KR101208162B1 - Polyorganosilsesquioxane-based Microparticles and Method for Preparing the Same - Google Patents

Abstract

The present invention does not treat the surface of the isolated polymethylsilsesquioxane fine particles, does not use a compound containing a fluoroalkyl group, has a high water repellency, polyorganosil having excellent dispersibility and affinity for various materials. It relates to sesquioxane-based fine particles.

On the surface of the polyorganosilsesquioxane-based fine particles invention, R ¹ or higher SiO _3/2 units (wherein, R ¹ is the same or a different carbon atoms of 1 to 20 monovalent organic group in) is 70 mol%, Si (OR ² ) ₄ , wherein R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, the same or different, and (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH ( Here, R ³ is a hydrogen atom or an alkyl group having the same or different carbon atoms of 1 to 6), which is hydrolyzed and condensed to obtain polyorganosilsesquioxane-based fine particles having a melting point of 300 ° C. or higher or no melting point. .

Polyorgano silsesquioxane type microparticles

Description

Polyorganosilsesquioxane microparticles | fine-particles and its manufacturing method {Polyorganosilsesquioxane-based Microparticles and Method for Preparing the Same}

[Patent Document 1] Belgian Patent No. 572412

[Patent Document 2] Japanese Unexamined Patent Publication No. 6-179751

[Patent Document 3] Japanese Patent Publication No. 40-16917

[Patent Document 4] Japanese Patent Application Laid-Open No. 54-72300

[Patent Document 5] Japanese Patent Application Laid-Open No. 3-244636

[Patent Document 6] Japanese Unexamined Patent Publication No. 1-185367

[Patent Document 7] Japanese Patent Application Laid-Open No. 9-87532

[Patent Document 8] Japanese Patent Application Laid-Open No. 11-255615

[Patent Document 9] Japanese Unexamined Patent Publication No. 2-150426

[Patent Document 10] Japanese Unexamined Patent Publication No. 2003-13047

[Patent Document 11] Japanese Unexamined Patent Application Publication No. 4-122731

The present invention relates to a surface-modified polyorganosilsesquioxane-based fine particles and a method for producing the same, and more particularly, a surface lubricity and water repellency imparting agent for paints, inks and coatings; Cosmetics, extenders of the wax, surface lubricity, water repellency imparting agents; Antiblocking agents of plastic films; And a polyorganosilsesquioxane-based fine particle suitable as a light diffusing agent of a plastic sheet or sheet, and a method for producing the same.

Various methods are conventionally proposed about the manufacturing method of the polyorgano silsesquioxane microparticles | fine-particles which are comprised substantially from the trifunctional siloxane unit, and have the structure bridge | crosslinked in the three-dimensional mesh shape. For example, the method of hydrolyzing and condensing methyl trichlorosilane in water (refer patent document 1), and the method of adding trichloroorganosilane to saturated aqueous solution of hydrogen chloride, and hydrolyzing and condensation reaction (refer patent document 2). ), Hydrolysis and condensation reaction of methyltrialkoxysilane in aqueous solution of alkali metal hydroxide, ammonia or organic amine (see Patent Document 3), hydrolysis of methyltrialkoxysilane in aqueous solution of alkaline earth metal hydroxide or alkali metal carbonate, The method of making condensation reaction (refer patent document 4), the method of dissolving organo trialkoxysilane in aqueous organic carboxylic acid solution, and hydrolyzing and condensation reaction in aqueous alkali solution (refer patent document 5), etc. are mentioned.

 The polyorganosilsesquioxane microparticles | fine-particles obtained by these methods are a synthetic resin, a natural rubber, the lubrication property and abrasion resistance provision of a synthetic rubber; Surface lubricity of paints, inks and coatings; Cosmetics, the extension of the wax, imparting surface lubricity; Imparting antiblocking properties of plastic films; It is added to various materials for the purpose of providing the light diffusivity of a plastic plate or a sheet | seat. In particular, although the polyorganosilsesquioxane microparticles | fine-particles added to a coating material, a coating agent, cosmetics, a wax, etc. may require high water repellency as the characteristic, the polyorgano silsesquioxane microparticles | fine-particles obtained by the above-mentioned conventional method are water repellent It is not necessarily enough from a point of view. Moreover, the said polyorgano silsesquioxane microparticles | fine-particles manufactured by the above-mentioned conventional method have a problem that the dispersibility to synthetic resin, natural rubber, and synthetic rubber is inferior.

Therefore, in order to improve the water repellency, dispersibility, etc. of polyorgano silsesquioxane microparticles | fine-particles, various methods are proposed, For example, the method of treating the surface of isolated polymethyl silsesquioxane microparticles | fine-particles with a silylating agent (patent Document 6), a method of treating the surface of the isolated polymethylsilsesquioxane fine particles with organosiloxane diol (see Patent Document 7), and treating the surface of the isolated polymethylsilsesquioxane fine particles with hydrogenmethylmethylsiloxane After dissolving the organotrialkoxysilane in the aqueous organic carboxylic acid solution, condensation reaction in an aqueous alkali solution, then disilazane is added, and the polyorganosilsesquioxane fine particles The method of silylating a surface (refer patent document 5), etc. are proposed.

Among these methods, the method for treating the surface of the isolated polymethylsilsesquioxane fine particles is expensive because the prepared polymethylsilsesquioxane fine particles are prepared and then the surface treatment step is performed. Although the water repellency of the polyorganosilsesquioxane microparticles | fine-particles obtained by the method was improved to some extent, it is still inadequate.

Therefore, as a method of imparting higher water repellency to the polyorganosilsesquioxane fine particles, a method of treating the surface of the isolated polymethylsilsesquioxane fine particles with a silylating agent containing a fluoroalkyl group (see Patent Documents 9 and 10). And polyorganosilsesquioxane microparticles | fine-particles containing a perfluoroalkyl silsesquioxane unit (refer patent document 11), etc. are proposed.

However, since halogen liberalization is demanded in recent years as environmental awareness becomes high, it is gaining attention to use a compound containing a fluoroalkyl group.

The problem to be solved by the present invention is not treating the surface of the polymethylsilsesquioxane fine particles isolated on the basis of the above problems, without using a compound containing a fluoroalkyl group, having a high water repellency, The present invention provides a polyorganosilsesquioxane-based fine particle having excellent dispersibility and affinity.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors found that Si (OR ² ) ₄ and (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] on the surface of polyorganosilsesquioxane-based fine particles. _The present invention has been completed by discovering that the above problems can be solved by reacting ₂ NH.

That is, the present invention R ¹ SiO _3/2 units (wherein, R ¹ are the same or different carbon atoms of 1 to 20 monovalent organic group being a) is 70 mol% or more polyorganosilsesquioxane based on the surface of the fine particles , Si (OR ² ) ₄ , wherein R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, the same or different, and (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ It is obtained by hydrolysis and condensation reaction of NH (wherein R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms having the same or different carbon atoms), and a polyolefin having a melting point of 300 ° C. or higher or no melting point Nosilsesquioxane type microparticles | fine-particles are related.

BEST MODE FOR CARRYING OUT THE INVENTION [

Hereinafter, the present invention will be described in more detail.

In the surface of polyorganosilsesquioxane-based fine particle is R ¹ SiO _3/2 polyorganosilsesquioxane-based fine particles or more units of 70 mol% of the present invention as described above, Si (OR ²⁾ ₄ and (CH ₃ ) It is obtained by hydrolyzing and condensing ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH.

R ¹ SiO _3/2 units is 70% less than the polyorganosilsesquioxane-based fine particles mole, as other units R ¹ ₂ SiO _2/2 units, R _{¹ 3} SiO _^1/2 units, or SiO _4/2 units It may include. The reason why the R ¹ SiO _3/2 unit is 70 mol% or more is that when the unit is less than 70 mol%, the polyorganosilsesquioxane-based fine particles may be soft and the surface lubricity may be insufficient. The higher the specific gravity, the easier it is to cause sedimentation when blended with the material, and the lower the specific gravity is, and the material containing the organic solvent is insufficient in surface lubricity, water repellency, and the like.

R ¹ constituting each unit is one or two or more monovalent organic groups having 1 to 20 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl groups Alkyl groups such as octyl group, nonyl group, decyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, nonadecyl group, and isosil group; Aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; Cycloalkyl groups such as cyclobutyl group, cyclopentyl group and cyclohexyl group; Unsaturated alkyl groups such as vinyl group, allyl group, propenyl group and butenyl group; Aralkyl groups such as benzyl, phenethyl and β-phenylpropyl; And halogenated organic groups such as trifluoropropyl group, β- (perfluorobutyl) ethyl group and β- (perfluorooctyl) ethyl group in which part or all of the hydrogen atoms of these organic groups are substituted with halogen atoms; Moreover, it selects from the said organic group containing some functional groups, such as an amino group, an epoxy group, an acryloxy group, a methacryloxy group, a mercapto group, and a cyano group. In this, a methyl group is preferable.

R ¹ SiO _3/2 units is 70% less than the polyorganosilsesquioxane-based fine particles mol to the alkoxysilane added to the aqueous solution of the alkaline substance hydrolysis, to condensation reaction, or an alkoxy silane in an aqueous solution of neutral or acidic It can be obtained as an aqueous dispersion of the said polyorgano silsesquioxane microparticles | fine-particles by adding and hydrolyzing, and then adding an alkaline substance or its aqueous solution and condensing reaction.

The alkoxysilane added to the aqueous solution is represented by the formula R ¹ Si (OR ⁴ ) ₃ , R ¹ ₂ Si (OR ⁴ ) ₂ , R ¹ ₃ SiOR ⁴ and Si (OR ⁴ ) ₄ , the hydrolyzate and / or The partial hydrolysis condensate can also be used. In said formula, R <^1> is the same as the above, R <^4> is 1 type or 2 or more types of alkyl groups which consist of 1-6 carbon atoms, For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group And methyl group is particularly preferable.

The blending ratio of R ¹ Si (OR ⁴ ) ₃ , R ¹ ₂ Si (OR ⁴ ) ₂ , R ¹ ₃ SiOR ^4, and Si (OR ⁴ ) ₄ is appropriately determined so as to have the desired structure of the polyorganosilsesquioxane-based fine particles. Can be. That is, the desired mole ratio of R ¹ SiO _3/2 units to R ¹ ₂ SiO _2/2 units to R _{¹ 3} SiO _^1/2 units to SiO _4/2 unit ^{= R 1 Si (OR 4)} 3: R 1 2 Si (OR ⁴ ) ₂ : R ¹ ₃ SiOR ⁴ : Si (OR ⁴ ) ₄ .

The alkaline substance serves as a catalyst for the hydrolysis and condensation reaction of the alkoxysilane (condensation reaction when alkoxysilane is added to a neutral or acidic aqueous solution) and has excellent catalytic activity and can be easily removed by volatilization from the preparation. As such, ammonia, or a low boiling amine such as monomethylamine or monoethylamine is preferable. Moreover, you may mix | blend water-soluble organic solvents, such as water-soluble polymers, such as surfactant and polyvinyl alcohol, and alcohol, with the aqueous solution of the said alkaline substance.

Similarly, the aqueous solution of neutral or acid may be blended with a water-soluble polymer such as a surfactant, a water-soluble polymer such as polyvinyl alcohol, and an alcohol.

The polyorganosilsesquioxane-based fine particles of the present invention hydrolyze and condensate Si (OR ² ) ₄ on the surface of the polyorganosilsesquioxane-based fine particles, and (CH ₃ ) ₃ SiOR ³ and / or [(CH _{3) 3} Si] ₂ NH can be prepared by hydrolysis and condensation reaction. Specifically, Si (OR ² ) ₄ and (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH are added to the aqueous dispersion of the polyorganosilsesquioxane fine particles obtained by the above method under stirring. Or it is added dropwise gradually, and these are subjected to hydrolysis and condensation reaction.

Here, R ² is a hydrogen atom or an alkyl group having the same or different carbon atoms of 1 to 6, and examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group, and methyl group is particularly preferable. . In addition, R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms having the same or different carbon atoms, and examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group, and especially hydrogen atom or methyl group. Is preferred.

Si (OR ² ) ₄ and (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH are hydrolyzed and condensed by the catalysis of the previously added alkaline substances, but polyorganosilsesqui When the pH of the aqueous dispersion of the oxane-based fine particles is low, the reaction rate of Si (OR ² ) ₄ and (CH ₃ ) ₃ SiOR ³ and / or (CH ₃ ) ₃ SiOR ³ decreases, so that Si (OR ² ) ₄ and ( The alkaline substance described above may be added and added before or after the addition of CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH.

The polyorganosilsesquioxane-based fine particles of the present invention are introduced onto the surface of the polyorganosilsesquioxane-based fine particles by hydrolysis and condensation reaction of (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH. Although it is thought that the effect of this invention, such as water repellency, is imparted by the trimethylsilyl group which was made, in this invention, in order to form many trimethylsilyl groups on the surface of polyorgano silsesquioxane type microparticles | fine-particles, on the surface of polyorgano silsesquioxane type microparticles | fine-particles, Si (OR ² ) ₄ is hydrolyzed and condensed. That is, in the present invention, by hydrolysis and condensation reaction of Si (OR ² ) ₄ on the surface of the polyorganosilsesquioxane-based fine particles, (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH Many silanol groups and / or alkoxysilyl groups which can be reacted are formed, thereby increasing the trimethylsilyl group.

If the amount of Si (OR ² ) ₄ added to the aqueous dispersion of the polyorganosilsesquioxane-based fine particles is less than 0.1 part by weight based on 100 parts by weight of the polyorganosilsesquioxane-based fine particles, the water repellency is insufficient, and more than 20 parts by weight. Since a water repellency does not improve at most, 0.1-20 weight part is preferable and the range of 1-10 weight part is more preferable.

If the amount of (CH ₃ ) ₃ SiOR ³ added to the aqueous dispersion of the polyorganosilsesquioxane fine particles is less than 1 mole with respect to 1 mole of Si (OR ² ) ₄ , the water repellency is lowered. Since it is not, 1-4 mol is preferable and the range of 2-3.5 mol is more preferable.

If the amount of [(CH ₃ ) ₃ Si] ₂ NH added to the aqueous dispersion of the polyorganosilsesquioxane fine particles is less than 0.5 mole with respect to 1 mole of Si (OR ² ) ₄ , the water repellency is lowered. Since silver does not improve, 0.5-2 mol is preferable and the range of 1-1.8 mol is more preferable.

Stirring when adding Si (OR ² ) ₄ and (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH to an aqueous dispersion of polyorganosilsesquioxane-based fine particles is performed by vigorous stirring. If agglomerates occur between the particles and the water repellency is insufficient, it is preferable to use smooth agitation using propeller blades, flat blades, or the like, but Si (OR ² ) ₄ and (CH ₃ ) ₃ SiOR ³ and / or [( CH _{3) 3} Si] the stirring intensity is required to be ₂ NH is a poly Organic nosil sesquioleate dispersed in the aqueous dispersion of the siloxane-based fine particles.

The temperature when Si (OR ² ) ₄ and (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH is added to the aqueous dispersion of polyorganosilsesquioxane fine particles is lower than 0 ° C. If it is, the aqueous dispersion solidifies, and if it is higher than 60 ° C, the particles will aggregate and the water repellency will be insufficient, so that the temperature is preferably 0 to 60 ° C, more preferably 0 to 40 ° C.

Si (OR ² ) ₄ and (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH are added simultaneously to the aqueous dispersion of polyorganosilsesquioxane-based fine particles, or Si (OR ² ) ₄ Is added first, followed by (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH. It is preferable to continue stirring for a while until completion | finish of hydrolysis and condensation reaction after completion | finish of addition, and you may heat at 40-100 degreeC in order to complete a hydrolysis and condensation reaction. If necessary, acidic substances may be added to neutralize them.

Since the polyorganosilsesquioxane microparticles | fine-particles obtained as mentioned above are an aqueous dispersion liquid, in order to make the polyorgano silsesquioxane microparticles | fine-particles of this invention, it is necessary to remove water and methanol which are a side product from now on. These may be removed by heating or heating under reduced pressure, but for this, a method may be performed by standing the dispersion liquid, a method of stirring and flowing the dispersion liquid, a method of spraying and dispersing the dispersion liquid in a hot air stream such as a spray dryer, or using a fluidized heating medium. The method may be used. At this time, the dispersion liquid may be concentrated as a pretreatment by heating dehydration, filtration separation, centrifugation, decantation, etc., or may be washed with water if necessary. And the polyorgano silsesquioxane type microparticles | fine-particles of this invention can be obtained by removing water and methanol by these methods.

Moreover, when the polyorgano silsesquioxane type microparticles | fine-particles taken out are aggregated, it is also necessary to disintegrate with grinders, such as a jet mill, a ball mill, and a hammer mill.

Although the shape of the polyorgano silsesquioxane type microparticles | fine-particles of this invention is not specifically limited, spherical shape, amorphous form, flaky shape, needle shape, plate shape, etc., It is preferable that it is spherical in order to acquire favorable dispersibility and affinity for a base material.

In addition, the average particle diameter of the polyorganosilsesquioxane-based fine particles of the present invention is preferably in the range of 0.1 to 50 µm, particularly 1 to 30 µm, to provide characteristics such as surface lubricity, antiblocking properties, light diffusivity, dispersibility, and the like. It is preferable to obtain.

Since the melting | fusing point of the polyorgano silsesquioxane type microparticles | fine-particles of this invention obtained by the said manufacturing method is 300 degreeC or more, it is necessary not to show clear melting | fusing point. When the melting point of the polyorganosilsesquioxane-based fine particles is less than 300 ° C, the inside of the particles is exposed to the particle surface by heat, the water repellency, the dispersibility, etc. are lowered, and the molecular weight is small, so that they are dissolved in the organic solvent.

The polyorganosilsesquioxane-based fine particles of the present invention can be used to impart water repellency, extension property, surface lubricity, antiblocking property, etc. to various materials, and specifically, provide surface lubricity and water repellency of paints, inks and coating agents. My; Cosmetics, extenders of the wax, surface lubricity, water repellency imparting agents; Antiblocking agents of plastic films; And light diffusing agents for plastic plates and sheets.

<Examples>

Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited by these.

<Evaluation method of water repellency>

The aqueous methanol solution of each concentration which increased the methanol concentration from 20% by 2% was prepared. Then, the polyorganosilsesquioxane-based fine particles were added to 100 g of these aqueous methanol solutions, stirred for 10 seconds with a glass rod, and the methanol concentration was obtained when the polyorganosilsesquioxane-based fine particles began to disperse the whole amount without floating in the aqueous methanol solution. And the water repellency of the polyorgano silsesquioxane microparticles | fine-particles were evaluated from the value of this concentration. That is, the higher the methanol concentration, the higher the water repellency of the polyorganosilsesquioxane-based fine particles.

(Example 1)

3,657 g of ion-exchanged water and 86 g of ammonia water (concentration 28%) were put into a 5 L glass flask, and the water temperature was 20 degreeC. It stirred by the anchor type stirring blade on the conditions of blade | wing rotation speed of 150 rpm, 743 g of methyl trimethoxysilane was dripped over 3 hours, and the liquid temperature was hold | maintained at 15-25 degreeC in the meantime. After completion of the dropwise addition, the mixture was stirred at 15 to 25 ° C. for 15 minutes, and then 5 g of tetramethoxysilane and 9 g of trimethylsilanol (tetramethoxysilane / trimethylsilanol (molar ratio) = 1.0 / 3.0, trimethylsilanol were polymethylsil). 2.5 parts by weight based on 100 parts by weight of the sesquioxane-based fine particles) was added, and further maintained at 15 to 25 ℃ stirred for 1 hour, then heated to 55 to 60 ℃, and then stirred for 1 hour It was. The obtained solution was degreased using a pressure filter to obtain a cake-like substance, the cake-like substance was dried at a temperature of 105 ° C. in a hot air circulation dryer, and the dried product was pulverized with a jet mill to obtain polymethylsilsesquioxane-based fine particles (melting point). : None).

It was 2.3 micrometers when the average particle diameter of this polymethylsilsesquioxane type silicone microparticles | fine-particles was measured using Multisizer II (particle size distribution measuring apparatus, a Beckman Coulter company make, brand name).

Moreover, when the shape of the said polymethylsilsesquioxane microparticles | fine-particles was observed with the optical microscope, it was spherical.

Moreover, when the water repellency of the said polymethylsilsesquioxane microparticles | fine-particles was evaluated by the said method, the methanol concentration when it started to disperse | distribute whole quantity in methanol aqueous solution was 44%.

(Example 2)

3,643 g of ion-exchanged water and 86 g of ammonia water (concentration 28%) were put into a 5 L glass flask, and the water temperature was 20 degreeC. It stirred by the anchor type stirring blade on the conditions of blade | wing rotation speed of 150 rpm, 743 g of methyl trimethoxysilane was dripped over 3 hours, and the liquid temperature was hold | maintained at 15-25 degreeC in the meantime. After completion of the dropwise addition, the mixture was stirred at 15 to 25 ° C. for 15 minutes, and then 10 g of tetramethoxysilane and 18 g of trimethylsilanol (tetramethoxysilane / trimethylsilanol (molar ratio) = 1.0 / 3.0 and trimethylsilanol were polymethylsil). The amount of 4.9 parts by weight based on 100 parts by weight of the sesquioxane-based fine particles) was added, and the mixture was further maintained at 15 to 25 ° C and stirred for 1 hour, then heated to 55 to 60 ° C, followed by stirring for 1 hour. It was. The obtained solution was degreased using a pressure filter to obtain a cake-like substance, the cake-like substance was dried at a temperature of 105 ° C. in a hot air circulation dryer, and the dried product was pulverized with a jet mill to obtain polymethylsilsesquioxane-based fine particles (melting point). : None).

The average particle diameter of this polymethylsilsesquioxane type microparticles | fine-particles was 2.2 micrometers when it measured using the multisizer II (particle size distribution measuring apparatus, the Beckman Coulter company make, brand name).

Moreover, when the shape of the said polymethylsilsesquioxane microparticles | fine-particles was observed with the optical microscope, it was spherical.

Moreover, when the water repellency of the said polymethylsilsesquioxane type microparticles | fine-particles was evaluated by the said method, methanol concentration when it started to disperse | distribute whole quantity in methanol aqueous solution was 68%.

(Example 3)

3,642 g of ion-exchanged water and 86 g of ammonia water (concentration 28%) were put into a 5 L glass flask, and the water temperature was 20 degreeC. It stirred by the anchor type stirring blade on the conditions of blade | wing rotation speed of 150 rpm, 743 g of methyl trimethoxysilane was dripped over 3 hours, and the liquid temperature was hold | maintained at 15-25 degreeC in the meantime. After completion of the dropwise addition, the mixture was stirred at 15 to 25 ° C. for 15 minutes, and then 10 g of tetramethoxysilane was added thereto, followed by stirring for 15 minutes, and then 20 g of trimethylmethoxysilane (tetramethoxysilane / trimethylmethoxysilane (molar ratio) = 1.0 / 2.9, trimethylmethoxysilane is added in an amount of 5.5 parts by weight relative to 100 parts by weight of the polymethylsilsesquioxane-based fine particles), and further maintained at 15 to 25 ℃ stirred for 1 hour and then 55 to 60 Heat to C and continue stirring for 1 h. The obtained solution was degreased using a pressure filter to obtain a cake-like substance, the cake-like substance was dried at a temperature of 105 ° C. in a hot air circulation dryer, and the dried product was pulverized with a jet mill to obtain polymethylsilsesquioxane fine powder (melting point). : None).

The average particle diameter of this polymethylsilsesquioxane type microparticles | fine-particles was 2.3 micrometers when it measured using the multisizer II (particle size distribution measuring apparatus, the Beckman Coulter company make, brand name).

Moreover, when the shape of the said polymethylsilsesquioxane microparticles | fine-particles was observed with the optical microscope, it was spherical.

Moreover, when the water repellency of the said polymethylsilsesquioxane type microparticles | fine-particles was evaluated by the said method, methanol concentration when it started to disperse | distribute whole quantity in methanol aqueous solution was 64%.

(Example 4)

3,645 g of ion-exchange water and 86 g of ammonia water (concentration 28%) were put into the 5 L glass flask, and the water temperature was 20 degreeC. It stirred by the anchor type stirring blade on the conditions of blade | wing rotation speed of 150 rpm, 743 g of methyl trimethoxysilane was dripped over 3 hours, and the liquid temperature was hold | maintained at 15-25 degreeC in the meantime. After completion of the dropping, the mixture was stirred at 15 to 25 ° C. for 15 minutes, and then 10 g of tetramethoxysilane was added thereto, followed by stirring for 15 minutes, followed by 16 g of hexamethyldisilazane (tetramethoxysilane / hexamethyldisilazane (molar ratio). ) = 1.0 / 1.5, hexamethyldisilazane was added 4.3 parts by weight based on 100 parts by weight of the polymethylsilsesquioxane-based fine particles), and further maintained at 15 to 25 ℃ stirred for 1 hour Heat to 55-60 ° C. and continue stirring for 1 hour. The obtained solution was degreased using a pressure filter to obtain a cake-like substance, the cake-like substance was dried at a temperature of 105 ° C. in a hot air circulation dryer, and the dried product was pulverized with a jet mill to obtain polymethylsilsesquioxane-based fine particles (melting point). : None).

The average particle diameter of this polymethylsilsesquioxane type microparticles | fine-particles was 2.3 micrometers when it measured using the multisizer II (particle size distribution measuring apparatus, the Beckman Coulter company make, brand name).

Moreover, when the shape of the said polymethylsilsesquioxane microparticles | fine-particles was observed with the optical microscope, it was spherical.

Moreover, when the water repellency of the said polymethylsilsesquioxane type microparticles | fine-particles was evaluated by the said method, methanol concentration when it started to disperse | distribute whole quantity in methanol aqueous solution was 64%.

(Example 5)

3,738 g of ion-exchanged water was put into a 5 L glass flask, and the water temperature was 20 degreeC. The mixture was stirred with an anchor-type stirring blade under the condition of a blade rotation speed of 150 rpm, and 720 g of methyltrimethoxysilane was added thereto. Then, heat was generated, and after 15 minutes, the temperature was raised to 32 ° C to become a transparent state. After maintaining at 25-35 degreeC and stirring for 1 hour, 3.6g of 70% ethylamine aqueous solution was added and stirred for 1 minute, and stirring was stopped. Turbidity arises after 40 seconds of stoppage of stirring, and after 15 minutes, stirring is resumed and 10 g of tetramethoxysilane and 18 g of trimethylsilanol (tetramethoxysilane / trimethylsilanol (molar ratio) = 1.0 / 3.0, trimethylsilanol) 5.1 parts by weight with respect to 100 parts by weight of the polymethylsilsesquioxane-based fine particles) was added, and the mixture was further maintained at 25 to 35 ° C, stirred for 1 hour, and then 10 g of a 70% ethylamine aqueous solution was added thereto, Heat to 55-60 ° C. and continue stirring for 1 hour. The obtained solution was degreased using a pressure filter to obtain a cake-like substance, the cake-like substance was dried at a temperature of 105 ° C. in a hot air circulation dryer, and the dried product was pulverized with a jet mill to obtain polymethylsilsesquioxane-based fine particles (melting point). : None).

The average particle diameter of this polymethylsilsesquioxane type microparticles | fine-particles was 2.2 micrometers when it measured using the multisizer II (particle size distribution measuring apparatus, the Beckman Coulter company make, brand name).

Moreover, when the shape of the said polymethylsilsesquioxane microparticles | fine-particles was observed with the optical microscope, it was spherical.

Moreover, when the water repellency of the said polymethylsilsesquioxane microparticles | fine-particles was evaluated by the said method, the methanol concentration when it started to disperse | distribute whole quantity in methanol aqueous solution was 62%.

(Comparative Example 1)

3,671 g of ion-exchanged water and 86 g of ammonia water (concentration 28%) were put into a 5 L glass flask, and the water temperature was 20 degreeC. It stirred by the anchor type stirring blade on the conditions of blade | wing rotation speed of 150 rpm, 743 g of methyl trimethoxysilane was dripped over 3 hours, and the liquid temperature was hold | maintained at 15-25 degreeC in the meantime. After completion of the dropwise addition, the mixture was kept at 15 to 25 ° C, stirred for 1 hour, heated to 55 to 60 ° C, and stirred for 1 hour. The obtained solution was degreased using a pressure filter to obtain a cake-like substance, the cake-like substance was dried at a temperature of 105 ° C. in a hot air circulation dryer, and the dried product was pulverized with a jet mill to obtain polymethylsilsesquioxane-based fine particles (melting point). : None).

The average particle diameter of this polymethylsilsesquioxane type microparticles | fine-particles was 2.3 micrometers when it measured using the multisizer II (particle size distribution measuring apparatus, the Beckman Coulter company make, brand name).

Moreover, when the shape of the said polymethylsilsesquioxane microparticles | fine-particles was observed with the optical microscope, it was spherical.

Moreover, when the water repellency of the said polymethylsilsesquioxane type microparticles | fine-particles was evaluated by the said method, methanol concentration when it started to disperse | distribute whole quantity in methanol aqueous solution was 22%, and the water repellency in the case of not surface modification was low.

(Comparative Example 2)

3,662 g of ion-exchanged water and 86 g of ammonia water (concentration 28%) were put into a 5 L glass flask, and the water temperature was 20 degreeC. It stirred by the anchor type stirring blade on the conditions of blade | wing rotation speed of 150 rpm, 743 g of methyl trimethoxysilane was dripped over 3 hours, and the liquid temperature was hold | maintained at 15-25 degreeC in the meantime. After completion of the dropwise addition, the mixture was stirred at 15 to 25 ° C for 15 minutes, and then 9 g of trimethylsilanol (the amount of trimethylsilanol was 2.5 parts by weight based on 100 parts by weight of the polymethylsilsesquioxane fine particles) was added thereto. The mixture was kept at 25 DEG C and stirred for 1 hour, then heated to 55-60 DEG C, and then stirred for 1 hour. The obtained solution was degreased using a pressure filter to obtain a cake-like substance, the cake-like substance was dried at a temperature of 105 ° C. in a hot air circulation dryer, and the dried product was pulverized with a jet mill to obtain polymethylsilsesquioxane-based fine particles (melting point). : None).

The average particle diameter of this polymethylsilsesquioxane type microparticles | fine-particles was 2.2 micrometers when it measured using the multisizer II (particle size distribution measuring apparatus, the Beckman Coulter company make, brand name).

Moreover, when the shape of the said polymethylsilsesquioxane microparticles | fine-particles was observed with the optical microscope, it was spherical.

Moreover, when the water repellency of the said polymethylsilsesquioxane microparticles | fine-particles was evaluated by the said method, methanol concentration when it started to disperse | distribute whole quantity in methanol aqueous solution was 38%, and the water repellency in reaction of trimethylsilanolman was low.

(Comparative Example 3)

Into a 5 L glass flask, 3,663 g of ion-exchanged water and 86 g of ammonia water (concentration 28%) were placed, and the water temperature was 20 ° C. It stirred by the anchor type stirring blade on the conditions of blade | wing rotation speed of 150 rpm, 743 g of methyl trimethoxysilane was dripped over 3 hours, and the liquid temperature was hold | maintained at 15-25 degreeC in the meantime. After completion of the dropwise addition, the mixture was stirred at 15 to 25 ° C. for 15 minutes, and then 8 g of hexamethyldisilazane was added thereto, further maintained at 15 to 25 ° C., stirred for 1 hour, and then heated to 55 to 60 ° C., and continued. And stirred for 1 hour. The obtained solution was degreased using a pressure filter to obtain a cake-like substance, the cake-like substance was dried at a temperature of 105 ° C. in a hot air circulation dryer, and the dried product was pulverized with a jet mill to obtain polymethylsilsesquioxane-based fine particles (melting point). : None).

The average particle diameter of this polymethylsilsesquioxane type microparticles | fine-particles was 2.2 micrometers when it measured using the multisizer II (particle size distribution measuring apparatus, the Beckman Coulter company make, brand name).

Moreover, when the shape of the said polymethylsilsesquioxane microparticles | fine-particles was observed with the optical microscope, it was spherical.

Moreover, when the water repellency of the said polymethylsilsesquioxane type microparticles | fine-particles was evaluated by the said method, the methanol concentration when it started to disperse | distribute whole quantity in methanol aqueous solution was 34%, and the water repellency in reaction of hexamethyldisilazane only was low.

(Comparative Example 4)

200 g of polymethylsilsesquioxane-based fine particles obtained in Comparative Example 1 were placed in a 2 L planetary mixer, 4 g of water was added while stirring, and after being sealed, the mixture was further stirred at 60 ° C. for 10 hours. After cooling to room temperature, 4.4 g of hexamethyldisilazane was added under stirring, closed and stirred for a further 24 hours, after which the temperature was raised to 120 ° C. and the remaining hexamethyldisilazane was vented while venting nitrogen gas. Byproduct ammonia was removed. The obtained dried material was pulverized with a jet mill to obtain polymethylsilsesquioxane fine particles (melting point: none).

The average particle diameter of this polymethylsilsesquioxane type microparticles | fine-particles was 2.3 micrometers when it measured using the multisizer II (particle size distribution measuring apparatus, the Beckman Coulter company make, brand name).

Moreover, when the shape of the said polymethylsilsesquioxane microparticles | fine-particles was observed with the optical microscope, it was spherical.

In addition, when the water repellency of the polymethylsilsesquioxane-based fine particles was evaluated by the above method, the methanol concentration when starting to disperse completely in the aqueous methanol solution was 36%, and hexavalently hexahydrated to the isolated polymethylsilsesquioxane-based fine particles. The water repellency in the case of reacting methyldisilazane was low.

(evaluation)

The results of Examples and Comparative Examples are shown in Table 1. As can be seen from Table 1, it was confirmed that the polyorganosilsesquioxane-based microparticles of the example had excellent water repellency because the methanol concentration at the time of starting to disperse the total amount in the aqueous methanol solution was higher than that of the comparative example. Moreover, since the polyorgano silsesquioxane type microparticles | fine-particles of an Example have high water repellency, it contains many trimethylsilyl groups in the particle | grain surface, and is expected to be favorable also from the viewpoint of dispersibility to various materials, and affinity.

The water-repellent polyorganosilsesquioxane type microparticles | fine-particles of this invention have high water repellency, and are excellent also from a viewpoint of the dispersibility, affinity, etc. to various materials.

The effect of the present invention is that by reacting Si (OR ² ) ₄ (R ² is as described above) on the surface of the polyorganosilsesquioxane-based fine particles, silanol groups and And / or an alkoxysilyl group (≡Si-OR ² group) is formed, to which (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH (R ³ is as described above) react. It is guessed that it is obtained by increasing a trimethylsilyl group.

Claims (3)

R ¹ SiO _3/2 units at the surface of polyorganosilsesquioxane-based fine particles or greater (where, R ¹ is the same or different carbon atoms of 1 to 20 monovalent organic Im) is 70 mol%, Si (OR ² ) ₄ , wherein R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, the same or different, and (CH ₃ ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH, wherein R ³ is a hydrogen atom or an identical or different alkyl group having 1 to 6 carbon atoms), which is obtained by hydrolysis and condensation reaction, and has a melting point of 300 ° C. or higher or no melting point. Particulates. The polyorganosilsesquioxane microparticles | fine-particles of Claim ¹ whose R <^1> is a methyl group. The polyorganosilsesqui may be hydrolyzed and condensed by adding an alkoxysilane to an aqueous solution of an alkaline substance, or hydrolyzed by adding an alkoxysilane to a neutral or acidic aqueous solution, followed by condensation reaction by adding an alkaline substance or an aqueous solution thereof. After obtaining an aqueous dispersion of the oxane-based fine particles, Si (OR ² ) ₄ (wherein R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and (CH ₃ ) was added to the aqueous dispersion under stirring. ) ₃ SiOR ³ and / or [(CH ₃ ) ₃ Si] ₂ NH (wherein R ³ is a hydrogen atom or an alkyl group having the same or different carbon atoms of 1 to 6 carbon atoms) to undergo hydrolysis and condensation reaction. The manufacturing method of the polyorgano silsesquioxane microparticles | fine-particles of Claim 1 characterized by the above-mentioned.