, the area of the seal part is kept small, and the distance between the electrodes is kept constant while keeping the area of the display part large. It is required to keep.

In order to make the distance between the substrates of the seal portion and the thickness of the liquid crystal layer inside the liquid crystal cell uniform, conventionally, spherical particles having a uniform particle size are interspersed between the seal portion and the electrodes of the liquid crystal cell. That is, it is used as a sealing spacer and an in-plane spacer. As such spacer particles, organic resin particles such as polystyrene, silica fine particles or silica fine particles coated with an organic resin are used.

However, since organic resin particles such as polystyrene are too soft, in a liquid crystal display cell used as an in-plane spacer, if a non-uniform pressure is applied to the liquid crystal layer inside the liquid crystal cell, the variation in the pressure There is a problem that the spacer is deformed and the thickness of the liquid crystal layer inside the liquid crystal cell cannot be maintained uniformly. In addition, in order to use organic resin particles as in-plane spacers, it is necessary to increase the number of sprays. was there. Further, when organic resin particles are used as a sealing spacer, there is a problem that the deformation of the particles becomes large and it is difficult to make the distance between the electrodes a desired thickness.

In addition, when silica fine particles are used as in-plane spacers of the liquid crystal cell, the thickness of the liquid crystal layer inside the liquid crystal cell is inadequate due to small compression deformation of the silica fine particles unless the particle size distribution of the silica fine particles is sharp. There was a problem that it became uniform. Further, when the liquid crystal display device is exposed to a low temperature, the thermal expansion coefficient of the liquid crystal layer is different from the thermal expansion coefficient of the spacer inside the liquid crystal cell, so that a gap is generated between the electrode of the liquid crystal cell and the liquid crystal layer. There was a problem that low-temperature bubbles were generated.
In addition, when silica fine particles are used as a sealing spacer, the electrode is damaged or further disconnected because it is too hard.

In order to solve the above problems, Japanese Patent Laid-Open No. 6-250193 prepares silica fine particles by hydrolyzing a hydrolyzable silicon compound such as tetraethoxysilane, and the silanol groups on the surface of the silica fine particles. It has been proposed to use silica fine particles prepared by esterifying a benzene with an organic compound as a spacer between electrodes (in-plane) of a liquid crystal cell.
Although the silica fine particles produced by this method have moderate hardness and mechanical resilience, it is said to be suitable as an interelectrode spacer of a liquid crystal cell, but not necessarily as an interelectrode spacer of a liquid crystal cell. It was insufficient.

Japanese Patent Laid-Open No. 7-14472 discloses R ¹ _m Si (OR ² ) _4-m
(R ¹ and R ² in the formula each represent a specific organic group. M is an integer of 0 to ^3. )
The particles obtained by hydrolysis and polycondensation of the organosilicon compound represented by formula (1) can be obtained by subjecting the particles to a heat treatment while changing the temperature in the range of 100 to 1000 ° C. to obtain spacer particles for liquid crystal cells having a specific compression modulus. It is disclosed.
The compression elastic modulus of the spacer particles is controlled by the amount of residual organic groups after thermally decomposing part of the organic groups present in the particles in the heat treatment step. In such elastic fine particles using a silicon compound, the R ¹ group remains due to hydrolysis of the silicon compound, the OR ² group is converted into alcohol (R ² OH) by hydrolysis, and the generated OH group is dehydrated. Elastic fine particles are formed by the formation of a polysiloxane bond accompanied by a reaction, followed by drying and heat treatment. The compression elastic modulus and elastic recovery rate of the elastic fine particles depend on the amount of carbon derived from the hydrocarbon group (R ¹ group) directly bonded to the silicon atom remaining after the heat treatment.

However, in the spacer particles described in JP-A-7-140472, if the particle diameter is different, the amount of organic groups remaining in the particles after the heat treatment step may be different, and the heat treatment amount, atmosphere, and heating rate It was difficult to make the heat treatment conditions such as the holding temperature and the processing temperature holding time the same for each batch. For this reason, it is difficult to precisely control the amount of residual organic groups in the elastic fine particles, and it is very difficult to control the compression deformation rate for each particle and batch to be the same. There was a problem that the elastic modulus could not be adjusted to a desired value.
In addition, since the amount of residual organic groups is different between the outside and inside of the particle, the compression modulus is not uniform throughout the particle, and voids are generated in the organic group portion inside the particle thermally decomposed in the heat treatment step. As a result, there was a problem that the compressive strength of the obtained spacer particles for liquid crystal cells was lowered.

In JP-A-63-94224, the present inventors agglomerate particles in which a synthetic resin powder is fixed on the surface of inorganic insulator particles without moving in the liquid crystal display device such as a liquid crystal layer. Therefore, it is proposed that it can cope with subtle changes in thickness and that the cell gap can be made uniform.

In addition, in the Japanese Patent Application Laid-Open No. 9-59384, the present inventors have produced organopolysiloxane fine particles using a specific organosilicon compound, so that the inside of the organopolysiloxane fine particles can be obtained without going through the above heat treatment step. It is proposed that fine particles having a high elastic recovery rate and uniform particle size can be obtained, and that these fine particles are suitable as a spacer between electrodes of a liquid crystal cell. Yes.
However, in the above method, depending on the type of organosilicon compound, hydrolysis / condensation polymerization may not be complete, or hydrolysis / polycondensation is slow. In some cases, the reproducibility of the particle size was insufficient.

Furthermore, JP-A-4-313727 and JP-A-5-80343 propose using spherical particles having elasticity in a specific range as spacers between electrodes of a liquid crystal cell. It is disclosed that these are plastic beads or hybrid particles of inorganic and organic materials.
However, conventional spacer particles such as these have a desired compression modulus and a high elastic recovery rate on average, but there is a large variation between the particles, and the function as a spacer can be fully expressed. could not. Moreover, in order to obtain particles having such a uniform physical property value, it has been necessary to reduce the production scale or strictly manage the production conditions.
Furthermore, even when the manufacturing scale is reduced, there are cases in which variations among manufacturing batches become a problem.

In addition, the applicant of the present application prepares silica particles (core particles) having a uniform average particle diameter, hydrophobizes them, and forms a coating layer having elasticity derived from an organosilicon compound in the presence of a surfactant. A method for producing siloxane-coated elastic fine particles has been proposed (Japanese Patent Laid-Open Nos. 2000-204168 and 2000-212422).
However, it takes a long time to obtain silica core particles having a large particle size as the core particles, and further, since an elastic coating layer is formed, there are difficulties in productivity and economy. Furthermore, a gel-like substance was generated and needed to be removed.

Nagao et al., When preparing silica particles by hydrolyzing tetraorthosilicate, if hydrolyzed in the presence of an electrolyte such as Kcl, Licl, etc., the particle growth rate is high, and the generation of new particles is suppressed. Reported that monodispersed particles of about 1 μm can be obtained and the particle size distribution can be adjusted. (Non-patent literature: D. Nagao et al., J. Chem Eng., Japan 33,468 (2000)).
However, in order to use it as a spacer for a liquid crystal display device, particles having a larger particle size are required, and in addition, there is a problem that the particle size varies from production to production.

JP-A-6-250193 Japanese Patent Laid-Open No. 7-140472 Japanese Patent Laid-Open No. 7-140472 JP 63-94224 A JP-A-9-59384 JP-A-4-313727 Japanese Patent Laid-Open No. 5-80343 JP 2000-204168 A JP 2000-212422 A

D. Nagao et al., J. Chem Eng., Japan 33,468 (2000)

  In the present invention, the hydrolyzable organosilicon compound phase is disposed in the upper layer, the water / alcohol mixed solvent phase of the hydrolysis catalyst is disposed in the lower layer, and the hydrolyzable organosilicon compound and the hydrolysis catalyst are brought into contact with each other. It is an object of the present invention to provide a method for producing polyorganosiloxane particles having a desired particle size with high reproducibility, with a small variation in average particle size for each production of polyorganosiloxane particles.

In the method for producing polyorganosiloxane particles according to the present invention, the hydrolyzable organosilicon compound phase represented by the following formula (1) is disposed in the upper layer, and the water / alcohol mixed solvent phase of the hydrolysis catalyst is disposed in the lower layer. and, in the manufacturing method of polyorganosiloxane particles of contacting a hydrolyzable organic silicon compound and a hydrolyzable catalyst, alcohol is characterized in that it comprises a monohydric alcohol having 5 to 10 carbon atoms (ROH _1).
R ¹ _n Si (OR ² ) _4-n ... (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group, and R ² represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 2 to 5 carbon atoms. And n is a positive number of 0 to 3)

The hydrolyzable organosilicon compound is preferably a hydrolyzable organosilicon compound in which n is 1 in formula (1).
The hydrolyzable organosilicon compound may be a mixture of hydrolyzable organosilicon compounds in which n is 0 and 1 in formula (1).

The alcohol may further comprise a monohydric alcohol having 1 to 4 carbon atoms (ROH _2).
It is preferable that the content of ROH ₁ in the total alcohol is 10% by weight or more.

The polyorganosiloxane particles preferably have an average particle size in the range of 0.5 to 30 μm and a particle size variation coefficient (1) (CV value (1)) of 3% or less.
The average particle size variation coefficient (2) (CV value (2)) for each production is preferably 3% or less.

According to the present invention, the hydrolyzable organosilicon compound phase is disposed in the upper layer, the water / alcohol mixed solvent phase of the hydrolysis catalyst is disposed in the lower layer, and the hydrolyzable organosilicon compound and the hydrolysis catalyst are brought into contact with each other. In the method for producing polyorganosiloxane particles to be used, alcohol containing 5 or more carbon atoms is contained in a short time so that the particle diameter is large, the particle diameter is uniform, and alcohol having 1 to 4 carbon atoms is mixed in a predetermined ratio. When used, polyorganosiloxane particles having a desired particle size can be produced with good reproducibility with little variation in average particle size from production to production.

Hereinafter, the manufacturing method of the polyorganosiloxane particle concerning this invention is demonstrated.
In the method for producing polyorganosiloxane particles according to the present invention, the hydrolyzable organosilicon compound phase represented by the following formula (1) is disposed in the upper layer, and the water / alcohol mixed solvent phase of the hydrolysis catalyst is disposed in the lower layer. and, in the manufacturing method of polyorganosiloxane particles of contacting a hydrolyzable organic silicon compound and a hydrolyzable catalyst, alcohol is characterized in that it comprises a monohydric alcohol having 5 to 10 carbon atoms (ROH _1).
R ¹ _n Si (OR ² ) _4-n ... (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group, and R ² represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 2 to 5 carbon atoms. And n is a positive number of 0 to 3)

Hydrolyzable organosilicon compounds Hydrolyzable organosilicon compounds used in the present invention include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, and diphenyl. Dimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3, 3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, glycid Carboxymethyl methyltrimethoxysilane, glycidoxy methyl triethoxysilane silane, beta-glycidoxyethyl trimethoxysilane, beta-glycidoxyethyl triethoxysilane, .gamma.-glycidoxypropyltrimethoxysilane, gamma - glycidoxypropyl Triethoxysilane , γ- (β-glycidoxyethoxy ) propyltrimethoxysilane , (meth) acrylooxymethyltrimethoxysilane , (meth) acrylooxymethyltriethoxysilane , β- (meth) acrylooxyethyl Trimethoxysilane , β- (meth) acrylooxyethyltriethoxysilane , γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltri Ethoxysilane, hexyl lithoate Sisilane, octyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane , Trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, dimethoxydimethylsilane, diethoxy-3-glycidoxypropylmethylsilane, dimethoxydiphe Rushiran, diacetoxy dimethyl silane, trimethyl methoxy silane, trimethyl ethoxy silane, trimethyl silanol, and the like.

  In the present invention, the hydrolyzable organosilicon compound is preferably a hydrolyzable organosilicon compound in which n is 1 in formula (1). When a hydrolyzable organosilicon compound having n of 1 is used, polyorganosiloxane particles having a high hydrolysis rate and a large particle size can be obtained in a short time.

In the present invention, the hydrolyzable organosilicon compound may be a mixture of hydrolyzable organosilicon compounds wherein n is 0 and 1 in the formula (1). When the mixture is used, polyorganosiloxane particles having a relatively high compression modulus can be obtained.

Hydrolyzable organosilicon compound at this time (n = 0) the number of moles of (M ₀₎ and the hydrolyzable organosilicon compound the number of moles of _{(n = 1) (M 1} ) and the molar ratio of (M ₀₎ / ( M ₁ ) is preferably in the range of 0.01 to 0.5, more preferably 0.02 to 0.4.
When the molar ratio (M ₀ ) / (M ₁ ) is less than 0.01, the effect of mixing and using the hydrolyzable organosilicon compound (n = 0), for example, particles having high particle strength cannot be obtained. There is a case.
When the molar ratio (M ₀ ) / (M ₁ ) exceeds 0.5, the highly reactive hydrolyzable organosilicon compound (n = 0) is hydrolyzed and the hydrolyzable organosilicon compound (n = 1) In some cases, it is difficult to control the particle size because the true spherical particles cannot be obtained.

The catalyst for hydrolysis is not particularly limited as long as it can hydrolyze the hydrolyzable organosilicon compound, and examples thereof include an aqueous alkali metal solution, an aqueous amine solution, an aqueous ammonia solution, and ammonia gas. Among these, an aqueous ammonia solution and ammonia gas are preferable because they do not remain in the particles after drying, which will be described later, and are inexpensive.

As the alcohol , monohydric alcohol (ROH ₁ ) having 5 to 10 carbon atoms is used. Specifically, 1-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2 dimethyl-1-propanol, 2-pentanol, 3-methyl-2-butanol, 3- Examples include pentanol, 2-methyl-2-butanol, hexanol, heptanol, octanol, nonanol, decanol and the like. These alcohols can be mixed and used as necessary.

If the alcohol has 4 or less carbon atoms, the hydrolysis rate of the hydrolyzable organosilicon compound may be high, or a large particle size may not be obtained, or the particle size may not be controlled.
If the alcohol has 11 or more carbon atoms, the solubility in water is low, and micelles may not be formed, which may cause gelation or the like, resulting in failure to obtain desired particles.

When monohydric alcohol (ROH ₁ ) having 5 to 10 carbon atoms is used, polyorganosiloxane particles having a large average particle size and a small particle size variation coefficient (CV value) can be obtained.
The average particle size at this time varies depending on the type of alcohol, but is approximately 5 μm or more, the CV value is 3% or less, and the required time is approximately 2 hours or less.

In the present invention, in addition to said alcohol (ROH ₁₎ may be mixed and used monohydric alcohol having 1 to 4 carbon atoms (ROH _2).
Examples of the monohydric alcohol having 1 to 4 carbon atoms include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, and mixtures thereof. Is mentioned.
When such an alcohol is used alone without being mixed with the monohydric alcohol (ROH ₁ ) having 5 to 10 carbon atoms, the average particle diameter is generally 3 μm or less in the method of the present invention, although it varies depending on the type of alcohol. The CV value is 3% or less, and the required time is approximately one hour.

In addition, although monohydric alcohol is used in this invention, a polyhydric alcohol can also be mixed and used as needed.
The mixing ratio of the alcohol (ROH ₁ ) and the alcohol (ROH ₂ ) is such that the content of ROH _{1 in} the total alcohol is 10% by weight or more, more preferably 20% by weight or more.
When the content of ROH ₁ in the total alcohol is less than 10% by weight, there is no significant difference from using a monohydric alcohol having 1 to 4 carbon atoms alone, and the effect of increasing the growth rate of particles is small. In some cases, polyorganosiloxane particles having a large particle size cannot be obtained.

In the present invention, the average particle diameter of the polyorganosiloxane particles obtained can be easily adjusted by using a mixture of alcohol (ROH ₁ ) and alcohol (ROH ₂ ) and adjusting the mixing ratio. On the other hand, in order to adjust the particle diameter when only one of the alcohols is used, the average particle diameter can be adjusted only by any one of the conditions such as solid content concentration, temperature, stirring speed, pH, and the like described later. Therefore, it is difficult to accurately obtain polyorganosiloxane particles having a desired average particle size, and in addition, there is a problem that variation in average particle size for each production becomes large.

Next, the manufacturing method will be specifically described.
First, a mixed solvent of alcohol and water is prepared. The concentration of the alcohol in the mixed solvent is preferably in the range of 0.1 to 20% by weight, more preferably 0.2 to 10% by weight.
When the alcohol concentration in the mixed solvent is less than 0.1% by weight, the resulting particles tend to be small because the formation of uniform and large micelles does not occur, and the hydrolysis reaction time tends to be long. .
If the alcohol concentration in the mixed solvent exceeds 20% by weight, the hydrolysis reaction time is shortened but difficult to control, the particle size uniformity and reproducibility may be insufficient, and depending on the type of alcohol. Insufficient separation of the upper layer of the hydrolyzable organosilicon compound and the lower layer of alcohol / water may result in insufficient uniformity and reproducibility of the particle size. Alcohol (ROH ₁ ) and alcohol (ROH ₂ ) can be mixed and used.

Next, the aforementioned organosilicon compound is added. At this time, the organosilicon compound is added without stirring or under gentle stirring so that the organic silicon compound is separated into the upper layer and the mixed solvent is separated into the lower layer.
The amount of the organosilicon compound added is such that the concentration of the organosilicon compound in the total of the mixed solvent and the organosilicon compound is a solid content (R ¹ _n Si O _{(4-n) / 2} or SiO ₂ + R ¹ _n Si O _{(4- n) / 2} ) is preferably in the range of 0.5 to 15% by weight, more preferably 1 to 10% by weight.

When the concentration of the organosilicon compound is less than 0.5% by weight as the solid content, the particle diameter of the resulting polyorganosiloxane particles may be too small, and there is a problem in that productivity is lowered.
When the concentration of the organosilicon compound exceeds 15% by weight as a solid content, the reaction is fast, control becomes difficult, and the particle size fluctuation tends to increase. To be more.

Next, the above-mentioned hydrolysis catalyst is continuously or intermittently added to the lower layer while gently stirring the mixed solvent phase of alcohol and water in the lower layer.
The addition amount of the catalyst for hydrolysis is not particularly limited as long as all of the organosilicon compound can be hydrolyzed, and varies depending on the kind of the organosilicon compound, but the pH of the dispersion is preferably 7 to 13, more preferably 8 to 12. It is preferable to add so that it may become a range.
When the pH of the dispersion is less than 7, hydrolysis of the organosilicon compound does not occur easily and the formation of spherical micelles tends to be insufficient, or the particle size variation tends to increase.
When the pH of the dispersion exceeds 13, the reaction is fast, spherical micelles are not formed, the particle size fluctuation tends to increase, and there are cases where the particles are irregular (non-spherical) or a lot of gel is formed. is there.

The temperature at the time of hydrolysis varies depending on the type, boiling point, concentration and the like of the alcohol used, but is preferably in the range of −10 to 60 ° C., more preferably 5 to 50 ° C.
When the hydrolysis temperature is lower than −10 ° C., the organosilicon compound does not readily hydrolyze, and the formation of spherical micelles tends to be insufficient.
When the hydrolysis temperature exceeds 60 ° C., the organosilicon compound is rapidly hydrolyzed and the particle size variation tends to increase.

  After completion of the addition of the hydrolysis catalyst, it can be aged as necessary. By aging, the unreacted organosilicon compound disappears, the resulting polyorganosiloxane particles become more uniform (CV value decreases), and the production reproducibility is improved. The aging temperature may be the same as at the time of hydrolysis, but it may be high, and it is usually maintained at a temperature of about 20 to 95 ° C., preferably 30 to 90 ° C. for about 0.5 to 2 hours.

After the addition of the hydrolysis catalyst or after aging, the particles are separated from the dispersion, washed with an organic solvent such as alcohol as necessary, and then dried and / or heat-treated.
The drying conditions and heat treatment conditions are preferably appropriately selected depending on the use of the particles. For example, when particles having a low compression modulus are desired as in-plane spacers, drying is performed at about 50 to 200 ° C. or 200 to 500. Heat treatment may be performed at a relatively low temperature of about ° C. In addition, when particles having a high compression modulus are desired as the sealing spacer, the heat treatment may be performed at a relatively high temperature of about 500 to 1200 ° C.

The average particle size of the polyorganosiloxane particles thus obtained is preferably 0.5 to 30 μm, more preferably 1 to 25 μm.
The average particle diameter (Dn) of the polyorganosiloxane particles was photographed with a scanning electron microscope (JEOL Ltd .: JSM-5300 type), and an image analyzer (Asahi Kasei Co., Ltd.) was used for 250 particles of this image. ): IP-1000).

The particle diameter variation coefficient (1) (CV value (1)) of the polyorganosiloxane particles is preferably 3% or less, more preferably 2% or less.
If the particle size variation coefficient (1) exceeds 3%, when using polyorganosiloxane particles as spacers for liquid crystal display devices, the distance between electrodes must be kept precisely constant against uneven pressure from the outside. May not be possible.
The CV value (1) is calculated by the following equation (2).
CV value (1) = (particle diameter standard deviation (σ ₁ ) / average particle diameter (Dn)) × 100 (2)
Particle diameter standard deviation (σ ₁ ) = Σ ⁿ | D _i −D _n | / (n−1) × D _n
D _i : particle diameter of individual particles, n: 250

The average particle size variation coefficient (2) (CV value (2)) for each production of the polyorganosiloxane particles is preferably 3% or less, more preferably 2% or less.
The average particle diameter variation coefficient (2) for each production is calculated by the following formula (3).
CV value (2) = (particle diameter standard deviation (σ ₂ ) / average particle diameter (D _m )) × 100 (3)
Particle diameter standard deviation (σ ₂ ) = Σ ⁿ | D _h −D _m | / (m−1) × D _m
D _h : average particle diameter per production, m: 10

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

[Example 1]
Preparation of polyorganosiloxane particles (1) 420 g of 1-pentanol was mixed with 16760 g of water to prepare a water-alcohol mixed solvent (1) adjusted to a temperature of 20C.
To the water-alcohol mixed solvent (1), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Next, 96.4 g of 2.8 wt% ammonia water was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (1). The pH of the mixed solvent phase after the addition was 10.5. It took 60 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, it was separated and washed with a centrifuge, then dried at 110 ° C. for 15 hours and then calcined at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (1).
The resulting polyorganosiloxane particles (1) were measured for average particle size and particle size variation coefficient (1) (CV value (1)), and the results are shown in the table.
Next, the polyorganosiloxane particles (1) were further prepared 9 times, and the average particle diameter variation coefficient (2) (CV value (2)) for each production was measured, and the results are shown in the table.

[Example 2]
Preparation of polyorganosiloxane particles (2) A water-alcohol mixed solvent (2) adjusted to a temperature of 20C was prepared by mixing 16760 g of water with 336 g of 1-pentanol and 84 g of methanol.
To the water-alcohol mixed solvent (2), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Next, 96.4 g of 2.8 wt% ammonia water was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (2). The pH of the mixed solvent phase after the addition was 10.3. It took 50 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, it was separated and washed with a centrifugal separator, then dried at 110 ° C. for 15 hours and then calcined at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (2).
The average particle diameter and particle diameter variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (2) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (2) were further prepared 9 times, and the average particle size variation coefficient (2) (CV value (2)) for each production was measured, and the results are shown in the table.

[Example 3]
Preparation of polyorganosiloxane particles (3) 252 g of 1-pentanol and 168 g of methanol were mixed with 16760 g of water to prepare a water-alcohol mixed solvent (3) adjusted to a temperature of 20C.
To the water-alcohol mixed solvent (3), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Subsequently, 96.4 g of aqueous ammonia having a concentration of 2.8% by weight was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (3). The pH of the mixed solvent phase after the addition was 10.8. It took 40 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, it was separated and washed with a centrifugal separator, then dried at 110 ° C. for 15 hours and then calcined at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (3).
The average particle size and particle size variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (3) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (3) were further prepared 9 times, and the average particle diameter variation coefficient (2) (CV value (2)) for each production was measured, and the results are shown in the table.

[Example 4]
Preparation of polyorganosiloxane particles (4) 168 g of 1-pentanol and 252 g of methanol were mixed with 16760 g of water to prepare a water-alcohol mixed solvent (4) adjusted to a temperature of 20C.
To the water-alcohol mixed solvent (4), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Next, 96.4 g of 2.8 wt% ammonia water was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (4). The pH of the mixed solvent phase after the addition was 10.4. It took 30 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, it was separated and washed with a centrifugal separator, then dried at 110 ° C. for 15 hours and then calcined at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (4).
The average particle size and particle size variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (4) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (4) were further prepared 9 times, and the average particle diameter variation coefficient (2) (CV value (2)) for each production was measured, and the results are shown in the table.

[Example 5]
Preparation of polyorganosiloxane particles (5) A water-alcohol mixed solvent (5) adjusted to a temperature of 20C was prepared by mixing 16760 g of water with 84 g of 1-pentanol and 336 g of methanol.
To the water-alcohol mixed solvent (5), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Subsequently, 96.4 g of 2.8 wt% ammonia water was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (5). The pH of the mixed solvent phase after the addition was 10.6. It took 25 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, it was separated and washed with a centrifuge, then dried at 110 ° C. for 15 hours and then calcined at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (5).
The average particle diameter and particle diameter variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (5) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (5) were further prepared 9 times, and the average particle diameter variation coefficient (2) (CV value (2)) for each production was measured, and the results are shown in the table.

[Example 6]
Preparation of polyorganosiloxane particles (6) 16760 g of water was mixed with 42 g of 1-pentanol and 378 g of methanol to prepare a water-alcohol mixed solvent (6) adjusted to a temperature of 20C.
To the water-alcohol mixed solvent (6), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Subsequently, 96.4 g of aqueous ammonia having a concentration of 2.8% by weight was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (6). The pH of the mixed solvent phase after the addition was 10.5. It took 15 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, it was separated and washed with a centrifugal separator, then dried at 110 ° C. for 15 hours and then calcined at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (6).
The average particle size and particle size variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (6) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (6) were further prepared 9 times, and the average particle diameter variation coefficient (2) (CV value (2)) for each production was measured, and the results are shown in the table.

[Example 7]
Preparation of polyorganosiloxane particles (7) Water-alcohol mixed solvent (7) adjusted to a temperature of 20C was prepared by mixing 420 g of heptanol with 16760 g of water.
To the water-alcohol mixed solvent (7), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Next, 96.4 g of 2.8 wt% ammonia water was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (7). The pH of the mixed solvent phase after the addition was 10.7. It took 80 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, it was separated and washed with a centrifugal separator, then dried at 110 ° C. for 15 hours and then calcined at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (7).
The average particle size and particle size variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (7) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (7) were repeatedly prepared 9 times, and the average particle diameter variation coefficient (2) (CV value (2)) for each production was measured. The results are shown in the table.

[Example 8]
Preparation of polyorganosiloxane particles (8) 420 g of nonanol was mixed with 16760 g of water to prepare a water-alcohol mixed solvent (8) adjusted to a temperature of 20 ° C.
To the water-alcohol mixed solvent (8), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Next, 96.4 g of 2.8 wt% ammonia water was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (8). The pH of the mixed solvent phase after the addition was 10.4. It took 110 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, it was separated and washed with a centrifugal separator, then dried at 110 ° C. for 15 hours and then calcined at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (8).
The resulting polyorganosiloxane particles (8) were measured for average particle size and particle size variation coefficient (1) (CV value (1)), and the results are shown in the table.
Next, the polyorganosiloxane particles (8) were further prepared 9 times, and the average particle diameter variation coefficient (2) (CV value (2)) for each production was measured, and the results are shown in the table.

[Example 9]
Preparation of polyorganosiloxane particles (9) 420 g of 1-pentanol was mixed with 16728 g of water to prepare a water-alcohol mixed solvent (9) adjusted to a temperature of 20C.
1294 g (9.5 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) as an organosilicon compound in a water-alcohol mixed solvent (9), and tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd.): 104 g (0.5 mol) of normal ethyl silicate-A) was added dropwise.
Next, 96.4 g of 2.8 wt% ammonia water was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (9). The pH of the mixed solvent phase after the addition was 10.3. It took 50 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, it was separated and washed by a centrifugal separator, then dried at 110 ° C. for 15 hours and then calcined at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (9).
The average particle diameter and particle diameter variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (9) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (9) are further prepared 9 times, and the average particle diameter variation coefficient (2) (CV value (2)) for each production is measured, and the results are shown in the table.

[Example 10]
Preparation of polyorganosiloxane particles (10) A water-alcohol mixed solvent (10) adjusted to a temperature of 40C was prepared by mixing 420 g of 1-pentanol with 16760 g of water.
To the water-alcohol mixed solvent (10), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Subsequently, 96.4 g of 2.8 wt% ammonia water was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (10). The pH of the mixed solvent phase after the addition was 10.4. It took 14 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, it was separated and washed with a centrifugal separator, then dried at 110 ° C. for 15 hours and then calcined at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (10).
The average particle diameter and particle diameter variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (10) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (10) were further prepared 9 times, and the average particle size variation coefficient (2) (CV value (2)) for each production was measured, and the results are shown in the table.

[Example 11]
Preparation of polyorganosiloxane particles (11) 168 g of 1-pentanol and 252 g of methanol were mixed with 15218 g of water to prepare a water-alcohol mixed solvent (11) adjusted to a temperature of 20 ° C.
To the water-alcohol mixed solvent (11), 2904 g ( 11.7 mol) of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added dropwise as an organosilicon compound.
Subsequently, 96.4 g of aqueous ammonia having a concentration of 2.8% by weight was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (11). The pH of the mixed solvent phase after the addition was 10.4. It took 70 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, it was separated and washed with a centrifugal separator, then dried at 110 ° C. for 15 hours and then calcined at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (11).
The average particle diameter and particle diameter variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (11) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (11) were repeatedly prepared 9 times, and the average particle diameter variation coefficient (2) (CV value (2)) for each production was measured, and the results are shown in the table.

[Comparative Example 1]
Preparation of polyorganosiloxane particles (R1) Water-alcohol mixed solvent (R1) adjusted to a temperature of 20C was prepared by mixing 420g of methanol with 16760g of water.
To the water-alcohol mixed solvent (R1), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Subsequently, 96.4 g of aqueous ammonia having a concentration of 2.8% by weight was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (R1). The pH of the mixed solvent phase after the addition was 10.6. It took 12 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, separation and washing were performed with a centrifugal separator, followed by drying at 110 ° C. for 15 hours and then baking at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (R1).
The average particle diameter and particle diameter variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (R1) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (R1) were further prepared 9 times, and the average particle size variation coefficient (2) (CV value (2)) for each production was measured, and the results are shown in the table.

[Comparative Example 2]
Preparation of polyorganosiloxane particles (R2) A water-alcohol mixed solvent (R2) adjusted to a temperature of 20C was prepared by mixing 16760 g of water with 21 g of 1-pentanol and 399 g of methanol.
To the water-alcohol mixed solvent (R2), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Next, 96.4 g of 2.8 wt% ammonia water was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (R2). The pH of the mixed solvent phase after the addition was 10.4. It took 13 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, separation and washing were performed with a centrifugal separator, followed by drying at 110 ° C. for 15 hours and then baking at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (R2).
The average particle diameter and particle diameter variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (R2) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (R2) were repeatedly prepared 9 times, the average particle size variation coefficient (2) (CV value (2)) for each production was measured, and the results are shown in the table.

[Comparative Example 3]
Preparation of polyorganosiloxane particles (R3) 420 g of butanol was mixed with 16760 g of water to prepare a water-alcohol mixed solvent (R3) adjusted to a temperature of 20C.
To the water-alcohol mixed solvent (R3), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Next, 96.4 g of 2.8 wt% ammonia water was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (R3). The pH of the mixed solvent phase after the addition was 10.5. It took 30 minutes for the organic solvent compound phase to disappear in the mixed solvent phase. Subsequently, aging was performed at 80 ° C. for 15 hours.
Subsequently, separation and washing were carried out with a centrifugal separator, followed by drying at 110 ° C. for 15 hours and then baking at 1000 ° C. for 3 hours to prepare polyorganosiloxane particles (R3).
The average particle diameter and particle diameter variation coefficient (1) (CV value (1)) of the obtained polyorganosiloxane particles (R3) were measured, and the results are shown in the table.
Next, the polyorganosiloxane particles (R3) were repeatedly prepared 9 times, and the average particle diameter variation coefficient (2) (CV value (2)) for each production was measured. The results are shown in the table.

[Comparative Example 4]
Preparation of polyorganosiloxane particles (R4) A water-alcohol mixed solvent (R4) adjusted to a temperature of 20C was prepared by mixing 420 g of undecanol with 16760 g of water.
To the water-alcohol mixed solvent (R4), 1362 g (10 mol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13) was added dropwise as an organosilicon compound.
Subsequently, 96.4 g of aqueous ammonia having a concentration of 2.8% by weight was added in about 1 minute while gently stirring the lower layer water-alcohol mixed solvent (R4). The pH of the mixed solvent phase after the addition was 10.8. The mixed solvent phase was stopped after 2 hours because gel formation was observed.

Claims (5)

In the following formula (1), the hydrolyzable organosilicon compound phase with n = 1 is placed in the upper layer, the water / alcohol mixed solvent phase of the hydrolysis catalyst is placed in the lower layer, and the hydrolyzable organosilicon compound and the hydrolyzate In the method for producing polyorganosiloxane particles in contact with a catalyst, the alcohol contains a monohydric alcohol (ROH ₁ ) having 5 to 10 carbon atoms, and the content of ROH _{1 in} the total alcohol is 10% by weight or more. A process for producing polyorganosiloxane particles.
R ¹ _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group, and R ² represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 2 to 5 carbon atoms. And n is 1 )
In the following formula (1), a mixture phase of hydrolyzable organosilicon compounds having n of 0 and 1 is disposed in the upper layer, and a water / alcohol mixed solvent phase of the hydrolysis catalyst is disposed in the lower layer, and the hydrolyzable organosilicon compound In the method for producing polyorganosiloxane particles in which the catalyst for hydrolysis is brought into contact, the alcohol contains a monohydric alcohol (ROH ₁ ) having 5 to 10 carbon atoms, and the content of ROH _{1 in} the total alcohol is 10% by weight or more. A method for producing polyorganosiloxane particles, wherein
R ¹ _n Si (OR ² ) _4-n (1)
(In the formula, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group, and R ² represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 2 to 5 carbon atoms. And n is 0 or 1) Method for producing polyorganosiloxane particles of claim 1 or 2, wherein the alcohol is further characterized to include a monohydric alcohol having 1 to 4 carbon atoms (ROH _2). The average particle diameter of the polyorganosiloxane particles have a range of 0.5 to 30 m, according to claim 1 to 3, characterized in that the particle diameter coefficient of variation (1) (CV value (1)) is 3% or less The manufacturing method of the polyorganosiloxane particle in any one of. The method for producing polyorganosiloxane particles according to any one of claims 1 to 4 , wherein an average particle diameter variation coefficient (2) (CV value (2)) for each production is 3% or less.