JP3045471B2 - Reactive organic-inorganic composite particles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to reactive organic-inorganic composite particles.

[0002]

2. Description of the Related Art Conventionally, organic-inorganic composite particles containing an organic polymer skeleton and a polysiloxane skeleton have been known and used as fillers for paints, plastic molding materials, rubbers, films and the like. For example, JP
-279244, JP-A-4-236266, and the organic-inorganic composite particles described in JP-A-4-258636, after absorbing an alkoxysilane compound to particles of a copolymer latex of an organic monomer, The alkoxysilane compound is obtained by a condensation reaction.
These composite particles have low hardness due to low SiO ₂ content in the particles, have no radical polymerizable groups in the particles, and have a Si-C bond between the polysiloxane skeleton and the organic polymer skeleton. is not.

The organic-inorganic composite particles described in JP-A-3-33165 and JP-A-3-247669 are prepared by treating the surface of an organic polymer particle with a silane coupling agent such as vinyltriethoxysilane. It has a two-layer structure in which a polysiloxane coating is formed on the particle surface.
Although these composite particles have a radical polymerizable group on the particle surface, the amount thereof is small, so there is almost no radical polymerizability, and since the amount of SiO _{2 in} the particles is small, the hardness is low. The bond with the polymer skeleton is not a Si-C bond.

On the other hand, the organic-inorganic composite particles described in JP-A-3-285944, JP-A-4-33933, JP-A-4-39336 and JP-A-5-287213 are made of silica or the like. It has a two-layer structure in which the organic polymer is physically adsorbed on the surface of the inorganic oxide fine particles by static electricity. Also, JP-A-2-115285,
JP-A-4-180921, JP-A-5-26936
The organic-inorganic composite particles described in JP-A No. 5 (1993) -175, the organic polymer of Si-
It has a two-layer structure joined by C bonds. These composite particles have a very high SiO ₂ content in the particles (because the core particle is an inorganic oxide) and are inferior in mechanical resilience, and have a radical polymerizable group in the particles. not exist.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide organic-inorganic composite particles having high hardness and excellent mechanical resilience and high radical polymerizability.

[0006]

According to a first aspect of the present invention, there is provided a reactive polymer containing an organic polymer skeleton and a polysiloxane skeleton and containing a radically polymerizable group in an amount of 0.05 mmol / g or more. Provided are organic-inorganic composite particles. The polysiloxane skeleton comprises at least one of the organic polymer skeletons.
Organic silicon in which silicon atoms are directly chemically bonded to carbon atoms in the molecule. The ratio of the polysiloxane skeleton is 25 to 85 in terms of SiO _{2 based on} the weight of the composite particles.
wt%.

According to the second aspect, the reactive organic-inorganic composite particles of the present invention have a radical polymerizable group of 0.1 to 0.1.
It has the same configuration as that of the first embodiment except that it is contained in an amount of 20 mmol / g and the average particle diameter is in the range of 25 μm or less. According to the third embodiment, the reactive organic-inorganic composite particles of the present invention have the same configuration as that of the first embodiment or the second embodiment except that the radical polymerizable group has a CＣC bond. .

[0008]

The reactive organic-inorganic composite particles of the present invention comprise an organic polymer skeleton and at least one of the organic polymer skeleton.
And a polysiloxane skeleton having in its molecule an organosilicon in which a silicon atom is directly chemically bonded to carbon atoms, and the ratio of the polysiloxane skeleton is 25 to 85 w in terms of SiO _2.
When the content is within the range of t%, the composition has both high hardness, which is a characteristic of the polysiloxane skeleton, and high mechanical restorability, which is a characteristic of the organic polymer skeleton. Moreover, the composite particles have high radical polymerizability by containing the radical polymerizable group in an amount of 0.05 mmol / g or more.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The reactive organic-inorganic composite particles of the present invention contain an organic polymer skeleton and a polysiloxane skeleton, contain a radical polymerizable group in an amount of 0.05 mmol / g or more, and have a particle diameter of not less than 0.05 mmol / g . The coefficient of variation is 30% or less. The polysiloxane skeleton has in its molecule an organosilicon in which a silicon atom is chemically bonded directly to at least one carbon atom in the organic polymer skeleton. The ratio of the polysiloxane skeleton is 25 to 85 w in terms of SiO _{2 based on} the weight of the composite particles.
t%.

[0010] The organic polymer skeleton contains at least the main chain of the main chain, side chain, branched chain and crosslinked chain derived from the organic polymer. The molecular weight, composition, structure, presence or absence of a functional group, and the like of the organic polymer are not particularly limited. The organic polymer is, for example, at least one selected from the group consisting of (meth) acrylic resin, polystyrene, polyvinyl chloride, polyvinyl acetate, polyolefin, and polyester. Preferred organic polymer backbones have repeating units -C because they form particles with particularly good mechanical resilience.
-Having a main chain composed of -C-
"Vinyl-based polymer").

The vinyl-based polymer is, for example, (meth)
It is at least one selected from the group consisting of acrylic resin, polystyrene, polyvinyl chloride, polyvinyl acetate, and polyolefin. Preferred vinyl polymers are (meth) acrylic resin and (meth) acryl-
It is at least one selected from the group consisting of styrene resins. A more preferred vinyl polymer is a (meth) acrylic resin.

The polysiloxane has the following formula 1:

[0013]

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A siloxane unit represented by the following formula is defined as a compound which forms a three-dimensional network by continuous chemical bonding. The silicon atom in the polysiloxane is directly chemically bonded to at least one of the carbon atoms constituting the organic polymer skeleton. The proportion of the polysiloxane skeleton is Si
In terms of O _2, the weight of the composite particles of the present invention is ₂ %.
5 to 85% by weight. Within the above range, effective,
The resulting particles have hardness and mechanical resilience. 25wt%
If it is lower than the above, hardness which is a characteristic of the inorganic material is not exhibited. 85
If the content is more than wt%, the mechanical resilience of the organic polymer skeleton is impaired or the particles are broken. More effective,
In order to have hardness and mechanical resilience, the proportion of the polysiloxane skeleton is preferably 30 to 80 wt%, more preferably 33 to 70 wt%.

The proportion of the polysiloxane skeleton was determined by measuring the weight before and after firing the composite particles at a temperature of 1000 ° C. or more in an oxidizing atmosphere such as air.
_{2 is} the weight percentage. The composite particles of the present invention can contain an inorganic component other than polysiloxane. The inorganic component other than the polysiloxane is, for example, an oxide such as boron, aluminum, titanium, and zirconium. The amount of inorganic components other than polysiloxane is 0 to 20 wt%.
Is preferable, and 0 to 10 wt% is more preferable. If the ratio is outside the above range, the hardness or the mechanical restoring property may not be effectively exhibited.

The composite particles of the present invention contain both a polysiloxane skeleton (inorganic structural unit represented by the above formula 1) and an organic polymer skeleton. Moreover, the inorganic structural units and the organic polymer backbone is chemically bonded, the proportion of the polysiloxane backbone is in the range of 25～85Wt% in terms of SiO ₂ amount. Therefore, the composite particles of the present invention have both high hardness, which is a characteristic of an inorganic material, and high mechanical resilience, which is a characteristic of an organic polymer.

The composite particles of the present invention have a content of 1 g per particle.
It contains at least 0.05 mmol of a radical polymerizable group.
When the amount is less than 0.05 mmol / g, the radical polymerizability of the particles decreases. From the viewpoint that the reactivity of the radical polymerizable group of the composite particles is increased and the reaction is easily controlled, the composite particles of the present invention have a radical polymerizable group of 0.1 to
It is preferable to contain 20 mmol / g. From the viewpoint that the reactivity of the radical polymerizable group of the composite particle is made higher and the reaction is more easily controlled, the composite particle of the present invention contains the radical polymerizable group at 0.2 to 15 mmol / mol. g, more preferably 0.4 to 12 mmol / g. The amount of the radical polymerizable group can be determined by a method described in Examples described later.

The radically polymerizable group referred to in the present invention means a radically polymerizable double bond group. This double bond has a C = C bond. The presence or absence of C = C bond is determined by FT-
Confirmed by IR analysis. The preferred radically polymerizable group is at least one selected from the group consisting of a vinyl group, an acryl group and a methacryl group. The average particle size of the composite particles of the present invention is not particularly limited, but the composite particles of the present invention have an average particle size of, for example, 25 μm or less. If it exceeds the above range, the area becomes so large that it is hard to use for the above-mentioned purpose. From the viewpoint that aggregation is more unlikely to occur and that it has a size suitable for use in various applications, the composite particles of the present invention have a particle size of 0.01 to 25 μm.
Having an average particle size of 0.1 to 15 μm.
More preferably, it has an average particle diameter of m. If the ratio is less than the above range, the composite particles tend to agglomerate, and it is often difficult to use them for various applications.

The composite particles of the present invention have a particle size variation coefficient of 30 % or less, preferably 20% or less, more preferably 15% or less. If the upper limit is exceeded, when used as a spacer for a liquid crystal display panel, the uniformity of the gap of the liquid crystal is reduced and image unevenness is likely to occur. The coefficient of variation of the particle size is given by:

[0020]

(Equation 1)

Defined by In the present invention, the average particle diameter and the standard deviation between the particle diameters are calculated for any particle 2 in an electron micrograph.
The particle diameter of 00 particles is actually measured, and is obtained from the following equation.

[0022]

(Equation 2)

The scale indicating hardness is 10% compression modulus, and the scale indicating mechanical resilience is residual displacement after 10% deformation. Here, the 10% compression modulus is a value measured by the following measurement method. Using a Shimadzu micro compression tester (MCTM-200 manufactured by Shimadzu Corporation) at room temperature (25
(° C.), a load is applied to one sample particle sprayed on a sample stage (material: SKS flat plate) at a constant load speed in the direction of the center of the particle using a 50 μm diameter circular flat indenter (material: diamond). , Compression displacement is 10% of particle diameter
The particles are deformed until the following is satisfied, and the load at the time of 10% deformation and the number of millimeters of the compressive displacement are obtained. The required compression load,
The compression displacement of the particle and the radius of the particle are calculated by

[0024]

(Equation 3)

[Where E: compression modulus (kg / mm ² ) F: compression load (kg) K: Poisson's ratio of particles (constant, 0.38) S: compression displacement (mm) R: radius of particles (Mm). ] Is 10% compression elastic modulus. After that, immediately remove the load at the same speed as when the load was applied, unload until the load became 0.1 g, extrapolated the load-displacement curve along the tangent line so that the load finally becomes 0 g, The magnitude of the deformation still remaining on the particles is determined. The residual displacement is calculated as a percentage of the particle diameter. This operation is performed for three different particles, and the average value is defined as the 10% compression modulus and the residual displacement of the particles, which are used as a measure of the hardness and the mechanical resilience of the particles, respectively.

The composite particles of the present invention, 10% compressive elasticity modulus, preferably in the range of 350~3000kg / mm ^2, more preferably in the range of 400~2500kg / mm ^2, even more preferably 500~2000kg / mm The hardness can be adjusted to any value in the range of ² . If the 10% compression modulus is less than the above range, when used as a spacer for a liquid crystal display panel, there is a risk of an increase in production cost due to an increase in the number of particles scattered, a decrease in contrast, and an increase in roughness.
When used as an additive, carrier contamination may occur and the transfer efficiency or fluidity of the toner may be reduced. On the other hand, if the 10% compression modulus exceeds the above range, when used as a spacer for a liquid crystal display panel, the adhesive layer or the coating layer on the electrode substrate may be physically damaged or foamed at a low temperature. When used as an agent, the photoreceptor may be damaged.

Regarding the residual displacement after 10% deformation, the composite particles of the present invention preferably have a residual displacement in the range of 0 to 15%, more preferably 0 to 10%, and still more preferably 0 to 7%. It is a composite particle having excellent mechanical restorability having the following. If the residual displacement after 10% deformation exceeds the above range, image unevenness is likely to occur when used as a spacer for a liquid crystal display panel.

The 10% compression modulus and the degree of residual displacement in the above range can be achieved by adjusting the amount of the polysiloxane skeleton or the organic polymer skeleton in the particles. For example, when the amount of the polysiloxane skeleton is reduced, the 10% compression modulus and the residual displacement are reduced, and when the amount of the polysiloxane skeleton is increased, the 10% compression modulus and the residual displacement are increased.

Preferred embodiments of the composite particles of the present invention are as follows. (1) The amount of the polysiloxane skeleton is 25 to 85 wt%, the amount of the radical polymerizable group is 0.1 to 20.0 mmol / g, and the average particle diameter is 25 μm or less. (2) The amount of the polysiloxane skeleton is 25 to 85 wt%, the amount of the radical polymerizable group is 0.2 to 15.0 mmol / g, and the average particle diameter is 0.1 to 15 μm.

(3) Amount of polysiloxane skeleton 30 to 80 w
t%, the amount of the radical polymerizable group is 0.4 to 12.0 mmol / g,
In addition, the average particle size is 0.1 to 15 μm. (4) The amount of the polysiloxane skeleton is 30 to 70 wt%, the amount of the radical polymerizable group is 0.4 to 12.0 mmol / g, and the average particle diameter is 0.1 to 10 μm. The shape of the composite particles of the present invention may be any particle shape such as a spherical shape, a needle shape, a plate shape, a flake shape, a crushed shape, a bale shape, a cocoon shape, a confetti-like shape, and is not particularly limited, but is used for a liquid crystal display panel. When used as a spacer, a spherical shape is preferable in order to make the gap of the liquid crystal uniform, and when used as a toner additive, in order to improve the fluidity of the toner.

The composite particles of the present invention can be produced, for example, by the production method described below, but may be produced by another production method. The method for producing the reactive organic-inorganic composite particles of the present invention includes a condensation step and a polymerization step. The production method can also include a recondensation step after the polymerization step.

In the condensation step, the silicon compound is hydrolyzed and
This is a step of condensation. The silicon compound is at least one selected from the group consisting of compounds represented by at least one general formula selected from the group consisting of the following general formulas 2, 3 and 4, and derivatives thereof.

[0033]

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(Wherein, R ¹ represents a hydrogen atom or a methyl group; R ² has 1 to 5 carbon atoms which may have a substituent)
10 represents an alkylene group; R ³ represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms)

[0035]

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(Where R ⁴ represents a hydrogen atom or a methyl group; R ⁵ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms) Represents at least one monovalent group)

[0037]

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(Wherein, R ⁶ represents a hydrogen atom or a methyl group; R ⁷ has 1 to 5 carbon atoms which may have a substituent)
R represents 10 alkylene groups or phenylene groups;
⁸ represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. The functional group is CH ₂ ＣC (—R ¹ ) —COOR ² —,
^{_{CH 2 = C (-R 4)}} -, or, CH ₂ = C (-
R ⁶⁾ -R ⁷ - it is. By subjecting the radical polymerizable group to a radical polymerization reaction, an organic polymer skeleton derived from the vinyl polymer described above is generated. The radical polymerizable group is an acryloxyalkyl group (R ^{1 in the} general formula 2).
Is a hydrogen atom), a methacryloxyalkyl group (when R ¹ is a methyl group in the general formula 2), a vinyl group (when R ⁴ is a hydrogen atom in the general formula 3),
An isopropenyl group (when R ⁴ is a methyl group in the general formula 3), a 1-alkenyl group (a R ^{6 in the} general formula 4)
Is a hydrogen atom) or an isoalkenyl group (when R ⁶ is a methyl group in the general formula 4).

In the general formulas 2 to 4, the hydrolyzable group is R
³ O, R ⁵ O, and R ⁸ O. R ³ O group, R ⁵ O
Group, and R ⁸ O group is a monovalent group selected from the group consisting of a hydroxyl group and an alkoxy group and 2 to 5 acyloxy group having a carbon number of 1 to 5 carbon atoms. In the general formulas 2 to 4, the three R ³ O groups, the three R ⁵ O groups, and the R ⁸ O groups may be different from each other, or two or more may be the same. Preferred R ³ O, R ⁵ O, and R ⁸ O groups are selected from the group consisting of methoxy, ethoxy, propoxy, and acetoxy in view of high hydrolysis / condensation rate. And ethoxy groups are more preferred. The silicon compound is an R ³ O group / R ⁵ O
The group and R ⁸ O group are hydrolyzed by water and further condensed to form a polysiloxane skeleton represented by the above general formula 1.

In the general formulas 2 to 4, R ² and R ⁷
The group is an alkylene group having 1 to 10 carbon atoms which may have a substituent. The alkylene group is not particularly restricted but includes, for example, ethylene, propylene, butylene, hexylene and octylene. From the viewpoint of being easily available, those having a radical polymerizable group in which R ² and R ⁷ are propylene groups are preferred.

The compound represented by at least one general formula selected from the group consisting of general formulas 2, 3 and 4 has one silicon atom, three hydrolyzable groups bonded to the silicon atom, It has one radically polymerizable group bonded to a silicon atom. A specific example of the compound represented by the general formula 2 is γ-
Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltriacetoxysilane, etc. Any one may be used alone or two or more may be used in combination.

Specific examples of the compound represented by the general formula 3 include vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyltriacetoxysilane and the like, and any one of them is used alone or two or more are used in combination. A specific example of the compound represented by the general formula 4 is 1-
Hexenyltrimethoxysilane, 1-octenyltrimethoxysilane, and the like. Any one of these is used alone, or two or more are used in combination.

Derivatives of the compounds represented by the general formulas 2 to 4 include, for example, a compound represented by the general formulas 2 to 4 in which some R ³ O groups are β-dicarbonyl groups and / or other chelates. From the group consisting of a compound substituted with a group capable of forming a compound and a low condensate obtained by partially hydrolyzing and condensing a compound represented by formulas 2 to 4 and / or a chelate compound thereof. At least one selected.

As the silicon compound, a compound represented by the general formula 2 is preferable from the viewpoint that reactive organic-inorganic composite particles having a sharp particle size distribution are easily formed, and γ-methacryloxypropyltrimethoxysilane,
γ-methacryloxypropyltriethoxysilane, γ-
At least one selected from the group consisting of acryloxypropyltrimethoxysilane and γ-acryloxypropyltriethoxysilane is particularly preferred.

In order to obtain the reactive organic-inorganic composite particles of the present invention, in addition to the silicon compound described above, a silane compound represented by the following general formula 5; a derivative thereof; boron, aluminum, gallium, indium, phosphorus, titanium And at least one hydrolyzable / condensable metal compound selected from the group consisting of organometallic compounds such as zirconium and inorganic metal compounds.

[0046]

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(Where R ⁹ is the same as R ³ ; R ¹⁰
Is an alkyl group or a phenyl group which may have a substituent; and p is 0 or 1.) The R ⁹ group of the silane compound represented by the general formula 5 has a high hydrolysis-condensation rate. Is preferably a methyl group or an ethyl group. p is 0 or 1, but p = 0 is preferable since the hardness of the obtained reactive organic-inorganic composite particles can be increased.

In the derivative of the silane compound represented by the general formula 5, some R ⁹ O groups of the compound represented by the general formula 5 can form a β-dicarbonyl group and / or another chelate compound. At least one selected from the group consisting of a compound substituted with a group and a low-condensate obtained by partially hydrolyzing and condensing a compound represented by the general formula 5 and / or a chelate compound thereof. .

The amount of the metal compound which can be hydrolyzed and condensed other than the silicon compound is not particularly limited, but the amount of the radical polymerizable group in the reactive organic-inorganic composite particles obtained when used in a large amount is 0.05 mmol / g. , The shape of the particles may not be spherical, the control of the particle size may be difficult, or the particle size distribution may be widened. For this reason, the amount of the metal compound that can be hydrolyzed and condensed is 200 w
The content is preferably at most t%, more preferably at most 100 wt%, even more preferably at most 50 wt%.

The silicon compound and a metal compound that can be hydrolyzed and condensed as required (hereinafter, sometimes referred to as “raw material”) are hydrolyzed in a solvent containing water to condense. . The hydrolysis and condensation can be performed by any method such as batch, division, and continuous. For hydrolysis and condensation, ammonia, urea, ethanolamine,
A catalyst such as tetramethylammonium hydroxide, alkali metal hydroxide, or alkaline earth metal hydroxide may be used. Further, an organic solvent other than water and a catalyst may be present in the solvent. Specific examples of the organic solvent include methanol, ethanol, isopropanol, n-
Butanol, isobutanol, sec-butanol, t
Alcohols such as butanol, pentanol, ethylene glycol, propylene glycol, and 1,4-butanediol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; (cyclo) paraffins such as isooctane and cyclohexane; dioxane And ethers such as diethyl ether; aromatic hydrocarbons such as benzene, toluene and the like are used alone or in combination.

The hydrolysis and condensation are carried out, for example, by adding the above-mentioned raw material or its organic solvent solution to a solvent containing water,
To 100 ° C., preferably 0 to 70 ° C. for 30 minutes to 1
It is performed by stirring for 00 hours. When the radical polymerization initiator is added to the raw material before the condensation step, the condensation step is performed at a temperature of T _1/2 + 15 ° C. [T _1/2 : a temperature [° C.] of a 10-hour half-life of the radical polymerization initiator]. , Or in an oxygen gas-containing atmosphere such as air, which suppresses radical polymerization.

The particles obtained by the above method may be charged as seed particles in a synthesis system in advance, and the raw materials may be added to grow the seed particles. Thus, the raw material is hydrolyzed and condensed in a solvent containing water under appropriate conditions, whereby particles are precipitated and a slurry is formed. Moreover, the precipitated particles are particles having a sharp particle size distribution. Here, the appropriate condition is, for example, that the obtained slurry has a raw material concentration of 2%.
0% by weight or less, water concentration of 50% by weight or more, and catalyst concentration of 10% by weight or less are preferably used.

The average particle size of the particles formed by hydrolysis / condensation may be determined by determining the water concentration, catalyst concentration, organic solvent concentration, raw material concentration, raw material addition time, temperature, and seed particle concentration, for example, from 50 to 99, respectively. .99% by weight, 0.01 to 10% by weight, 0 to 90% by weight, 0.1 to 30% by weight, 0.001%
By setting the temperature to 0 to 100 ° C. and 0 to 10% by weight for 500 hours, the average particle diameter of the reactive organic-inorganic composite particles of the present invention can be set within the above-mentioned range. The coefficient of variation of the particle diameter of the particles to be generated is such that the water concentration, the catalyst concentration, and the organic solvent concentration are each set within the above ranges, whereby the reactive organic-inorganic composite particles of the present invention have the above-mentioned particle diameter. It can be within the range of the coefficient of variation.

Further, when hydrolyzing and condensing the silicon compound and a metal compound which can be hydrolyzed and condensed as required, it is preferable to further use inorganic fine particles having an average particle diameter of 0.4 μm or less. . The reason for this is that the obtained reactive organic-inorganic composite particles have higher hardness by containing inorganic fine particles chemically bonded to the polysiloxane skeleton.

Specific examples of the inorganic fine particles include, for example, silica, alumina, aluminum hydroxide, titanium oxide, and zirconium oxide. However, they are easily introduced into particles obtained by hydrolyzing and condensing the raw material. Silica is preferred. As these inorganic fine particles, a sol dispersed in water or an organic solvent is preferable in that the aggregation of fine particles is small.

A radical polymerization reaction is carried out during and / or after the condensation step. That is, the intermediate product / particle obtained by hydrolysis / condensation of the silicon compound undergoes radical polymerization. The radical polymerizable group undergoes a radical polymerization reaction to form an organic polymer skeleton. As a method of radical polymerization, a water-soluble or oil-soluble radical polymerization initiator may be added and dissolved in a solvent slurry containing water of particles obtained by hydrolysis and condensation, and the polymerization may be carried out as it is. The particles obtained by decomposition / condensation are isolated from the slurry using a conventionally known method such as filtration, centrifugation, and concentration under reduced pressure, and then dispersed in a solution containing a radical polymerization initiator, such as water or an organic solvent. The polymerization may be carried out without limitation. In particular, a method in which a radical polymerization initiator is allowed to coexist while the above-mentioned raw materials are hydrolyzed and condensed to simultaneously perform radical polymerization is preferable. The reason for this is that the production of the polysiloxane represented by the formula 4 and the production of the organic polymer by polymerization occur in parallel, so that the above-mentioned reactive organic-inorganic composite particles of the present invention have hardness and hardness which are characteristics of inorganic substances. Because, it is easy to obtain reactive organic-inorganic composite particles having mechanical resilience which is a characteristic of an organic polymer, and it becomes reactive organic-inorganic composite particles that effectively exhibit hardness or mechanical resilience. is there.

Here, as the radical polymerization initiator, conventionally known ones can be used and are not particularly limited.
Preferably, it is at least one compound selected from azo compounds, peroxides and the like. The temperature at the time of radical polymerization has a great effect on the amount of radically polymerizable groups. The radical polymerization reaction is carried out while maintaining the temperature (T _1/2 ) of the half-life of 10 hours of the radical polymerization initiator to be used + 15 ° C. or less. The 10-hour half-life temperature of the radical polymerization initiator means a temperature at which the time required for the radical polymerization initiator used to decompose and halve is 10 hours. When the temperature is maintained at a temperature higher than the above range, the radical polymerization proceeds excessively, so that the obtained particles have a radical polymerizable group of 0.1.
It is not contained in an amount of 05 mmol / g or more, or it is difficult to control a radical polymerization reaction. Taking into account the advantage that a large amount of radically polymerizable groups can be contained in the particles, in the present invention, the radical polymerization initiator is maintained at a temperature of 10 hours half-life (T _1/2 ) + 10 ° C. or lower and the radical polymerization It is preferred to carry out the reaction.

In the radical polymerization, a monomer having a radical polymerizable group and a radical polymerizable group may coexist. As the monomer, for example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid; acrylic esters, methacrylic esters, crotonic esters, itaconic esters, maleic esters,
Unsaturated carboxylic acid esters such as fumaric acid esters; acrylamides; methacrylamides; aromatic vinyl compounds such as styrene, α-methylstyrene, divinylbenzene, etc .; vinyl esters such as vinyl acetate; Examples include vinyl compounds such as vinyl compounds, and one or more of these may be used. Of these, monomers containing two or more radically polymerizable groups, such as divinylbenzene, trimethylolpropane trimethacrylate, and ethylene glycol dimethacrylate, are preferred.

However, if the content of the polysiloxane skeleton in the reactive organic / inorganic composite particles is less than 25 wt% by using a large amount of the monomer, the hardness becomes insufficient, which is not preferable. Therefore, the amount of the monomer is, for example, 0 to 50% by weight, and preferably 0 to 30% by weight, based on the total weight of the silicon compound. After the radical polymerization, the following recondensation step is preferably performed because the hardness and mechanical resilience of the finally obtained reactive organic / inorganic composite particles are improved. The recondensation step is a step of further condensing polymer particles generated by radical polymerization in an organic solvent. In promoting the condensation, the above-mentioned catalysts may be used, but preferred catalysts in terms of further promoting the condensation include titanium tetraisopropoxide, titanium tetrabutoxide, diisopropoxy-bis (acetylacetonate) titanate and the like. Organic titanium compounds;
Aluminum triisopropoxide, aluminum tri
Organic aluminum compounds such as sec-butoxide, aluminum trisacetylacetonate, aluminum isopropoxide-bisacetylacetonate; organic zirconium compounds such as zirconium tetrabutoxide, zirconium tetrakis (acetylacetonate); dibutyltin diacetate, dibutyltin dilaurate , Dibutyltin diethylhexanoate, dibutyltin dimaleate and other organic tin compounds; (CH ₃ O) ₂ P (＝ O) OH, (C
_{H 3 O) P (= O} ) (OH) 2, (C 4 H 9 O) 2 P
Acidic phosphate esters such as (＝ O) OH and (C ₈ H ₁₇ O) P (＝ O) (OH) ₂ , and any one of them is used alone or two or more are used in combination Or Among them, at least one selected from the group consisting of an organotin compound and an acidic phosphoric acid ester is preferable.

In the recondensation step, the polymer particles preferably do not contain water. The reason for this is that dehydration condensation of silanol groups proceeds more easily. Therefore, in the recondensation step, when the slurry obtained in the polymerization step does not contain water, the slurry can be used as it is, and when the slurry contains water, the polymer particles are filtered, centrifuged, After separation from the slurry using a conventionally known method such as concentration under reduced pressure, it is preferable to carry out the dispersion in an organic solvent. The organic solvent used is, for example, at least one selected from the group consisting of alcohols, ketones, esters, paraffins, ethers, and aromatic hydrocarbons described above. The recondensation step is performed, for example, by 10
0 ° C or less, preferably 70 ° C or less for 30 minutes to 1
This is performed by stirring the organic solvent slurry containing the polymer particles for 0 hour. The pressure may be any of normal pressure, reduced pressure, and increased pressure.

Next, the polymer particles produced by the radical polymerization are isolated from the slurry by a conventionally known method such as filtration, centrifugation, and concentration under reduced pressure.
By drying at a temperature of not more than 70 ° C., preferably not more than 70 ° C., the reactive organic-inorganic composite particles of the present invention having appropriate hardness, mechanical resilience, and having a radical polymerizable group can be obtained. .

In the condensation step of the above production method, the specific
By hydrolyzing and condensing the silicon compound of
Polysiloxane having C = C bond via i-C bond
A skeleton is generated. And during the condensation step and / or
In the polymerization step after the combining step, T _1/2+ 15 ° C (T_1/2: La
10 hours half-life temperature of the dical polymerization initiator [° C])
Lower, preferably T_1/2Radiograph while holding at + 10 ° C
A C = C bond is added by conducting the polymerization reaction
The polymerization reaction produces an organic polymer skeleton, and the remaining
The C = C bond remains without reaction. Therefore, this manufacturing method
According to the organic polymer skeleton and the organic polymer skeleton
Silicon atom directly bonded to at least one carbon atom
Polysiloxane skeleton having organic silicon in the molecule
And the proportion of the polysiloxane skeleton is SiO_TwoIn conversion amount
25-85 wt%, preferably 30-80 wt%, more
It is preferably in the range of 33 to 70 wt%,
0.05 mol / g or more, preferably 0.1 to 2
0 mmol / g, more preferably 0.2 to 15 mmol / g,
More preferably, the reaction containing 0.4 to 12 mmol / g.
Organic-inorganic composite particles can be easily produced.

When preparing the reactive organic-inorganic composite particles, the above-mentioned raw materials, inorganic fine particles, water and catalyst for hydrolytic condensation, monomers, radical polymerization initiators and / or their amounts, temperature and heating for radical polymerization By appropriately selecting the time, drying temperature and time, the amount of SiO _{2 in} the polysiloxane skeleton can be arbitrarily controlled within the range of 25 to 85 wt% (for example, 30 to 80 wt%, or 33 to 7 wt%).
0 wt%) and can be arbitrarily controlled with a radical polymerizable group content of 0.05 mmol / g or more (for example, 0.1 to 20 mmol / g, 0.2 to 15 mmol / g, or 0.4). To 12 mmol / g) can be obtained. Further, by these controls, the composite particles of the present invention, the preferred embodiment (1),
(2), (3) or (4) is obtained.

[0064]

EXAMPLES Examples of the present invention and comparative examples outside the scope of the present invention will be shown below, but the present invention is not limited to the following examples. The amount of the radical polymerizable group of the composite particles obtained in the examples and comparative examples was measured according to the following method. (Method of Quantifying Radical Polymerizable Group) In a 500 ml flask, 1 g of particles was precisely weighed (the exact weighing value is xg), and water
0 g and 30 g of tetrahydrofuran (THF) were added and mixed for 30 minutes. 0.1N-KBr is added to this mixture.
O ₃ was added 6N-HCl aqueous solution 25ml and 15 ml, was immediately stoppered flask, was slightly agitated (by which bromine is generated, bromine is added to the double bond group). After standing in a dark room for 25 minutes, 10 ml of a 15 wt% -KI aqueous solution was added to the flask while cooling the flask with ice water (this replaced iodine with unadded bromine). The generated iodine was titrated with 0.1N-Na ₂ S ₂ O ₃ aq. The end point of the titration was the point at which the black-brown liquid turned colorless or yellow. The amount of the radical polymerizable group was determined according to the following formula.

[0065]

(Equation 4)

[Here, the titration amount of the blank is
0.1N- when no sample (particles) is used in the method
Na_TwoS_TwoO_ThreeTitration (ml) of aqueous solution; sump
The sample (particles) is used for the titration of
0.1N-Na_TwoS _TwoO_ThreeTitration of aqueous solution
(Ml); f is 0.1 N Na_TwoS_TwoO_ThreeNo
X is the exact weighed value of the sample (particle)
(Example 1) Four-port fan with cooling pipe, thermometer, and dropping port
2.9 g of 25% aqueous ammonia solution in Lasco, methanol
Solution (solution A) obtained by mixing 10.1 g of water and 141.1 g of water
And kept at 25 ± 2 ° C. while stirring.
Γ-methacryloxypropyltrimethoxysilane 2
6g, methanol 54g, as radical polymerization initiator
2,2'-azobis- (2.4-dimethylvaleronitrile
(10 hours half-life temperature: 51 ° C) 0.14g mixed
The solution (Solution B) was added through the dropping port, and γ-methacrylic acid was added.
Hydrolysis and condensation of roxypropyltrimethoxysilane
went. After 10 minutes with continued stirring, N_TwoIn the atmosphere
The mixture was heated to 58 ° C. to perform radical polymerization.

After heating for 3 hours, the mixture was cooled to room temperature,
A suspension of polymer particles was obtained. This suspension was subjected to solid-liquid separation by filtration, and the obtained cake was washed with methanol for 3 hours.
The process was repeated twice, and the obtained polymer particles were vacuum-dried in a vacuum dryer at 50 ° C. for 2 hours to obtain composite particles (1). (Example 2) In Example 1, the amount of the 25% ammonia aqueous solution of the solution A was 5.8 g, and the composition of the solution B was 4.8 g of γ-methacryloxypropyltrimethoxysilane, 51 g of methanol, 2,2′-. 0.10 g of azobis- (2,4-dimethylvaleronitrile), 2 to pentamer of tetraethoxysilane ("Silicate 40" S manufactured by Tama Chemical Co., Ltd.)
Example 1 except that the temperature was changed to 8.4 g (40 wt% as iO ₂ ) and the temperature of radical polymerization was changed to 65 ° C.
By repeating the above operation, composite particles (2) were obtained.

(Example 3) In Example 1, 2
The amount of the 5% ammonia aqueous solution was 5.8 g, and the γ-
The amount of methacryloxypropyltrimethoxysilane is reduced to 0.
7 g and the heating temperature for radical polymerization was 60
Example 1 except that the heating time was changed to 45 ° C.
By repeating the above operation, composite particles (3) were obtained.

Example 4 In Example 1, the composition of Solution B was changed to γ-methacryloxypropyltrimethoxysilane 4
8.6 g, methanol 62.0 g, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile)
(10-hour half-life temperature: 30 ℃) 0.20g, instead of the divinylbenzene 5.4 g, holds the solution A to 45 ° C. N ₂
Solution B was added dropwise over 20 minutes while stirring in the atmosphere,
The procedure of Example 1 was repeated except that the radical polymerization was performed while performing hydrolysis and condensation, to obtain composite particles (4).

Example 5 In Example 1, 20 g of γ-methacryloxypropyltrimethoxysilane was used instead of 26 g of γ-methacryloxypropyltrimethoxysilane.
g, 13 g of vinyltrimethoxysilane and 20 g of tetraethoxysilane, and 2,2 was used as a radical polymerization initiator.
The procedure of Example 1 was repeated, except that 0.5 g of 2'-azobisisobutyronitrile (10-hour half-life temperature: 65 ° C) was used and the heating temperature for radical polymerization was changed to 70 ° C. Particles (5) were obtained.

(Example 6) In Example 1, 2
The amount of the 5% ammonia aqueous solution was 3.9 g, and the γ-
11 g of vinyltrimethoxysilane was used instead of methacryloxypropyltrimethoxysilane, 0.5 g of 2,2'-azobisisobutyronitrile was used as a radical polymerization initiator, and the heating temperature of radical polymerization was changed to 70 ° C. Except for this, the procedure of Example 1 was repeated to obtain a composite particle (6).

Composite particles (1) obtained in Examples 1 to 6
Table 1 shows the ratio of the polysiloxane skeleton (amount in terms of SiO ₂ ), the amount of the radical polymerizable group, the average particle diameter, and the coefficient of variation of (6).

[0073]

[Table 1]

For the composite particles (1) to (6), FT
The -IR analysis, -CH ₂ -CH organic polymer backbone
₂ - spectra attributed to (650~800cm ^-1) and -Si-CH ₂ - spectra attributed to (1150～
1300 cm ^-1 ) and the spectrum assigned to C = C (16
00 to 1700 cm ^-1 ) and a spectrum (1000 to 1200 cm ^-1 ) attributed to the polysiloxane skeleton.

From these results and the results shown in Table 1, in the composite particles (1) to (6), the silicon atom was directly chemically bonded to the organic polymer skeleton and at least one carbon atom in the organic polymer skeleton. A polysiloxane skeleton having an organosilicon in the molecule, and the ratio of the polysiloxane skeleton is S
It is in the range of 25 to 85 wt% in terms of iO ₂ , and it can be seen that the particles are reactive organic-inorganic composite particles containing 0.05 mmol / g or more of radical polymerizable groups.

Comparative Example 1 10 g of spherical polymethyl methacrylate particles synthesized by suspension polymerization were mixed with 30 g of water.
And 100 g of methanol, and then dispersed in 5 g of tetramethoxysilane. The mixture was stirred for 1 hour to allow the polymethyl methacrylate particles to absorb the tetramethoxysilane. The particles were separated by filtration and dried at 200 ° C. in a vacuum dryer to obtain composite particles for comparison (11).

(Comparative Example 2) 10 g of spherical divinylbenzene crosslinked particles were mixed with 30 g of water and 70 g of isopropyl alcohol.
g of the mixture, and vinyltriethoxysilane 5
g, and the mixture was stirred for 1 hour, and the surface of the crosslinked particles was coated with polysiloxane while hydrolyzing and condensing vinyltriethoxysilane. Next, the particles were taken out of the reaction solution by filtration, and dried at 75 ° C. for 2 hours in a vacuum dryer to obtain comparative composite particles (12).

Comparative Example 3 A mixture of 50 g of γ-methacryloxypropyltrimethoxysilane, 1 g of 2,2′-azobisisobutyronitrile and 50 g of isopropyl alcohol was heated at 80 ° C. for 4 hours in an N ₂ atmosphere. To perform solution polymerization of γ-methacryloxypropyltrimethoxysilane. 2 g of the obtained solution was collected, and ethyl cellosolve 1 was collected.
The mixture was mixed with 00 g and 20 g of water, 10 g of spherical silica fine particles were dispersed in the mixed solution, and the mixture was stirred for 1 hour, and the surface of the spherical silica fine particles was treated with a polymer of γ-methacryloxypropyltrimethoxysilane. Next, the particles were taken out of the reaction solution by filtration, and dried at 100 ° C. for 2 hours in a vacuum dryer to obtain comparative composite particles (13).

In the comparative composite particles (11) to (13) obtained in Comparative Examples 1 to 3, the ratio of the polysiloxane skeleton (S
Table 2 shows the amount of iO ₂ ), the amount of the radical polymerizable group, the average particle diameter, and the coefficient of variation.

[0080]

[Table 2]

For the composite particles (11) to (13) for comparison, the spectrum (650 to 800 cm ⁻¹ ) attributed to —CH ₂ —CH ₂ — and the polysiloxane skeleton were assigned in the same manner as in Example 1. Spectrum (1000 to 120
0 cm ^-1 ). The hardness and mechanical resilience of the composite particles obtained in Examples and Comparative Examples were examined. The hardness is
It is shown by the 10% compression modulus determined by the method described above. The mechanical restorability was indicated by the residual displacement after 10% deformation, which was examined by the above-described method.

Table 3 shows the results.

[0083]

[Table 3]

As shown in Table 3, in the composite particles (1) to (6) obtained in the examples, the amount of SiO ₂ constituting the polysiloxane skeleton was 25 to 85 wt%, preferably 30 to 85 wt%.
Since it is 80% by weight, more preferably 33 to 70% by weight (other than Example 4), it has high hardness and excellent mechanical resilience. On the other hand, the composite particles for comparison (11) to (1)
In 2), since the amount of SiO ₂ constituting the polysiloxane skeleton was extremely less than 25 wt%, the hardness and mechanical resilience were inferior to those of the composite particles (1) to (6) of the examples. Further, since the amount of SiO ₂ constituting the polysiloxane skeleton of the comparative composite particles (13) is larger than 85 wt%, the mechanical properties of the comparative composite particles (13) are higher than those of the composite particles (1) to (6) of the examples. The resilience was extremely poor. Moreover, the composite particles (1) to (6) obtained in the examples have a radical polymerizable group content of 0.05 mmol / g or more, preferably 0.1 to 2 mol / g.
0.0 mmol / g, more preferably 0.2 to 15.0 mmol
/ G, more preferably 0.4 to 12.0 mmol / g, so that the amount of radically polymerizable groups is lower than 0.05 mmol / g and higher than the comparative composite particles (11) to (13). It has polymerizability.

[0085]

The reactive organic-inorganic composite particles according to the present invention have a polysiloxane skeleton having an organic polymer skeleton and an organic silicon in which a silicon atom is directly chemically bonded to at least one carbon atom in the organic polymer skeleton. And
The proportion of the polysiloxane skeleton in terms of SiO ₂ amount 25-8
5% by weight, and the radical polymerizable group is 0.05 mm
Contains ol / g or more. Therefore, the reactive organic-inorganic composite particles of the present invention have a SiO ₂ content of 25 to 8 in terms of SiO ₂ content.
It has high hardness due to the polysiloxane skeleton at 5 wt% and excellent mechanical resilience due to the organic polymer skeleton, and also contains a radical polymerizable group in an amount of 0.05 mmol / g or more. By using the composite particles as they are, or by changing the radical polymerizable groups in the composite particles to other functional groups (by chemically modifying) and using them, desired functions are imparted to various uses. I can expect that. For example, when used as a filler in paints, plastic molding materials, and rubber compounds, it improves the scratch resistance and toughness of coatings, plastic molded products, and rubber products by taking advantage of its high hardness and mechanical resilience. Let me
The radical polymerizable group reacts with the organic matrix to improve the affinity with the organic matrix and the dispersibility in the organic matrix. When used as a filler of a heat, ultraviolet (UV), or electron beam (EB) curable coating composition, composite particles can be used in combination with a monomer or oligomer curable by heat, UV, or EB, and a polymerization initiator. Is expected to undergo a radical polymerization reaction with a monomer or oligomer to obtain a film having excellent scratch resistance and toughness. When used as a spacer for liquid crystal display panels, it can be expected to reduce the number of sprays and improve the uniformity of the liquid crystal gap by taking advantage of its high hardness and mechanical resilience. By suppressing the alignment, an improvement in the image quality of the liquid crystal display panel can be expected. When used as an additive in toners, high hardness and mechanical resilience are utilized to prevent carrier contamination and improve photoreceptor cleaning properties, and to control toner charging by chemically modifying radical polymerizable groups. By controlling the ratio, it is expected that the fluidity and transfer efficiency of the toner will be improved.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) C08F 299/08 C08L 1/00-101/16 C08K 3/00-13/08

Claims (6)

(57) [Claims] 1. An organic polymer skeleton comprising: a polysiloxane skeleton having in its molecule an organic silicon in which a silicon atom is directly chemically bonded to at least one carbon atom in the organic polymer skeleton; Is SiO
It is in the range of 25 to 85 wt% in terms of ₂ and contains a radical polymerizable group in an amount of 0.05 mmol / g or more ,
Reactive organic-inorganic composite particles having a coefficient of variation of 30% or less . 2. The method according to claim 1, wherein said radically polymerizable group is 0.1 to 20 mmol.
The reactive organic-inorganic composite particles according to claim 1, which are contained in an amount of 25 g / g or less and have an average particle diameter of 25 µm or less. 3. The reactive organic-inorganic composite particles according to claim 1, wherein the radical polymerizable group has a C ＝ C bond. 4. The method according to claim 1, wherein
A method for producing a responsive organic-inorganic composite particle, comprising a method selected from the group consisting of the following general formulas 2, 3 and 4.
Compounds represented by at least one general formula and derivatives thereof
At least one silicon selected from the group consisting of
A silane compound represented by the following general formula 5
Or hydrolysis using less than 200% by weight of a derivative thereof
And condensation process of condensation, [Formula 1] (Where R ¹ represents a hydrogen atom or a methyl group; R ²
Is an alkyl having 1 to 10 carbons which may have a substituent
R ³ represents a hydrogen atom and an alkyl group having 1 to 5 carbon atoms ;
From a group consisting of an alkyl group and an acyl group having 2 to 5 carbon atoms
Represents at least one monovalent group selected ) (Where R ⁴ represents a hydrogen atom or a methyl group; R ⁵
Is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
At least one selected from the group consisting of 2 to 5 acyl groups
( Shows one monovalent group) (Where R ⁶ represents a hydrogen atom or a methyl group; R ⁷
Is an alkyl having 1 to 10 carbons which may have a substituent
R ⁸ represents a hydrogen atom or a phenylene group;
And an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.
At least one monovalent group selected from the group consisting of
The show) [of 4] (Where R ⁹ is the same as R ³ ; R ¹⁰ has a substituent
And it is even better alkyl group or a phenyl group optionally; p
Is 0 or 1) a radical polymerizable group radical polymerization reaction
A reactive organic-inorganic composite, comprising:
Method for producing particles. (5) In the condensation step, ammonia, urine
Element, ethanolamine, tetramethylammonium high
Doxides, alkali metal hydroxides and alkalis
At least one catalyst selected from earth metal hydroxides
5. The method according to claim 4, which is used at a concentration of 0.01 to 10% by weight.
Production method of reactive organic-inorganic composite particles. 6. In the polymerization step, the silicon compound
Radical polymerizable group and radical polymerizable group
Having a monomer based on the total weight of the silicon compound.
6. The method according to claim 4, wherein 0 to 50% by weight coexist.
A method for producing the reactive organic-inorganic composite particles according to the above.