JPH0633337B2 - Spherical polyorganosilsesquioxane fine particles and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyorganosilsesquioxane and a method for producing the same, and more particularly to a spherical polyorganosilsesquioxane having a functional organic group and a method for producing the same. .

<< Prior Art >> Polymethylsilsesquioxane fine powder having excellent free-flowing property and a method for producing the same are known, and lubricity, water repellency, and antifouling properties are known in the fields of rubber, plastics, paints, inks, cosmetics, and the like. Used for the purpose of improving the releasability, releasability, stress relaxation, etc. (for example, JP-A-61-159427).
No. 61-159461 and No. 61-159463.
No. 61-159467, No. 61-159754
No. 61-159474, No. 62-121093.
No. 62-128162, No. 62-202325.
No. 62, No. 62-215646, No. 62-232448.
No. 62-232476, No. 62-233248.
No. 62-238792 and 62-259304.
Nos. 63-8461, 63-10662, 6
3-15848, 63-15849, 63-1
7958, 63-283908, 63-399.
29, 63-58450).

Since these polymethylsilsesquioxane powders have a spherical shape, as a filler and an additive for synthetic resin,
For example, it is used as a slipperiness-imparting agent and a mold-releasing agent for synthetic resin films and papers. Especially, since the particle size distribution is extremely narrow, it is suitable for applications where the thin film thickness is strictly controlled in paints and the like. It is said that However, for the purpose of imparting these various properties, even if the above-mentioned fine powder of polymethylsilsesquioxane is blended with rubber, plastic, etc., the rubber and plastic as the base and polymethylsilsesquioxane are not mixed with each other. Because there is no affinity for
It has a drawback that the durability of the above-mentioned various properties imparted to the obtained rubber or plastic is not sufficient.

On the other hand, in place of the above-mentioned fine powder of polymethylsilsesquioxane, it is also practiced to use fine particle silica which is surface-treated and functionalized.

As the fine powder having such functionality, there is, for example, one in which a vinyl group is bonded to the surface of fine particle silica by a silazane treatment, and this fine powder has a smell and a decrease in catalytic activity due to the residual ammonia. There is a problem. In addition, fine particle silica is also known in which organotrialkoxysilane is added dropwise to fine particle silica in an organic solvent in the presence of water and an acid catalyst for surface modification (JP-A-62-7).
No. 2515). However, in this case, a large amount of the organic solvent is discharged when the surface is modified, and the time spent for the treatment is very long.

In any case, the characteristics of excellent lubricity, water repellency, releasability, improvement of stress relaxation and the like obtained by using polymethylsilsesquioxane fine particles cannot be obtained only by surface modification of fine particle silica.

Therefore, it has been desired to develop a method for improving the sustainability of various properties obtained when the above polymethylsilsesquioxane fine particles are used.

The present inventors have conducted extensive studies to solve the above-mentioned drawbacks, and introduced an amino group, an epoxy group and a vinyl group into the polymethylsilsesquioxane spherical particles, and a specific particle diameter and The inventors have found that the persistence of various properties obtained by using polymethylsilsesquioxane fine particles as a particle size distribution can be remarkably improved and reached the present invention.

<< Problems to be Solved by the Invention >> Therefore, the first object of the present invention is to provide excellent lubricity, water repellency,
An object of the present invention is to provide polyorganosilsesquioxane spherical fine particles having a narrow particle size distribution, which can maintain various properties such as releasability and improvement of stress relaxation for a long period of time.

A second object of the present invention is to provide a method for producing polyorganosilsesquioxane spherical fine particles having any of an amino group, an epoxy group and a vinyl group and having a narrow particle size distribution.

<< Means for Solving the Problems >> The above various objects of the present invention are represented by the general formula (CH ₃ SiO _3/2 ) _m (ASiO _3/2 ) _n ...
(I) (where A is a group selected from an amino group, an epoxy group and a vinyl group, or a monovalent organic group having at least one of these functional groups, and n / (m + n) is 0.001 to 0. .400
And m and n are positive integers. ) A spherical polyorganosilsesquioxane fine particle represented, wherein the fine particles have an average particle diameter of 0.5 to 4.0 μm and a particle diameter distribution within a range of ± 30% of the average particle diameter. The present invention has been achieved by a spherical polyorganosilsesquioxane fine particle and a method for producing the same, which is characterized in that a certain proportion is 80% by weight or more.

The polyorganosilsesquioxane spherical fine particles obtained in the present invention are at least selected from the group consisting of methyltrialkoxysilane represented by the general formula CH ₃ Si (OR) ₃ : (II) and a partial hydrolyzate thereof. One compound and the general formula ASi
(OR) ₃ : A mixture with at least one compound selected from the group consisting of organotrialkoxysilane represented by (III) and a partial hydrolyzate thereof is used as a raw material. However, R in the general formulas (II) and (III) is
It is an alkyl group having 1 to 4 carbon atoms.

A in the general formula (III) is a group selected from an amino group, an epoxy group and a vinyl group, or a monovalent hydrocarbon group having 3 to 10 carbon atoms and having a functional group thereof.

The above alkoxysilanes are easily obtained by alkoxylating the corresponding trichlorosilane with a suitable alcohol.

Examples of the methyltrialkoxysilane represented by the general formula (II) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and methyltributoxysilane.
Specific examples of the organotrialkoxysilane represented by I) include the following silicon compounds.

Vinyltrimethoxysilane, vinyltriethoxysilane.

The partial hydrolyzate of these alkoxysilanes can be easily obtained by allowing the presence of a smaller amount of water than the theoretical amount required to completely hydrolyze the corresponding alkoxysilane.

The polyorganosilsesquioxane fine particles represented by the general formula (I) of the present invention is at least one kind selected from the group consisting of methyltrialkoxysilane represented by the general formula (II) and a partial hydrolyzate thereof. At least one compound selected from the group consisting of a compound (hereinafter, abbreviated as methyltrialkoxysilane), an organotrialkoxysilane represented by the general formula (III), and a partial hydrolyzate thereof (hereinafter, organotrialkoxy). (Abbreviated as silane)
And the raw materials mixed according to the target molar ratio (hereinafter this mixture is abbreviated as “raw material alkoxysilane”),
It can be obtained by hydrolysis / condensation in an aqueous solution containing an alkaline or acidic substance, followed by neutralization and drying.

In the general formula (I), the mole fraction of A group n / (m + n)
Is 0.001 to 0.400, particularly 0.005 to
It is preferably 0.200.

When the mole fraction of the A group is 0.001 or less, the reactivity function due to the A group does not appear, and thus the durability such as excellent lubricity caused by using the polymethylsilsesquioxane fine particles is improved. If it is 0.400 or more, the characteristics such as lubricity, water repellency, and releasability due to the methyl group are impaired, which is not preferable.

The alkaline substance used in the reaction of the present invention is an alkali catalyst for the hydrolysis / condensation reaction, and includes alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide, calcium hydroxide and water. Alkaline earth metal hydroxides such as barium oxide, potassium carbonate, alkali metal carbonates such as sodium carbonate (including those having crystal water), ammonia or monomethylamine, dimethylamine, monoethylamine, diethylamine, ethylenediamine, etc. The amines of can be used.

Of these, alkali metal hydroxides and ammonia are advantageous in terms of solubility in water, catalytic activity, and efficient production of desired spherical fine particles. As ammonia, an aqueous ammonia solution (concentration 28
%) Can be used. When an aqueous solution containing an alkali metal hydroxide is used as the alkali catalyst, the catalyst concentration is preferably in the range of 0.01 to 0.20 mol / kg.

If the amount is less than 0.01 mol / kg, the particles are fused with each other to form a gel, and if the amount is more than 0.2 mol / kg, the alkalinity is too strong and the hydrolysis rate becomes too fast to form an amorphous gel body, which is not preferable.

The hydrolysis / condensation reaction is performed by dropping the alkoxysilane represented by the general formula (II) or (III) into an aqueous solution containing an alkali metal hydroxide while stirring.
The reaction temperature is not particularly limited, but is preferably about 0 to 80 ° C, particularly preferably 5 to 50 ° C. Freezing may occur at 0 ° C. or lower, and hydrolysis at a temperature higher than 80 ° C. is too fast, which tends to cause formation of an amorphous gel body, which is not preferable.

The stirring during the reaction is not particularly limited, but when stirring with a large shearing force such as with a homogenizer, an amorphous gel body is generated due to collision between particles, which is not preferable. Therefore, 10-1,000 with the stirring blade
Stirring at about rpm is preferable, especially 20 to 300 rpm
It is preferable that With gentle agitation below 10 rpm, the particles will fuse together and gel.
If it is 000 rpm or more, an amorphous gel body is generated due to collision between particles, which is not preferable.

Further, the target spherical polyorganosilsesquioxane fine particles cannot be obtained when the dropping rate of the raw material alkoxysilane is too fast or too slow.

In general, the total amount V ₁ + V ₂ of the amount V ₁ of the aqueous solution of the alkali metal hydroxide and the amount V ₂ of the dropped alkoxysilane is V ₁ + V ₂ =
V [kg] and the dropping rate of the alkoxysilane v [g / m
in] ratio v / V is 0.6 to 6.0 [g / kg · mi
[n], and it is particularly preferable to add dropwise so as to be in the range of 0.8 to 4.0.

If this v / V is greater than 6.0, the dropping speed is too fast, and the temperature of the reaction rises due to the heat of reaction of the hydrolysis / condensation reaction. Even if the temperature rise is controlled, an amorphous gel body is formed, which is preferable. If it is less than 0.6, the dropping rate is too slow and the growth rate of the polyorganosilsesquioxane spherical fine particles varies, so that particles having a wide particle size distribution are obtained, which is not preferable.

In actual production, it is preferable to complete the dropping in about 30 minutes to 6 hours, preferably in 1 hour to 4 hours.

Further, in order to complete the reaction, it is preferable to carry out post-stirring for about 1 hour or more after dropping.

There is no particular limitation on the amount ratio of the aqueous solution containing the alkali metal hydroxide and the alkoxysilane as the raw material to be dropped,
It suffices that the amount of water contained is at least twice the theoretical amount necessary to hydrolyze the alkoxy group of the alkoxysilane, but in the present invention, the average particle size is 0.5 to 4.0 μm and the particle size is In order to obtain polyorganosilsesquioxane fine particles having a distribution of 80% by weight or more with a distribution of ± 30% of the average particle diameter, 100 parts by weight of an aqueous solution containing an alkali metal hydroxide It is preferable that the amount of the alkoxysilane is 5 to 50 parts by weight, especially 10 to 40 parts by weight. When the amount is 5 parts by weight or less, the produced particles are too fine to obtain a desired particle size distribution. Meanwhile, 5
If the amount is 0 parts by weight or more, the hydrolysis reaction is prolonged by the by-produced alcohol, the reaction time becomes long, the growth rate of the fine particles varies, and the particles have a wide particle size distribution, which is not preferable. Will increase the frequency of collisions, and cause problems such as formation of irregular gel bodies.

When ammonia is used as the alkaline catalyst, the concentration of ammonia is preferably 0.02 to 10.0% by weight. If the content is less than 0.02% by weight, the particles are fused with each other to form a gel, and if the content is more than 10.0% by weight, an amorphous gel is formed, which is not preferable.

The hydrolysis / condensation reaction is carried out by dropping an alkoxysilane as a raw material into an aqueous solution of an ammonia solution or an aqueous solution of a mixture of water and an organic solvent while stirring, but as another method, the alkoxysilane and / or the alkoxysilane It is also possible to perform a hydrolysis / condensation reaction at the interface between the alkoxysilane and the organic solvent as the upper layer and the aqueous ammonia solution and / or the mixture of the ammonia and the organic solvent as the lower layer. "Interfacial reaction method"). Examples of the organic solvent in this case include alcohols such as methanol, ethanol, propyl alcohol and n-butanol; ketones such as dimethyl ketone, methyl ethyl ketone and acetone; aliphatic hydrocarbon solvents; aromatics such as toluene and xylene. Examples include group hydrocarbon solvents.
The amount of the organic solvent blended is not particularly limited, but is preferably 20 parts by weight or less based on 100 parts by weight of the total amount of water and the organic solvent.

The reaction temperature is not particularly limited, but is preferably about 0 to 80 ° C., particularly 5 to 50 ° C. for the same reason as in the case of the alkali metal hydroxide catalyst.

The stirring conditions in the reaction differ depending on whether the reaction is carried out by the dropping method or the interfacial reaction method. In the dropping method, for the same reason as in the case of the alkali metal hydroxide catalyst, 10 to 1,000 rpm, particularly 20 to 300 rpm.
In the interfacial reaction method, the stirring speed is preferably about 2 to 100 rpm, and particularly 5 to 50 rpm in order to obtain desired spherical particles, particularly particles having a narrow particle size distribution. It is preferable.

If the stirring speed is too high, the alkoxysilane, which is the raw material before the reaction, is entrained in the alkaline solution, and the hydrolysis / condensation reaction rapidly occurs in the alkaline solution, and the particles adhere to each other, which is not preferable. If the stirring speed is too low,
The particles generated by the interfacial reaction are difficult to disperse in the lower alkaline solution, and thus settle and aggregate to form an amorphous gel body.

Therefore, in the present invention, the reaction is performed until the layer of the alkoxysilane, which is the raw material of the upper layer, disappears under the above conditions,
Further stirring is continued. The stirring time varies depending on the production amount of the target spherical polyorganosilsesquioxane fine particles and the like, but is preferably about 1 to 10 hours.

Further, the dropping rate of the alkoxysilane as a raw material in the dropping method using ammonia as a catalyst is the same as in the case of the alkali metal hydroxide catalyst, and the amount V _{3 of the} aqueous ammonia solution or the mixed liquid of water and the organic solvent is the total amount of the amount _{V 4} of dripping material serving alkoxysilane _V 3 _{+ V} 4 =
V '[kg] and the dropping speed v' [g of the alkoxysilane
/ Min] ratio v '/ V' is 0.6 to 6.0 [g / kg · m
in], preferably 0.8 to 4.0 [g / kg · min].

In actual production, it is preferable to complete the dropping within 30 minutes to 6 hours, particularly 1 to 4 hours.

Regarding the amount ratio of the aqueous solution of ammonia or the mixed liquid of water and the organic solvent and the alkoxysilane as a raw material, the amount containing water at least twice the theoretical amount necessary to hydrolyze the alkoxy group of the alkoxysilane is For the same reason as in the case of the alkali metal hydroxide catalyst, in order to obtain the target spherical particles having a particularly narrow particle size distribution, 100% by weight of an aqueous ammonia solution or a mixed solution of water and an organic solvent is preferable. The amount of the alkoxysilane as a raw material is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on parts.

In the present invention, if necessary, the alkali catalyst remaining in the suspension produced by the above method is neutralized. When an alkali metal hydroxide catalyst is used, any neutralizing agent can be used as long as it is an acidic substance, but in order to facilitate washing after neutralization, hydrochloric acid, sulfuric acid, carbonic acid, acetic acid, Formic acid or the like may be used. On the other hand, when an ammonia catalyst is used, an organic acid such as acetic acid or formic acid can be used as a neutralizing agent, but the produced suspension is heated to 50 to 100 ° C without using the neutralizing agent. Ammonia can be easily removed by the treatment.

The neutral suspension thus obtained is dehydrated by a centrifugal separation method, a centrifugal filtration method or the like, and the obtained paste-like material is dried by heating at 100 to 250 ° C, or the suspension is directly sprayed. After drying with a dryer or the like, crushing with a jet mill crusher etc. gives at least 95
A spherical polyorganosilsesquioxane powder is obtained with a yield of at least%.

Thus polyorganosilsesquioxane obtained the general formula _{(CH 3 SiO 3/2) m (} ASiO 3/2) n ( where, n / (m + n) is at 0.001 to 0.400 , M and n are positive numbers), and their shapes are independent spherical or substantially vacuum. Further, the average particle size of the spherical polyorganosilsesquioxane fine particles is 0.5 to 4.0 μm, and the ratio of the particles having a particle size distribution within ± 30% of the average particle size is 80% by weight or more. More detailed conditions for this may be set by conducting an experiment appropriately.

The spherical polyorganosilsesquioxane fine particles obtained in the present invention are used as fillers and additives for various synthetic resins, for example, to impart slipperiness and releasability to synthetic resin films and papers, and as a reinforcing agent. Further, it can be used in place of conventional talc or mica powder as an extender pigment of a heat-resistant paint which uses an epoxy resin or urethane resin as a vehicle. In particular, since the particle size distribution can be made extremely narrow, it is suitable for applications such as paints where the thickness of the thin film is severely limited.

In addition, it improves the abrasiveness and workability of the polish while retaining the gloss by blending it with a stress relaxation agent for epoxy resin as a semiconductor encapsulation material, a tape slip improver for magnetic recording media, and a polish such as car wax. It can be used in place of conventional talc or mica powder as a filler for improving the slipperiness of a release agent for tires or a release agent for urethanes.

<< Effects of the Invention >> The spherical polyorganosilsesquioxane of the present invention has any one of an amino group, an epoxy group and a vinyl group as a functional group. When used as a reinforcing agent, the spherical fine powder of the polyorganosilsesquioxane and the epoxy group, amino group or vinyl group in the resin bind to each other, so that the mechanical properties of the resin such as strength are improved. In addition, the durability of various properties such as excellent lubricity, water repellency, and releasability is also improved.

The average particle size of the spherical polyorganosilsesquioxane fine particles of the present invention is 0.5 to 4.0 μm, and the ratio of the particles having a particle size distribution within ± 30% of the average particle size is 80% by weight. %, It is possible to improve the uniformity of the thickness of the thin film when it is used in a paint or the like.

<Examples> The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1. 39.9 kg of water and K in a 60-stainless steel container equipped with a propeller-type stirring blade, a dropping roll and a cooling jacket.
100 g of OH was added and cooled to 15 ° C. Rotation speed 200
Methyltrimethoxysilane 12, while stirring at rpm
920 g and 3-aminopropyltrimethoxysilane 89
5 g of the mixed solution was added dropwise with a dropping funnel over 2 hours (v / V = 2.1 g / kg · min), while the temperature was kept at 2
The stirring was kept constant at 0 ° C. and 200 rpm. After the dropwise addition was completed, stirring was continued for another hour, and then 107 g of acetic acid was added to neutralize. The resulting suspension was filtered, dehydrated and washed twice with a centrifuge to form a cake, and then dried at 150 ° C. using a drier until the water content became 2.0% or less.

Next, the produced powder was crushed with a jet mill to obtain 6,490 g of a white powder having excellent free flowing property.

When this white powder was observed with an electron microscope, it was approximately 2 μm.
The particles were spherical particles having a particle size of m. When the particle size distribution of the fine particles was measured with a Coulter counter (MODEL TA-II type), the average particle size was 1.7 μm,
87% or more of all particles were contained within the range of 1.2 to 2.2 μm.

When the amino group content (amino value) of the obtained powder was measured by the following method, the amino value was 0.029 mol / 10.
It was 0g.

Next, the obtained powder was refluxed in xylene at 130 ° C. for 2 hours, dried and then the amino value was measured.
No difference from before reflux was observed. From this fact, it was proved that all the measured amino groups were bound to the polyorganosilsesquioxane fine particles.

(Method for measuring amino value) About 1.0 g of a sample was precisely weighed in a clean beaker (capacity 100 ml), 50 ml of a 1: 1 mixture of isopropyl alcohol and toluene was added and sufficiently stirred and dispersed, and then an automatic titrator And the amino value is calculated from the amount of hydrochloric acid consumed by titration with N / 10 hydrochloric acid solution.

Examples 2 and 3 The same operations as in Example 1 were carried out except for the composition shown in Table 1 and the conditions at the time of hydrolytic condensation, to obtain a polyorganosilsesquioxane powder shown in Table 1.

Examples 4 and 5 The same operations as in Example 1 were carried out except for the compounding conditions shown in Table 2 and the conditions at the time of hydrolytic condensation, to obtain polyorganosilsesquioxane powders shown in Table 2.

When the epoxy group content (epoxy value) of the obtained powder was measured by the following method, the results shown in Table 2 were obtained.

Next, when the obtained powder was refluxed in xylene at 130 ° C. for 2 hours and dried, and the epoxy value was measured, no difference from the epoxy value before the reflux was observed. From this, it was demonstrated that all the measured epoxy groups were bonded to the polyorganosilsesquioxane fine particles.

(Method for measuring epoxy value) About 2 g of a sample is accurately weighed and placed in a 100 ml stoppered flask with 10 ml of hydrochloric acid-dioxane solution (1.5 ml of concentrated hydrochloric acid).
Was dissolved in 100 ml of a solution prepared by purification and mixed with 100 ml of dioxane immediately before use), and the resulting solution was allowed to stand for 10 minutes, and then about 20 to 30 ml of neutral ethyl alcohol was added. It was Excess hydrochloric acid,
Titrate with 0.1N caustic soda solution using phenolphthalein as an indicator, and calculate the epoxy group content by calculation.

Example 6. 28 in a 60-stainless steel container equipped with a propeller type stirring blade, a reflux condenser, a dropping funnel, steam and a cooling jacket.
% Ammonia water 4 kg and water 36 kg were added and cooled to 15 ° C. While stirring at 170 rpm, 1,535 g of methyltrimethoxysilane was added dropwise with a dropping funnel over 15 minutes, and then methyltrimethoxysilane 11,
385 g and γ-aminopropyltrimethoxysilane 89
5 g of the mixed solution was dropped by a dropping funnel over 2 hours (v / V = 2.0 g / kg · min), and the temperature was raised to 2
The stirring speed was maintained constant at 0 ° C. and 170 rpm. After the completion of dropping, the mixture was heated with steam to reflux at 80 ° C., and stirring was continued at this temperature for 1 hour. After cooling, the resulting suspension was filtered, dehydrated and washed twice with a centrifuge to form a cake, and then dried at 150 ° C. using a dryer until the water content was 2.0% or less. . The resulting powder is crushed with a jet mill to produce a white powder with excellent free flow 6,62
0 g was obtained. The obtained polyorganosilsesquioxane was fine spherical particles having an average particle size of 1.9 μm, and 84% or more of all particles were contained within the range of ± 30% of the average particle size. When the amino value of the obtained powder was measured in the same manner as in Example 1, it was 0.032 mol / 100 g. Further, when the amino value was measured after refluxing and drying in xylene, the amino value was not different from that before rifura.

Example 7. In a stainless steel container of 60 equipped with a propeller type stirring blade, a dropping funnel and a cooling jacket, 39.9 kg of water and KO
100 g of H was added and the mixture was cooled to 15 ° C. Rotation speed 200r
Methyltrimethoxysilane 9,52 with stirring at pm
A mixed solution of 0 g and 740 g of vinyltrimethoxysilane was added dropwise with a dropping funnel over 2 hours (v / V = 1.7).
g / kg · min), during which temperature is 20 ° C. and stirring is 200
It was kept constant as rpm. After the dropwise addition was completed, stirring was continued for another hour, and 100 g of acetic acid was added to neutralize. The resulting suspension was filtered and dehydrated and washed with a centrifuge twice to form a cake. This was dried at 150 ° C. using a dryer until the water content became 2.0% or less.

Next, the generated powder was crushed with a jet mill to obtain 4,932 g of a white powder having excellent free flowing property.

When the white powder was observed with an electron microscope, it was found to be fine spherical particles having a particle diameter of about 2 μm. When the particle size distribution of the fine particles was measured with a Coulter counter (MODEL TA-II type), the average particle size was 1.7 μm,
93% or more of all particles were contained within the range of 1.2 to 2.2 μm.

The vinyl group content (vinyl value) of the obtained powder was measured by the Wijs method described below, and the vinyl value was 0.09 m.
It was ol / 100g. Next, the obtained powder was refluxed in xylene at 130 ° C. for 2 hours, dried, and the vinyl value was measured in the same manner. The vinyl value was not different from that before the reflux. From this, it was verified that all the measured vinyl groups were those of polymethylvinylsilsesquioxane fine particles.

<Measuring method by Wijs method> About 0.5 g of a sample was suspended in 15 ml of acetic acid, and 25 m of Wijs solution (0.2 N iodine bromide-acetic acid solution) was suspended in the suspension.
1 is added and the mixture is placed in a constant temperature dark place at 25 ° C. for 2 hours to react vinyl group with iodine bromide.

Then, 15 ml of a 20 wt% potassium iodide aqueous solution and 100 ml of water are added, and the liberated iodine is titrated with a 0.1 N sodium thiosulfate aqueous solution to the starch end point, and the vinyl group is calculated from the amount of iodine consumed.

Examples 8 to 11 The same operations as in Example 7 were carried out except for the compounding conditions shown in Table 3 and the conditions at the time of hydrolytic condensation, to obtain polymethylvinylsilsesquioxane powders shown in Table 3.

Example 12. 28 in a 60-stainless steel container equipped with a propeller type stirring blade, a reflux condenser, a dropping funnel, steam and a cooling jacket.
% Ammonia water 4 kg and water 36 kg were added and cooled to 15 ° C. While stirring at a rotation speed of 170 rpm, 9860 g of methyltrimethoxysilane and 3 vinyltrimethoxysilane
70 g of the mixed solution was added dropwise with a dropping funnel over 2 hours (v / V = 1.7 g / kg · min), and the temperature during that period was adjusted to 2
The stirring speed was maintained constant at 0 ° C. and 170 rpm. After the completion of dropping, the mixture was heated with steam to reflux at 80 ° C., and stirring was continued at this temperature for 1 hour. After cooling, the resulting suspension was filtered and dehydrated and washed with a centrifugal separator twice to form a cake. This was dried at 150 ° C. using a dryer until the water content became 2.0% or less. The resulting powder is crushed with a jet mill to give a free-flowing white powder 494.
2 g was obtained. This is a true spherical particle having an average particle size of 1.9 μm, and 90% or more of all particles were included within the range of ± 30% of the average particle size. About the obtained powder Wi
The vinyl value measured by the js method is 0.05 mol
It was / 100 g.

Further, it was refluxed in xylene and dried to measure the vinyl value, but there was no difference from that before the reflux.

Example 13. 2 in the same stainless steel container used in Example 12
8% aqueous ammonia solution 1.25 kg and water 48.75 kg
And cooled to 15 ° C. To this aqueous ammonia solution, a mixture of 6,690 g of methyltrimethoxysilane and 810 g of vinyltrimethoxysilane was quickly added to the aqueous ammonia solution while rotating the stirrer at 5 rpm so that the upper layer was an alkoxysilane layer and the lower layer was an aqueous ammonia solution. It was made to be a two-layered state. Then, the stirring speed was set to 20 rpm to allow the reaction to proceed at the interface between the alkoxysilane and the aqueous ammonia solution. When the reaction was continued for a time, the upper alkoxysilane layer completely disappeared. Meanwhile, the temperature was kept constant at 20 ° C. and the stirring speed was 20 rpm. After completion of the reaction, heating and reflux were performed in the same manner as in Example 12, and 3,770 g of white powder was obtained from the resulting suspension by the same method as in Example 12.

The polymethylvinylsilsesquioxane powder thus obtained is fine spherical particles having an average particle size of 1.8 μm,
92% or more of all particles were contained within the range of ± 30% of the average particle diameter. The vinyl value of the obtained powder was measured and found to be 0.15 mol / 100 g.

Comparative Example 1. Methyltrimethoxysilane as an alkoxysilane 6,
Instead of using a mixture of 690 g and vinyltrimethoxysilane 810 g, methyltrimethoxysilane 7,480
White polymethylsilsesquioxane powder (3,420 g) was obtained in the same manner as in Example 13 except that g was used. The polymethylsilsesquioxane powder thus obtained is fine spherical particles having an average particle size of 1.8 μm, and 89% or more of all particles are contained within ± 30% of the average particle size. Was there. The vinyl value of the obtained powder is 0 mol / 1.
It was 00 g.

Example 14. Blocked with dimethylvinylsiloxy groups at both ends, 25 ° C
And 100 parts of polymethylvinylsiloxane having a viscosity of 500 cs, and having both ends blocked with trimethylsiloxy groups, and consisting of methylhydrogensiloxy units.
5 parts of polymethyl hydrogen siloxane having a viscosity of 20 cs at 25 ° C. was placed in a container and sufficiently mixed with stirring. Next, the polymethylvinylsilsesquioxane powder obtained in Example 13 was added to the obtained mixture as shown in Table 4 and mixed to obtain a uniform silicone composition 1
Got 3.

For comparison, instead of the polymethylvinylsilsesquioxane powder, the polymethylsilsesquioxane powder obtained in Comparative Example 1 above, or Aerosil A-200 (fine powder silica, manufactured by Nippon Aerosil Co., Ltd., trade name) ) Was used in the same manner as above to obtain silicone compositions 4 and 5, and silicone composition 6 was obtained in the same manner as above except that polymethylvinylsilsesquioxane was not used.

To each of the silicone compositions 1 to 6, 2 parts of a complex of chloroplatinic acid and vinyl siloxane (platinum concentration 0.5%) was added and uniformly mixed, and the obtained silicone composition was made to a thickness of 50.
It was applied to a polyethylene terephthalate film of μm and polyethylene laminated paper by an offset printing machine so as to be 1 g / m ² and heated at 140 ° C. for 30 seconds to be cured, and then the slipperiness, releasability and releasability were relieved. Each item was evaluated. Each evaluation method is as follows.

<Sliding property> The coefficient of static friction between the treated film and the untreated film was measured using a static friction coefficient measuring device (manufactured by Shinto Kagaku Co., Ltd.) to evaluate the sliding property.

<Releasability> Acrylic solvent type adhesive (BPS-
After applying 5127 (manufactured by Toyo Ink Mfg. Co., Ltd.) to 130 μm (wet) and drying at 100 ° C. for 3 minutes, 64 g /
m2 ^high- quality paper was pasted, pressure-bonded back and forth once with a pressure roller of 2 kg, and after aging at room temperature for 1 day, the peeling force (g / 5 cm ² ) was measured by an autograph to evaluate the releasability.

<Releasing durability> A Lucile 31B tape (trade name, manufactured by Nitto Denko Corp.) is attached to the silicone-treated surface of the polyethylene terephthalate film, and it is peeled off by hand after being crimped back and forth with a 2 Kg pressure roller for one reciprocation. This operation was repeated until it stopped running, and evaluation was performed based on the following criteria.

The results of each evaluation are as shown in Table 4.

The results in Table 4 demonstrate that the composition of the present invention not only has excellent slipperiness, but also has excellent durability, in particular in releasability, as compared with the conventional one.

Example 15. Epicoat 828 (trade name of bisphenol A type epoxy resin, manufactured by Shell Chemical Co., Ltd .; epoxy equivalent of 190 to 2)
10, 10 parts of molecular weight 330) and 10 parts of triethylenetetramine and 10 parts of the amino group-containing polyorganosilsesquioxane powder obtained in Example 1 were mixed, and the mixture was mixed at room temperature for 10
Epoxy resin composition A was obtained by mixing and stirring for a minute. Similarly, 10 parts of the epoxy group-containing polyorganosilsesquioxane powder obtained in Example 4 was blended in place of the amino group-containing polyorganosilsesquioxane powder, and the epoxy resin composition B was prepared in the same manner as above. Got

As a comparative composition, instead of the amino group-containing polyorganosilsesquioxane powder, the polymethylsilsesquioxane powder obtained in Comparative Example 1 or Aerosil A200, 1
Epoxy resin composition C in the same manner as above with 0 parts blended
And D were obtained.

The resin composition thus obtained was poured into a molding die and cured by heating at 150 ° C. for 3 hours.

The fracture surface of the obtained molded product was observed with an electron microscope to evaluate the adhesion and compatibility between the epoxy resin and the fine powder particles, and the results shown in Table 5 were obtained.

The results in Table 5 demonstrate that the fine powder fine particles of the present invention have a good compatibility with the epoxy resin and have a very good adhesion, and thus various results obtained by using the fine particles of the present invention. It is understood that the persistence of properties is significantly improved.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masanori Sudo 2-13-1 Isobe, Annaka City, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) Reference JP-A-63-295637 ( JP, A) JP 60-13813 (JP, A) JP 54-72300 (JP, A) JP 63-77940 (JP, A) JP 58-59222 (JP, A) JP Flat 1-217039 (JP, A) JP-A-2-178330 (JP, A)

Claims (2)

[Claims] 1. A compound represented by the general formula (CH ₃ SiO _3/2 ) _m (ASiO _3/2 ) _n (I) (wherein A is a group selected from an amino group, an epoxy group and a vinyl group, or Monovalent hydrocarbon group having 3 to 10 carbon atoms having at least one functional group, n / (m
+ N) is 0.001 to 0.400, and m and n are positive integers. ) Are spherical polyorganosilsesquioxane fine particles, wherein the fine particles have an average particle size of 0.5 to 4.0 μm and a particle size distribution within a range of ± 30% of the average particle size. 80% by weight
Spherical polyorganosilsesquioxane fine particles, which are the above fine particles. 2. At least one selected from the group consisting of methyltrialkoxysilanes represented by the general formula CH ₃ Si (OR) ₃ (II) and partially hydrolyzed products thereof, and the general formula ASi (O).
R) ₃ ... An aqueous solution containing an alkaline substance in an amount of 5 to 50 parts by weight of a raw material composed of a mixture of the organotrialkoxysilane represented by (III) and at least one selected from the group consisting of partial hydrolysis products thereof. In 100 parts by weight,
The method for producing spherical polyorganosilsesquioxane fine particles according to claim 1, wherein hydrolysis and condensation are performed under stirring, followed by neutralization and drying (wherein A in the general formula (II) is amino). A group selected from a group, an epoxy group and a vinyl group, or a monovalent hydrocarbon group having at least one functional group and having 3 to 10 carbon atoms, which is represented by the general formulas (II) and (III R in) is an alkyl group having 1 to 4 carbon atoms).