JPH0881561A - Organic/inorganic composite particle, its production and its use - Google Patents

Abstract

PURPOSE: To obtain an organic/inorganic composite particles by use of which the gap between a pair of members to be arranged at an exact interval can be kept constant and which scarcely damages the members by using specified polymers. CONSTITUTION: This particle is one containing an organic polymer skeleton and a polysiloxane skeleton having an organic silicon in which the constituent silicon atom is directly and chemically bonded to at least one carbon atom of the organic polymer skeleton, wherein the amount of SiO2 constituting the siloxane skeleton is 25wt.% or above, and the mean particle diameter is 0.5μm or above. This particle is obtained by hydrolytically condensing a compound (derivative) selected from among compounds of formulas I, II and III (wherein R<1> , R<4> and R<6> are each H or methyl; R<2> and R<7> are each (substituted) 1-20C organic group; and R<3> , R<5> and R<8> are each H, 1-5C alkyl or 2-5C acyl), radical- polymerizing the condensate during and/or after the condensation, and drying and firing the polymer at 800 deg.C or below.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to organic-inorganic composite particles, a method for producing the same, conductive particles, a spacer for a liquid crystal display panel, and a liquid crystal display panel.

[0002]

2. Description of the Related Art A liquid crystal display (LCD) is composed of two opposing electrode substrates, a spacer and a liquid crystal substance interposed between the electrode substrates. The spacer is used to keep the thickness of the liquid crystal layer uniform and constant. The display performance required for practical use of a liquid crystal display panel generally includes high-speed response, high contrast, wide viewing angle, and the like. In order to realize these various performances, the thickness of the liquid crystal layer, that is, the gap distance between the two electrode substrates must be kept strictly constant.

As spacers for liquid crystal display panels which meet such demands, silica particles produced by a sol-gel method (Japanese Patent Laid-Open No. 269933/1987) and those obtained by firing the silica particles (Japanese Patent Laid-Open No. 1-1989) 234826), styrene-based or divinylbenzene-based polymer particles obtained by suspension polymerization of styrene-based monomers, divinylbenzene-based monomers, and the like (JP-A-61-95016).
All of these are spherical particles having a narrow particle size distribution and a uniform particle size.

However, the above conventional technique has the following problems. (A) The one obtained by firing the silica particles produced by the sol-gel method has poor deformability and is very hard, so when a press is performed to produce a liquid crystal display plate, a vapor deposition layer such as electrodes on the substrate is formed. In addition, the coating layer such as the alignment film and the color filter is physically damaged to cause pixel defects due to image unevenness and TFT disconnection. Further, since the difference in thermal expansion coefficient between the silica calcined product particles and the liquid crystal is large, the liquid crystal shrinks when the liquid crystal display panel using the silica calcined product particles is exposed to a low temperature environment of, for example, -40 ° C. Particles do not shrink,
There is a problem of so-called low temperature foaming in which a gap is formed between the liquid crystal layer and the electrode substrate and the display function does not operate at all. (B) The silica particles produced by the sol-gel method are softer than the silica calcined product particles. However, since the unfired silica particles are inferior in mechanical recoverability, the gap distance becomes nonuniform and image unevenness is likely to occur. Moreover, uncalcined silica particles cause a problem of low temperature foaming, similar to particles of calcined silica. (C) Styrene-based or divinylbenzene-based polymer particles are organic particles and are extremely soft, so that the number of sprayed particles must be increased. Therefore, not only the manufacturing cost is increased, but also the area of the portion where the image is not formed is increased as a result. Further, the amount of impurities such as ions and molecules eluting from the inside of the spacer into the liquid crystal layer increases the display quality such as a decrease in contrast and an increase in roughness.

Therefore, there has been proposed a polymer particle which is hard to be deformed by using a large amount of a crosslinkable monomer such as divinylbenzene or a suspension polymerization using a large amount of a polymerization initiator (JP-A-4-313727). Issue). Also,
Polymer particles prepared by suspension polymerization of tetramethylolmethane tetraacrylate or tetramethylolmethane tetraacrylate and divinylbenzene and then adjusting the average particle diameter and standard deviation by classification have been proposed (Japanese Patent Publication No. 6-503180). ).

These polymer particles have a problem that abnormal alignment of liquid crystal is likely to occur. In the liquid crystal display panel, it is not possible to display a portion where the abnormal alignment of the liquid crystal occurs. The inventors of the present invention have proposed a spacer for a liquid crystal display panel, in which the compressive elastic modulus is 10% and the residual displacement after 10% deformation is in a specific range and which is composed of specific organic-inorganic composite particles (Patent application No. 5-288536). Since the spacer for a liquid crystal display panel has a hardness higher than that of conventional polymer particles, the number of sprayed particles can be reduced. However, the reduction in the number of sprayed particles increases the load applied to each particle, so that the fracture strength may be insufficient.

The conventional conductive particles are provided with inorganic compound particles such as silica particles or polymer particles and a conductor layer formed on the surface of the particles. Generally, conductive particles are used in the electronics packaging field to connect between a pair of electrodes. That is, a pair of electrodes with conductive particles interposed therebetween is pressed to electrically connect both electrodes via the conductive particles.

When the conductive particles include polymer particles, they are too soft, so that the conductor layer cannot follow the deformation of the particles when pressed, and the conductor layer peels off from the particle surface, or the electrodes are excessively stuck to each other and short-circuited. To do On the other hand, when the conductive particles include the inorganic compound particles are too hard, the contact area with the electrode does not widen, the contact resistance value cannot be lowered, or the conductor layer is applied with excessive pressure during deformation. May peel off. In addition, when the mechanical restoration property of the conductive particles is poor, it is difficult to keep the gap distance constant, which causes a problem of poor contact.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide the mechanical restoration and a small number of gaps required to maintain a constant gap distance between a pair of members which should be arranged at precise intervals. An object of the present invention is to provide organic-inorganic composite particles which have hardness and breaking strength required to keep a distance constant and which hardly cause physical damage to the member.

Another object of the present invention is to make the gap distance constant with a small number of mechanical restorations required to keep the gap distance between a pair of members to be arranged at precise intervals constant. It is an object of the present invention to provide a manufacturing method capable of easily manufacturing an organic-inorganic composite particle which has hardness and breaking strength required for holding and is less likely to cause physical damage to the member.

Another object of the present invention is to provide conductive particles that easily maintain a constant gap distance between a pair of electrodes that are electrically connected to each other and are less likely to cause poor contact. Another object of the present invention is to maintain a constant gap distance between a pair of electrode substrates, which should be arranged at a precise distance, and to keep the gap distance constant with a small number. Therefore, it is to provide a spacer for a liquid crystal display panel which has hardness and breaking strength necessary for that purpose and which is hard to give physical damage to the electrode substrate.

[0012] Another object of the present invention is to provide a liquid crystal display panel in which the physical damage of the electrode substrate is reduced and the image quality is improved.

[0013]

The organic-inorganic composite particles of the present invention include an organic polymer skeleton and a polysiloxane skeleton. The polysiloxane skeleton has in its molecule organosilicon in which a silicon atom is directly chemically bonded to at least one carbon atom in the organic polymer skeleton. The amount of SiO ₂ constituting the polysiloxane skeleton is 25 with respect to the total weight of the particles.
wt% or more. The first organic-inorganic composite particles of the present invention have an average particle diameter of 0.5 μm or more.

In the organic-inorganic composite particles of the present invention, for example, the following formula

[0015]

[Equation 2]

(Here, G represents a breaking strength [kg]; Y
Has a breaking strength satisfying the particle size [mm]). The organic-inorganic composite particles of the present invention have, for example, a 10% compression elastic modulus of 350 to 3000 kg / mm ² , 1
Residual displacement after 0% deformation is 0-5%, average particle size is 0.5
˜50 μm, coefficient of variation of particle size is 20% or less.

The organic-inorganic composite particles of the present invention may be colored by containing at least one selected from the group consisting of dyes and pigments. The method for producing organic-inorganic composite particles of the present invention includes a condensation step, a polymerization step, and a heat treatment step. The condensation step is the first step of containing a radically polymerizable group.
It is a step of hydrolyzing and condensing using a silicon compound.

The first silicon compound has the following general formula 1:

[0019]

[Chemical 4]

(Wherein R ¹ represents a hydrogen atom or a methyl group; R ² represents 1 to 1 carbon atoms which may have a substituent)
20 represents a divalent organic 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. Show)
And the following general formula 2:

[0021]

[Chemical 5]

(Wherein 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. At least one monovalent group represented by the following general formula 3:

[0023]

[Chemical 6]

(Wherein R ⁶ represents a hydrogen atom or a methyl group; R ⁷ represents 1 to 1 carbon atoms which may have a substituent)
20 represents a divalent organic group; R 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. Show)
It is at least one selected from the group consisting of compounds represented by at least one general formula selected from the group consisting of and derivatives thereof.

The polymerization step is a step in which a radical polymerizable group is subjected to a radical polymerization reaction during and / or after the condensation step. The heat treatment step is a step of drying and firing the polymer particles produced in the polymerization step at a temperature of 800 ° C. or lower. In the condensation step, the inorganic fine particles having an average particle diameter of 0.4 μm or less can be further used for hydrolysis / condensation. The inorganic fine particles are, for example, silica having an average particle diameter of 0.1 μm or less.

The heat treatment step is performed in an atmosphere having an oxygen concentration of 10% by volume or less, for example. The production method of the present invention may further include a coloring step of coloring the produced particles during and / or after at least one step selected from the condensation step, the polymerization step and the heat treatment step.

The production method of the present invention further comprises a recondensation step of condensing the polymer particles produced in the polymerization step between the polymerization step and the heat treatment step, and the heat treatment step comprises the recondensed polymer particles. It may be a step of drying and baking at a temperature of 800 ° C or lower. When the production method of the present invention includes this recondensation step, it further comprises a coloring step of coloring the produced particles during and / or after at least one step selected from a condensation step, a polymerization step, a recondensation step and a heat treatment step. May be included.

The conductive particles of the present invention have the organic / inorganic composite particles of the present invention and a conductor layer formed on the surface of the organic / inorganic composite particles. The spacer for a liquid crystal display panel of the present invention comprises the organic-inorganic composite particles of the present invention. The liquid crystal display panel of the present invention uses the spacer for liquid crystal display panel of the present invention as a spacer interposed between electrode substrates.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION

 [Organic-inorganic composite particles] Organic-inorganic composite of the present invention
The body particles consist of an organic polymer skeleton and a small amount of the organic polymer skeleton.
At least one carbon atom is directly bonded to a silicon atom
And a polysiloxane skeleton containing organosilicon in the molecule
SiO that contains and constitutes the polysiloxane skeleton ₂The amount of 2
Since it is 5 wt% or more, it is characteristic of the polysiloxane skeleton.
A certain high hardness and high characteristic of organic polymer skeleton
It has mechanical recoverability and breaking strength. For this reason, the book
The organic-inorganic composite particles of the invention are placed at precise intervals.
To keep the gap distance between a pair of members to be constant
The mechanical distance required for
It has the hardness and breaking strength necessary to maintain
And damage the components physically.
It's hard to read. Moreover, the organic-inorganic composite particles of the present invention
Have an average particle size of 0.5 μm or more,
It is useful for forming a gap between members.

The organic polymer skeleton contains at least the main chain of the main chain, side chains, branched chains and crosslinked chains derived from the organic polymer. The molecular weight, composition, structure, presence or absence of a functional group 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. The preferred organic polymer skeleton has repeating units -C because it forms particles having particularly excellent mechanical resilience.
Those having a main chain composed of -C- (in the following,
Sometimes referred to as "vinyl-based polymer").

The vinyl 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. A preferred vinyl polymer is at least one selected from the group consisting of (meth) acrylic resin, (meth) acrylic-styrene resin, and polystyrene. More preferred vinyl polymers are (meth) acrylic resins and (meth) acrylic-styrene resins.

The polysiloxane has the following formula 4:

[0033]

[Chemical 7]

It is defined as a compound in which a siloxane unit represented by the formula (3) is chemically bonded continuously to form a three-dimensional network. The silicon atom in the polysiloxane is directly chemically bonded to at least one of the carbon atoms constituting the organic polymer skeleton. Si constituting the polysiloxane skeleton
The amount of O ₂ is 25 wt% or more, preferably 30 to 80 wt, based on the weight of the organic-inorganic composite particles of the present invention.
%, More preferably 33 to 70 wt%, and most preferably 37 to 60 wt%. Within the above range, the particles have effective hardness, mechanical recoverability and breaking strength. If it is less than 25 wt%, hardness, which is a characteristic of the inorganic material, is not developed, and there is a problem that the 10% compression elastic modulus described later is small. If the amount exceeds the above range, the mechanical resilience or fracture strength of the organic polymer skeleton may be impaired, and residual displacement may increase or particles may crack.

The amount of SiO ₂ constituting the polysiloxane skeleton is the weight percentage obtained by measuring the weight before and after firing the particles at a temperature of 1000 ° C. or higher in an oxidizing atmosphere such as air. The organic-inorganic composite particles of the present invention can contain an inorganic component other than polysiloxane. Inorganic components other than polysiloxane, for example,
It is an oxide of boron, aluminum, titanium, zirconium, or the like. The amount of inorganic components other than polysiloxane is 0
-20 wt% is preferable, and 0-10 wt% is more preferable. If the amount is out of the above range, the hardness, mechanical restoring property or breaking strength may not be effectively exhibited.

The organic-inorganic composite particles of the present invention have a particle size of 0.
It has an average particle size of 5 μm or more, preferably 0.5 to 5
It has an average particle size of 0 μm, more preferably 1 to 25 μm, and even more preferably 1.5 to 20 μm. 0.5 μm
When it is less than 1, it is difficult to form a gap between the pair of members. Outside of the above range, it is a region that is not used as a spacer for liquid crystal display plates or conductive particles.

When used as a spacer, the organic-inorganic composite particles of the present invention have a particle size of, for example, 20% or less, preferably 10% or less, more preferably 8% or less, from the viewpoint of uniformity of the gap distance of the electrode substrate. Has a coefficient of variation of. If the upper limit is exceeded, the uniformity of the gap distance is reduced and image unevenness is likely to occur. The coefficient of variation of particle size is calculated by the following formula:

[0038]

(Equation 3)

Is defined by In the present invention, the average particle diameter and the standard deviation of the particle diameter are the values of the arbitrary particles 2 in the electron microscopic image.
The particle size of 00 particles was measured and determined from the following formula.

[0040]

[Equation 4]

The organic-inorganic composite particle of the present invention contains both the inorganic constitutional unit represented by the above formula 4 and the organic polymer skeleton, and the inorganic constitutional unit and the organic polymer skeleton are chemically bonded. It is a particle. Therefore, the organic-inorganic composite particles of the present invention have both high hardness, which is a characteristic of an inorganic substance, and high mechanical resilience and fracture strength, which are a characteristic of an organic polymer.

The hardness scale is 10% compression elastic modulus, and the mechanical resilience scale is residual displacement after 10% deformation. Here, the 10% compressive elastic modulus is a value measured by the following measuring method. A Shimadzu microcompression tester (MCTM-200 manufactured by Shimadzu Corporation) was used at room temperature (25
At 50 ° C), a sample particle scattered on a sample table (material: SKS flat plate) is applied with a constant load speed toward the center of the particle using a circular flat plate indenter (material: diamond) with a diameter of 50 μm. , Compression displacement is 10% of particle size
The particles are deformed until it becomes, and the number of millimeters of the load and compressive displacement at the time of 10% deformation is obtained. The calculated compressive load,
The compressive displacement of particles and the radius of particles are calculated by the following formulas:

[0043]

(Equation 5)

[Where E is compression elastic modulus (kg / mm ² ), F is compression load (kg), K is Poisson's ratio of particles (constant, 0.38), S is compression displacement (mm), R is radius of particles. (Mm). ] The compressive elastic modulus calculated by substituting into] is 10% compressive elastic modulus. Immediately thereafter, the load is removed at the same speed as the load, unloading is performed until the load becomes 0.1 g, and the load-displacement curve is extrapolated along the tangent line so that the load finally becomes 0 g, Find the displacement that still remains on the particles. The residual displacement is calculated as a percentage of the particle size. This operation is performed for three different particles, and the average value is taken as the 10% compressive elastic modulus of the particles and the residual displacement, which are used as the scales of the hardness and mechanical recoverability of the particles, respectively.

The breaking strength can be examined by using the above-mentioned micro compression tester. As described above, with respect to one sample particle scattered on the sample table, a circular flat plate indenter is used to apply a load to the center of the particle at a constant speed, and the compressive load at which the particle breaks can be obtained. When the 10% compressive elastic modulus of particles used as a conventional spacer is measured by the above measuring method, the calcined silica particles are 4400 kg / mm ² , and the styrene polymer particles are 300 kg.
It was / mm ² .

On the other hand, the organic-inorganic composite particles of the present invention have a 10% compression elastic modulus, preferably 350 to 30.
Range of 00 kg / mm ² , more preferably 400 to 2500
kg / mm ² range, more preferably 500-2000
Adjusted to any hardness within the range of kg / mm ² . 10%
If the compression modulus is below the above range, as described above, when used as a spacer for a liquid crystal display panel, there is a risk of increase in manufacturing cost due to an increase in the number of dispersed particles, a decrease in contrast, and an increase in roughness, which is higher. Then, as described above, there is a risk of physical damage to the vapor-deposited layer or coat layer on the substrate and low-temperature foaming.

Regarding the residual displacement after 10% deformation, the unsintered silica particles had a residual displacement of 8%, but the organic-inorganic composite particles of the present invention are preferably in the range of 0 to 5%, more preferably. Is 0-4%, more preferably 0-3%
It is a composite particle having a residual displacement in the range of and excellent in mechanical restoration. When 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.

Regarding the breaking strength, the organic-inorganic composite particles of the present invention preferably have the following formula:

[0049]

(Equation 6)

(Where G and Y are as described above), more preferably, the following formula:

[0051]

(Equation 7)

(Here, G and Y are the same as those mentioned above). If the breaking strength does not satisfy the above expression, the breaking strength is so small that the particles may break when the liquid crystal display panel is manufactured, and the gap distance between the electrode substrates cannot be kept constant. The 10% compression modulus and the degree of residual displacement in the above range are achieved by adjusting the amount of the polysiloxane skeleton or the organic polymer skeleton in the particles. For example, when the amount of polysiloxane skeleton is reduced, the 10% compressive elastic modulus and residual displacement are reduced, and when the amount of polysiloxane skeleton is increased,
10% compressive elastic modulus and residual displacement are increased.

The organic-inorganic composite particles of the present invention may be colored by containing at least one selected from the group consisting of dyes and pigments. The color of the particles is preferably a color that does not transmit light. A color that does not transmit light is preferable as a color of the spacer for the liquid crystal display plate because it can prevent light leakage and improve the contrast of image quality. Examples of the color that does not transmit light include colors such as black, dark blue, dark blue, purple, blue, dark green, green, brown, and red, but black, dark blue, and dark blue are particularly preferable. The dye is appropriately selected and used according to the color to be colored, and examples thereof include a disperse dye, an acid dye, a basic dye, a reactive dye, and a sulfur dye, which are classified by a dyeing method. Specific examples of these dyes include pages 1399 to 1427 of "Chemical Handbook Applied Chemistry, Ed. )It is described in.

As a method for dyeing the organic-inorganic composite particles of the present invention, a conventionally known method can be used. For example, it can be carried out by the method described in the above-mentioned "Chemical Handbook Applied Chemistry, edited by The Chemical Society of Japan" and "Japan Kayaku Dye Handbook". Since the dyed organic-inorganic composite particles of the present invention have both the hardness and the mechanical restoring property described above, they are particularly useful for improving the image quality of a liquid crystal display panel.

The preferred embodiment of the organic-inorganic composite particles of the present invention when used as a spacer for a liquid crystal display panel is as follows. The breaking strength G satisfies Expression 6 above, and more preferably Expression 7 above. Amount of polysiloxane skeleton 25 wt% or more, 10% compression elastic modulus 350 to 3000 kg / mm ² , 10% residual displacement after deformation 0 to 5%, average particle size 0.5 to 50 μm, and particle size variation coefficient 20 % Or less.

Amount of polysiloxane skeleton 30-80w
t%, 10% compression elastic modulus 400 to 2900 kg / mm ² , 1
Residual displacement after 0% deformation 0-4%, average particle size 1-25μ
The coefficient of variation of m and the particle diameter is 10% or less. Amount of polysiloxane skeleton 33-70 wt%, 10%
The compression elastic modulus is 500 to 2800 kg / mm ² , the residual displacement after 10% deformation is 0 to 3%, the average particle diameter is 1.5 to 20 μm, and the variation coefficient of the particle diameter is 8% or less.

Amount of polysiloxane skeleton 37-60w
t%, 10% compression elastic modulus 550 to 2700 kg / mm ² , 1
Residual displacement after 0% deformation 0-2%, average particle size 2-15μ
The coefficient of variation of m and the particle diameter is 6% or less. In the above items, the breaking strength G and the above equation 6 are
More preferably, the above expression 7 is satisfied.

In the above items (1) to (4), at least one selected from the group consisting of dyes and pigments is included to be colored. The shape of the organic-inorganic composite particles of the present invention may be any particle shape such as spherical, needle-shaped, plate-shaped, scale-shaped, crushed, bale-shaped, eyebrows-shaped, and sugar-flavoured, and is not particularly limited, but liquid crystal display When used as a plate spacer, a spherical shape is preferable in order to make the gap distance uniform and constant. This is because spherical particles have a constant or nearly constant particle size in all or almost all directions.

The organic-inorganic composite particles of the present invention can be produced, for example, by the method for producing the organic-inorganic composite particles of the present invention described below, but may be produced by other production methods. [Method for producing organic-inorganic composite particles] The method for producing organic-inorganic composite particles of the present invention includes a condensation step, a polymerization step and a heat treatment step.

The condensation step is a step of hydrolysis / condensation using the first silicon compound. The first 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 above general formulas 1, 2 and 3 and derivatives thereof.
In the condensation step, both the first silicon compound and the following second silicon compound can be used. The second silicon compound has the following general formula 5:

[0061]

Embedded image

(Where X is CH ₂ = C (-R ¹ )-
_{^{COOR 2 -, CH 2 = C}} (-R 4) - , or CH ₂ =
C (-R ⁶⁾ -R ⁷ - represents a monovalent radical-polymerizable functional group represented by; R ¹ and R ⁴ and R ⁶ represents a hydrogen atom or a methyl group; R ² and R ⁷ is a substituted Represents a divalent organic group having 1 to 20 carbon atoms which may have a group; R ⁹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acyl group having 2 to 5 carbon atoms; At least one 1 selected from the group consisting of
Represents a valent group; R ¹⁰ represents at least one monovalent group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms which may have a substituent and an aryl group having 6 to 10 carbon atoms. Shown; m shows an integer of 2-3; n shows an integer of 0-2; m + n shows an integer of 2-3. The plurality of Xs may be different from each other, or two or more may be the same.
When n is 2, two R ^10's may be different from each other or the same. When 4-m-n is 2, two R ⁹ may be different from each other or may be the same) and are at least one selected from the group consisting of compounds represented by .

In the general formulas 1 to 3 and 5, radicals
The polymerizable group is CH₂= C (-R¹) -COOR²-, C
H₂= C (-R^Four)-Or CH₂= C (-R⁶)
-R ⁷− In the general formula 5, a radically polymerizable group
When there are two or more, they may be different from each other.
However, two or more may be the same. Radical polymerizable group
The radical polymerization reaction of
An organic polymer skeleton derived from the base polymer is generated. La
The dical polymerizable group is an acryloxy group (general formulas 1 and 5).
At R¹Is a hydrogen atom), methacryloxy
A group (in the general formulas 1 and 5, R¹Is a methyl group
Vinyl group (in the general formulas 2 and 5, R^FourIs hydrogen
Atom), an isopropenyl group (general formula 2 and
R in 5^FourIs a methyl group), 1-alkenyl
Group or vinylphenyl group (in formulas 3 and 5)
And R⁶Is a hydrogen atom) or isoalkene
Nyl group or isopropenylphenyl group (general formula 3 or
And R in 5⁶Is a methyl group).

In the general formulas 1 to 3 and 5, the hydrolyzable groups are R ³ O, R ⁵ O, R ⁸ O and R ⁹ O. R
^{The 3} O group, R ⁵ O group, R ⁸ O group and R ⁹ O group are monovalent groups selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms and an acyloxy group having 2 to 5 carbon atoms. Is. In the general formulas 1 to 3, the three R ³ O groups, the three R ⁵ O groups, and the R ⁸ O group may be different from each other, or two or more may be the same. In the general formula 5, when there are two R ⁹ O groups, they may be different from each other or the same. Preferred R ³ O group / R
^{The 5} O group, R ⁸ O group, and R ⁹ O group are selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group, and an acetoxy group in terms of a large hydrolysis / condensation rate,
More preferred are methoxy and ethoxy groups. The first silicon compound and the second silicon compound are R ³ O groups and R
^{The 5} O group, R ⁸ O group, and R ⁹ O group are hydrolyzed by water and further condensed to form the polysiloxane skeleton represented by the general formula 4.

In the general formulas 1 to 3 and 5, the R ² group and the R ⁷ group have 1 to 2 carbon atoms which may have a substituent.
It is a divalent organic group of 0. As the divalent organic group,
Although not particularly limited, for example, optionally having a substituent, an ethylene group, a propylene group, a butylene group, a hexylene group, an alkylene group such as an octylene group, a phenylene group optionally having a substituent, or, Examples thereof include an alkylene group which may have these substituents and a group in which a phenylene group is bonded via an ether bond. It is preferable that R ² and R ^{7 each} have a radically polymerizable group such as a propylene group or a phenylene group because they are easily available.

In the general formula 5, the R ¹⁰ group is an alkyl group or an aryl group bonded to a silicon atom. This alkyl group has 1 to 1 carbon atoms which may have a substituent.
It is an alkyl group of 0, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. The aryl group is an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a tolyl group. In the general formula 5, when there are two R ¹⁰ groups, they may be different from each other or the same.

The compound represented by at least one general formula selected from the group consisting of general formulas 1, 2, and 3 comprises one silicon atom, three hydrolyzable groups bonded to the silicon atom, and It has one radically polymerizable group bonded to a silicon atom. Specific examples of the compound represented by the general formula 1 include γ-
Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltriacetoxysilane, γ-methacryloxyethoxypropyltri Methoxysilane (or γ-trimethoxysilylpropyl-β-methacryloxyethyl ether) and the like, and any one of them is used alone, or two or more are used in combination.

Specific examples of the compound represented by the general formula 2 include vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyltriacetoxysilane and the like, and any one of these 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 1-
Hexenyltrimethoxysilane, 1-octenyltrimethoxysilane, 1-decenyltrimethoxysilane, γ-
Examples thereof include trimethoxysilylpropyl vinyl ether, ω-trimethoxysilylundecanoic acid vinyl ester, p-trimethoxysilylstyrene, etc., and any one of these may be used alone or two or more may be used in combination.

In the derivative of the compound represented by the general formulas 1 to 3, for example, a part of the R ³ O groups of the compound represented by the general formulas 1 to ³ is a β-dicarbonyl group and / or another chelate. From a group consisting of a compound substituted with a group capable of forming a compound and a low condensation product obtained by partially hydrolyzing and condensing the compound represented by the general formulas 1 to 3 and / or its chelate compound. It is at least one selected.

The first silicon compound is preferably the compound represented by the general formula 1 from the viewpoint of easily forming organic-inorganic composite particles having a sharp particle size distribution, and γ-methacryloxypropyltrimethoxysilane,
γ-methacryloxypropyltriethoxysilane, γ-
At least one selected from the group consisting of acryloxypropyltrimethoxysilane and γ-acryloxypropyltriethoxysilane is particularly preferable.

The compounds represented by the general formula 5 are the following five compounds. (1) One silicon atom, one radically polymerizable group bonded to the silicon atom, one alkyl group or aryl group bonded to the silicon atom, and two hydrolyzable groups bonded to the silicon atom. And a group (m = 1, n = 1). Specific examples of this compound include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldiethoxysilane, vinylmethyldimethoxysilane, Vinylmethyldiethoxysilane and the like, and any one of them may be used alone, or two or more may be used in combination. (2) One silicon atom, one radically polymerizable group bonded to the silicon atom, two alkyl groups and / or aryl groups bonded to the silicon atom, and one radical bonded to the silicon atom. With a hydrolyzable group (m = 1, n =
2). Specific examples of this compound include γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyldimethylethoxysilane, vinyldimethylmethoxysilane and the like. , One of them is used alone, or two or more are used together. (3) It has one silicon atom, two radically polymerizable groups bonded to the silicon atom, and two hydrolyzable groups bonded to the silicon atom (m = 2, n = 0). Specific examples of this compound include bis (γ-acryloxypropyl) dimethoxysilane, bis (γ-methacryloxypropyl) dimethoxysilane, and the like. Any one of them may be used alone, or two or more may be used in combination. To do. (4) One silicon atom, two radically polymerizable groups bonded to silicon atom, one alkyl group or aryl group bonded to silicon atom, and one hydrolyzable group bonded to silicon atom And a group (m = 2, n = 1). A specific example of this compound is bis (γ-methacryloxypropyl)
Examples thereof include methylmethoxysilane and bis (γ-acryloxypropyl) methylmethoxysilane, and any one of them may be used alone, or two or more thereof may be used in combination. (5) It has one silicon atom, three radically polymerizable groups bonded to the silicon atom, and one hydrolyzable group bonded to the silicon atom (m = 3, n = 0). Specific examples of this compound include tris (γ-methacryloxypropyl) methoxysilane, tris (γ-acryloxypropyl) methoxysilane, and any one of them may be used alone, or two or more thereof may be used in combination. To do.

As the second silicon compound, among the compounds represented by the general formula 5, from the viewpoint of easily forming organic-inorganic composite particles having a sharp particle size distribution,
Radically polymerizable group ^{_{CH 2 = C (-R 1)}} -COOR 2
Compounds which are-groups are preferred. The derivative of the compound represented by the general formula 5 is, for example, a group in which 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. It is at least one selected from the group consisting of a substituted compound and a low condensation product obtained by partially hydrolyzing and condensing the compound represented by the general formula 5 and / or its chelate compound.

When the second silicon compound is used for hydrolysis / condensation without using the first silicon compound, the hardness of the particles obtained tends to decrease.
Be sure to use silicon compounds. In order to obtain the organic-inorganic composite particles of the present invention, in addition to the above-mentioned first and second silicon compounds, silane compounds represented by the following general formulas 6 and 7; derivatives thereof; boron, aluminum, gallium, indium, phosphorus At least one hydrolyzable / condensable metal compound selected from the group consisting of organic metal compounds such as titanium and zirconium and inorganic metal compounds may be used in combination.

[0074]

[Chemical 9]

(Wherein R ¹¹ , R ¹³ and R ¹⁷ are the same as R ³ ; R ¹² , R ¹⁴ and R ¹⁶ are the same as R ¹⁰ ;
¹⁵ is the same as R ⁷ ; p, q, r are 0 or 1) R ¹¹ , R possessed by the silane compound represented by the general formulas 6 and 7
^{As the 13} and R ¹⁷ groups, a methyl group or an ethyl group is preferable from the viewpoint of high hydrolysis and condensation rate. p, q, r are 0 or 1
However, p, q, and r = 0 are preferable in that the hardness of the obtained organic-inorganic composite particles can be increased.

Examples of the silane compound represented by the general formula 7 include 1,2-bis (trimethoxysilyl) ethane,
1,2-bis (triethoxysilyl) ethane, 1-trimethoxysilyl-2-triethoxysilylethane and the like can be mentioned. The derivative of the silane compound represented by the general formulas 6 and 7 is a part of R contained in the compound represented by the general formulas 6 and 7.
¹¹ O, R ¹³ O and R ¹⁷ O groups are β-dicarbonyl groups and /
Or a compound substituted with a group capable of forming another chelate compound, and a low condensation product obtained by partially hydrolyzing and condensing the compound represented by the general formulas 6 and / or the chelate compound thereof. At least 1 selected from the group consisting of
Is one.

The amount of the hydrolyzable / condensable metal compound other than the first and second silicon compounds is not particularly limited, but the organic-inorganic composite particles obtained when used in a large amount do not have a spherical shape, Since it becomes difficult to control the diameter and the particle size distribution is widened, it may be unsuitable as a spacer for a liquid crystal display panel. Therefore, the amount of the hydrolyzable / condensable metal compound is preferably 200 wt% or less, more preferably 100 wt% or less, and further preferably 50 wt% with respect to the total weight of the first and second silicon compounds.
% Or less is even more preferable.

The first silicon compound and the second silicon compound and / or the metal compound capable of being hydrolyzed / condensed, which are used as necessary (hereinafter, sometimes referred to as "raw material"), contain water. It is hydrolyzed and condensed in a solvent. For the hydrolysis and condensation, any method such as batch, division, continuous, etc. can be adopted. Upon hydrolysis or condensation, a catalyst such as ammonia, urea, ethanolamine, tetramethylammonium hydroxide, alkali metal hydroxide or alkaline earth metal hydroxide may be used. In addition, water and an organic solvent other than the catalyst may be present in the solvent. Specific examples of the organic solvent include methanol, ethanol, isopropanol, n-butanol,
Alcohols such as isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, 1,4-butanediol;
Ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; (cyclo) paraffins such as isooctane and cyclohexane; ethers such as dioxane and diethyl ether; aromatic hydrocarbons such as benzene and toluene alone Alternatively, they are mixed and used.

Hydrolysis and condensation are carried out, for example, by adding the above-mentioned raw material or an organic solvent solution thereof to a solvent containing water, and
To 100 ° C, preferably in the range of 0 to 70 ° C for 30 minutes to 1
It is performed by stirring for 00 hours. Alternatively, the particles obtained by the above method may be charged as seed particles in a synthetic system in advance, and the above raw materials may be added to grow the seed particles.

As described above, the raw material is hydrolyzed and condensed in a solvent containing water under appropriate conditions, whereby particles are precipitated and a slurry is produced. The deposited particles are particles having an average particle size of 0.5 μm or more and a sharp particle size distribution, because the silicon compound having a radically polymerizable group is hydrolyzed and condensed.
Here, suitable conditions are, for example, preferably 20% by weight or less for the raw material concentration, 50% by weight or more for the water concentration, and 10% by weight or less for the catalyst concentration with respect to the obtained slurry.

The average particle size of the particles produced by hydrolysis / condensation is 50 to 99, respectively, for water concentration, catalyst concentration, organic solvent concentration, raw material concentration, raw material addition time, temperature and seed particle concentration. 0.99% by weight, 0.01 to 10% by weight, 0 to 90% by weight, 0.1 to 30% by weight, 0.001
By setting to 0 to 100 ° C. and 0 to 10% by weight for 500 hours, the average particle diameter can be within the above-mentioned range of the organic-inorganic composite particles of the present invention. The coefficient of variation of the particle diameter of the particles to be generated, the water concentration, the catalyst concentration, the organic solvent concentration, respectively, by setting within the above range, the organic-inorganic composite particles of the present invention, the variation of the particle diameter described above. It can be within the range of the coefficient.

Further, when the first silicon compound is hydrolyzed and condensed with the second silicon compound and / or the metal compound capable of being hydrolyzed and condensed, which is used as required, the average particle diameter is 0.4 μm or less. It is preferable to further use the above inorganic fine particles. The reason for this is that the obtained organic-inorganic composite particles contain inorganic fine particles chemically bonded to the polysiloxane skeleton, and thus have higher hardness and improved fracture strength.

Specific examples of the inorganic fine particles include, for example, silica, alumina, aluminum hydroxide, titanium oxide, zirconium oxide and the like, but they are easily introduced into the particles obtained by hydrolyzing and condensing the raw materials. Silica is preferred. Further, if the average particle size of the inorganic fine particles exceeds 0.4 μm, it is difficult to introduce them into the particles obtained by hydrolyzing and condensing the raw material, which is not preferable. Therefore, the smaller the average particle size of the inorganic fine particles, the better, and preferably 0.1 μ.
m or less, more preferably 30 nm or less, still more preferably 10 nm or less. Examples of the inorganic fine particles include silica having an average particle diameter of 0.1 μm or less, more preferably 30 nm or less, or even more preferably 10 nm or less.

As these inorganic fine particles, a sol dispersed in water or an organic solvent is preferable because the aggregation of the fine particles is small. More preferably, it is a sol of inorganic fine particles having an average particle diameter of 30 nm or less, and even more preferably 10 nm or less.
As a specific example, for example, as a sol of silica particles having an average particle diameter of 30 nm or less (silica sol), product names “Snowtex 20”, “Snowtex O”, “Snowtex-C”, and “Snow” manufactured by Nissan Chemical Co., Ltd. Tex-
"N", "Snowtex-S", "Snowtex-2"
0L "," Snowtex-XS "," Snowtex-XL "," Snowtex-YL "," Snowtex-ZL "," Methanol silica sol "," IPA-S "
Examples of the alumina sol include "Alumina sol-100", "Alumina sol-200", and "Alumina sol-520" manufactured by Nissan Kagaku Co., Ltd.

During the condensation step and / or after the condensation step, the radical polymerizable group is subjected to radical polymerization reaction. That is, the first silicon compound and the second silicon compound used as necessary are radically polymerized with the intermediate product / particles obtained by hydrolysis / condensation. 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 / condensation, and polymerization may be carried out as it is. The particles obtained by decomposing / condensing are isolated from the slurry by using a conventionally known method such as filtration, centrifugation, or concentration under reduced pressure, and then dispersed in a solution containing a radical polymerization initiator, such as water or an organic solvent. You can let it polymerize,
It is not limited to these. Particularly preferred is a method in which the radical polymerization is coexistent while the above raw materials are hydrolyzed and condensed to coexist with the radical polymerization initiator. The reason for this is that the formation of the polysiloxane represented by the formula 4 and the formation of the organic polymer by the polymerization occur in parallel, so that the hardness of the inorganic-inorganic composite particles of the present invention described above, which is a characteristic of the inorganic substance, and the organic Since it is easy to obtain an organic-inorganic composite particle containing mechanical resilience and puncture strength, which are characteristics of a polymer, and an organic-inorganic composite particle that effectively exhibits hardness, mechanical resilience and puncture strength is obtained. Is.

Here, as the radical polymerization initiator, a conventionally known one can be used, and it is not particularly limited,
It is preferably at least one compound selected from azo compounds and peroxides. The amount of the above-mentioned radical polymerization initiator is not particularly limited, however, when used in a large amount, the amount of heat generated increases and it becomes difficult to control the reaction. On the other hand, when a small amount is used, radical polymerization may not proceed,
For example, 0.1 to 5 wt%, preferably 0.3 to 2 wt% based on the total weight of the first and second silicon compounds.
Range.

The temperature at which radical polymerization is carried out can be appropriately selected depending on the radical polymerization initiator used, but it is preferably 30 to 100 ° C., preferably 5 because of the ease of controlling the reaction.
It is in the range of 0 to 80 ° C. In addition, a monomer having a radical-polymerizable group and a radical-polymerizable group may coexist during radical polymerization. Examples of the monomer include unsaturated carboxylic acids such as acrylic acid and methacrylic acid; acrylic acid esters, methacrylic acid esters,
Unsaturated carboxylic acid esters such as crotonic acid esters, itaconic acid esters, maleic acid esters and fumaric acid esters; acrylamides; methacrylamides; aromatic vinyl compounds such as styrene, α-methylstyrene, divinylbenzene Examples thereof include vinyl esters such as vinyl acetate; vinyl compounds such as vinyl halide compounds such as vinyl chloride; and one or more of these may be used. Among them, monomers such as divinylbenzene, trimethylolpropane trimethacrylate, and ethylene glycol dimethacrylate containing two or more radically polymerizable groups are preferable.

However, the content of the polysiloxane skeleton in the organic-inorganic composite particles is 2 by using a large amount of the monomer.
If it is less than 5 wt%, the hardness becomes insufficient, which is not preferable. Therefore, the amount of the monomer is, for example, 0 to 50 w with respect to the total weight of the first and second silicon compounds.
t%, preferably 0 to 30 wt%. After radical polymerization, it is better to carry out the following recondensation step to obtain the hardness / mechanical recoverability of the organic / inorganic composite particles finally obtained.
It is preferable because the breaking strength is improved. The recondensation step is a step in which the polymer particles generated by radical polymerization are further condensed in an organic solvent. In advancing the condensation, the above-mentioned catalyst may be used, but preferable catalysts in terms of further accelerating the condensation include titanium tetraisopropoxide, titanium tetrabutoxide, diisopropoxy-bis (acetylacetonate) titanate and the like. An organotitanium compound; an aluminum compound such as aluminum triisopropoxide, aluminum trisec-butoxide, aluminum trisacetylacetonate, aluminum isopropoxide-bisacetylacetonate;
Organozirconium compounds such as zirconium tetrabutoxide and tetrakis (acetylacetonate) zirconium; organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diethylhexanoate, dibutyltin dimaleate; (CH ₃ O) ₂ P ( =
_{O) OH, (CH 3 O} ) P (= O) (OH) 2, (C 4
_{H 9 O) 2 P (=} O) OH, (C 8 H 17 O) P (= O)
Examples thereof include acidic phosphoric acid esters such as (OH) ₂ , and any one of them may be used alone, or two or more thereof may be used in combination. Among them, at least one selected from the group consisting of organic tin compounds and acidic phosphoric acid esters 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 is more likely to proceed. 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, It is preferable to separate from the slurry using a conventionally known method such as concentration under reduced pressure and then disperse 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. Further, the recondensation step is performed, for example, at 50
It is carried out by stirring the organic solvent slurry containing polymer particles at a temperature of ˜200 ° C., preferably 60˜150 ° C. for 30 minutes to 100 hours. Also, the pressure is normal pressure,
Either reduced pressure or increased pressure may be used.

Then, the polymer particles produced by radical polymerization are isolated from the above slurry by a conventionally known method such as filtration, centrifugation, concentration under reduced pressure and the like, and then the temperature is 800 ° C. or lower, preferably 100 to 600 ° C. Of the organic-inorganic composite particles of the present invention, which have appropriate hardness, mechanical recoverability, and fracture strength, by subjecting to a heat treatment for drying and firing at a temperature of, more preferably 150 to 500 ° C. can get. This composite particle has an organic polymer skeleton,
The main component is 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. However, the heat treatment at a low temperature results in the following formula 8 present in the siloxane unit represented by the formula 5:

[0091]

[Chemical 10]

Dehydration condensation reaction between silanol groups represented by
If the required hardness cannot be obtained because the response does not occur sufficiently.
There is a match. That is, the 10% compression modulus of the particles is 350.
kg / mm ²It may not be the above. Also, it ’s 800 ℃
Degradation of organic polymer is remarkable when heat treatment at higher temperature
Therefore, the required mechanical restoration and fracture strength cannot be obtained.
That is, the residual displacement after 10% deformation of the particles is 0 to 5
%, And it is too hard to compress particles by 10%
The sex rate is 3000 kg / mm²Will exceed. Furthermore, heat treatment
There are no restrictions on the atmosphere in which the organic polymer is used.
In order to suppress the disassembly of the machine and to obtain the necessary mechanical resilience
May have an oxygen concentration of 10% by volume or less in the atmosphere.
More preferable. Heat treatment temperature is in the range of 200 ℃ to 800 ℃
Then, in order to obtain the organic-inorganic composite particles of the present invention
When the oxygen concentration in the atmosphere during heat treatment is 10% by volume or less
If the heat treatment temperature is 200 ° C. or lower,
The organic-inorganic composite particles of the present invention are formed even in air.
It

When organic-inorganic composite particles are prepared, the types and / or amounts of the above-mentioned raw materials, inorganic particles, water / catalyst for hydrolysis / condensation, monomers and radical polymerization initiators, heat treatment temperature / time / atmosphere By appropriately selecting the oxygen concentration, it is possible to obtain organic-inorganic composite particles in which the amount of SiO _{2 in} the polysiloxane skeleton can be arbitrarily controlled at 25 wt% or more and the average particle size can be arbitrarily controlled at 0.5 μm or more. .

Since the method for producing organic-inorganic composite particles of the present invention includes the above-mentioned condensation step, polymerization step and heat treatment step, the polysiloxane skeleton and the organic polymer skeleton are S.
An organic-inorganic composite particle having a structure chemically bound by an i-C bond and having high hardness characteristic of a polysiloxane skeleton and high mechanical resilience and fracture strength characteristic of an organic polymer skeleton is produced. be able to. Therefore, the generated composite particles have a mechanical resilience necessary for maintaining a constant gap distance between a pair of members that should be arranged at accurate intervals, and keep the gap distance constant with a small number. In addition to having the hardness and breaking strength required for the purpose, it is difficult to give physical damage to those members. Moreover, since the composite particles obtained by the production method of the present invention have an average particle size of 0.5 μm or more,
It is useful for forming a gap between a pair of members.

In at least one step selected from the condensation step, the polymerization step, the recondensation step and the heat treatment step and /
Alternatively, after that, the produced particles are colored to obtain colored organic-inorganic composite particles. The production method of the present invention can produce colored organic-inorganic composite particles by allowing dyes and / or pigments to coexist in the particles and introducing the dyes and / or pigments into the particles at an appropriate step during production. .

Preferably, it is colored by using a dye and / or a pigment in the condensation step in the production method of the present invention. Examples of the dye and the color of dyeing include those described above. Of these, basic dyes are preferable. this is,
This is because the silanol groups in the polysiloxane are acidic, and thus basic (cationic) dyes are easily adsorbed and dyed. The pigments include, for example, inorganic pigments such as carbon black, iron black, chrome vermillion, molybdenum red, red iron oxide, yellow lead, chrome green, cobalt green, ultramarine, and navy blue; phthalocyanine-based, azo-based, and quinacridone-based organic pigments. is there. However, since the pigment may not be introduced into the composite particles of the present invention unless the average particle diameter thereof is 0.4 μm or less, it is preferable to use the dye. The thus-colored organic-inorganic composite particles of the present invention have the above-mentioned hardness, mechanical restoring property and breaking strength, and are particularly useful for improving the image quality of the liquid crystal display panel. [Conductive Particle] The conductive particle of the present invention has the organic-inorganic composite particle of the present invention and a conductor layer formed on the surface of the organic-inorganic composite particle.

Since the conductive particles of the present invention have the organic-inorganic composite particles of the present invention, the mechanical resilience required for maintaining a constant gap distance between a pair of electrically connected electrodes. And having the hardness and breaking strength necessary to keep the gap distance constant with a small number,
Less likely to cause physical damage to the electrodes. For this reason,
It is easy to keep the gap distance between a pair of electrodes constant, and the conductor layer peels off due to pressure.-Shorts between electrodes that should not be electrically connected.-Poor contact between electrodes that should be electrically connected. Is prevented.

Examples of the metal used for the conductor layer include conventionally known metals such as nickel, gold, silver, copper, indium, and alloys thereof. In particular, nickel, gold and indium are conductive. It is preferable because it has high properties. The thickness of the conductor layer is not particularly limited as long as there is sufficient conduction,
The range of 0.01 to 5 μm is preferable, and 0.02 to 2 μm
Is particularly preferred. When the thickness is smaller than the above range, the conductivity may be insufficient, and when the thickness is larger than the above range, the conductor layer is likely to peel off due to the difference in thermal expansion coefficient between the particles and the conductor layer. The conductor layer may be one layer or two or more layers.
In the case of more than one layer, layers of different conductors may be arranged one above the other.

The method for forming the conductor layer on the surface of the organic-inorganic composite particles of the present invention may be any conventionally known method, and is not particularly limited. For example, chemical plating (electroless plating) method, coating method, PVD (Vacuum deposition, sputtering, ion plating, etc.) method and the like, among which the chemical plating method is preferable because the conductive particles of the present invention can be easily obtained. The conductive particles of the present invention thus obtained have both the hardness and the mechanical recoverability, which are the features of the organic-inorganic composite particles of the present invention described above. Therefore, it is particularly useful as an electrical connection material for electronics such as liquid crystal display boards, LSIs, and printed wiring boards. [Spacer for Liquid Crystal Display Plate] Since the first spacer for liquid crystal display plate of the present invention is composed of the organic-inorganic composite particles of the present invention, the gap distance between the pair of electrode substrates to be arranged at an accurate interval is set. It has the mechanical resilience necessary to keep it constant, the hardness and the breaking strength required to keep the gap distance constant with a small number, and it is hard to give physical damage to the electrode substrate. Therefore, 1
It is easy to keep the gap distance between the pair of electrode substrates constant, the vapor deposition layer / alignment film / coat layer is less likely to be damaged by the pressure, and the shrinkage in the low temperature environment becomes closer to the shrinkage of the liquid crystal, and the dispersion between the electrode substrates is spread. The number is reduced.

As described above, the organic-inorganic composite particles of the present invention contain both a polysiloxane skeleton and an organic polymer skeleton, and are composite particles in which the polysiloxane skeleton and the organic polymer skeleton are chemically bonded. In addition, since the particles have both a high hardness characteristic of an inorganic substance and a high mechanical resilience and breaking strength characteristic of an organic polymer, they are suitably used as a spacer for a liquid crystal display panel.

When the organic-inorganic composite particles of the present invention are colored by containing a dye and / or a pigment, the first spacer for a liquid crystal display panel of the present invention is useful as a colored spacer. In the liquid crystal display panel, when a voltage is applied between the electrode substrates, the liquid crystal causes an optical change to form an image. In contrast, the spacer is
It shows no optical change when a voltage is applied. Therefore, in the dark portion when the image is displayed, the spacer that is not colored may cause light leakage and may be confirmed as a bright spot, which may reduce the contrast of the image quality.

When the first spacer for a liquid crystal display panel of the present invention is composed of the organic-inorganic composite particles of the present invention colored by containing a dye and / or a pigment, light is less likely to cause light leakage because it is colored. In order to improve the image quality of the liquid crystal display panel, it is possible to prevent the deterioration of image quality contrast and to combine the characteristics of the composite particles of the present invention described above such as hardness, mechanical restoring property and breaking strength. It is useful. A preferred color of the colored spacer for a liquid crystal display panel is a color that does not transmit light or does not transmit light. For example, black, dark blue, navy blue, purple, blue, dark green, green, brown,
Examples of the color include red, but particularly preferably black, dark blue,
It is dark blue.

The spacer for a liquid crystal display plate (second spacer for a liquid crystal display plate) containing the organic-inorganic composite particles of the present invention and the adhesive layer formed on the surface of the organic-inorganic composite particles has an adhesive property. It is useful as a spacer.
The adhesive layer has adhesiveness when heated, for example. The second spacer for the liquid crystal display plate is interposed between the electrode substrates forming the liquid crystal display plate and is heated and pressed, whereby the adhesive layer is melted and adhered to the electrode substrate, and the adhesive layer is cooled. It is fixed by solidifying. For this reason, the second spacer for the liquid crystal display plate is less likely to move in the gap between the electrode substrates, so that the alignment film can be prevented from being damaged and the gap distance can be kept uniform to improve the image quality. A thermoplastic resin is preferable as the adhesive layer. The glass transition temperature of the thermoplastic resin is preferably 150 ° C or lower, and more preferably 80 ° C or lower. This is because it adheres to the substrate by heating and pressing for a short time. If the glass transition temperature is too high,
It may not adhere to the substrate even if it is heated. On the contrary, if it is too low, the spacers are likely to be fused with each other, so that it is most preferably in the range of 40 to 80 ° C. The type of thermoplastic resin is not particularly limited, but (meth) acrylic resin is preferable. The adhesive layer may be one layer or two or more layers, and in the case of two or more layers, layers made of different thermoplastic resins may be arranged on the upper and lower sides.

The second spacer for a liquid crystal display panel can be obtained, for example, by coating the organic-inorganic composite particles of the present invention with an adhesive layer. When a thermoplastic resin is used as the adhesive, specifically, an in situ polymerization method, a coacervation method, an interfacial polymerization method, a liquid hardening coating method,
The surface of the organic / inorganic composite particles of the present invention is coated with the thermoplastic resin layer by a conventionally known resin coating method such as a liquid drying method, a high-speed air current impact method, an air suspension coating method, and a spray drying method. The high-velocity impact method is preferable because it can be easily coated. The high-speed air flow impact method is, for example, mixing the organic-inorganic composite particles of the present invention and a powder of a thermoplastic resin, dispersing the mixture in a gas phase, and mechanical thermal energy mainly composed of impact force. Is applied to the composite particles and the thermoplastic resin powder to coat the surface of the organic-inorganic composite particles with the thermoplastic resin, which is preferable because it can be easily coated.

As a device utilizing such a high-speed air current impact method, a hybridization system manufactured by Nara Machinery Co., Ltd., a mechanofusion system manufactured by Hosokawa Micron Co., Ltd., or a Kryptron system manufactured by Kawasaki Heavy Industries, Ltd. is there. The second LCD panel spacer is
Since the organic-inorganic composite particles of the present invention described above have the characteristics of hardness, mechanical restoration and breaking strength, and have adhesiveness, they are particularly useful for improving the image quality of a liquid crystal display panel.

When the organic-inorganic composite particles are colored by containing a dye and / or a pigment, the second spacer for a liquid crystal display panel is colored so that light leakage is unlikely to occur and a reduction in image contrast is prevented. , The adhesiveness makes it difficult to move in the gap of the electrode substrate, the alignment film can be prevented from being damaged and the gap distance can be kept uniform, and the hardness and mechanical recovery characteristic of the composite particles of the present invention described above can be maintained. Since it has both properties and breaking strength, it is an adhesive spacer that is also useful as a colored spacer, and is particularly useful for improving the image quality of a liquid crystal display panel. [Liquid Crystal Display Plate] The liquid crystal display plate of the present invention is a conventional liquid crystal display plate in which the above-described spacer for a liquid crystal display plate of the present invention is interposed between electrode substrates in place of the conventional spacer. , Has the same or substantially the same gap distance as the particle diameter of the spacer. The amount of spacer used is usually 40 to 100 pieces / mm ² , preferably 40 to 100 pieces / mm ² .
The number is 80 / mm ² , which is about 10 to 50% less than that of the conventional organic particle spacer, the area of the part not forming an image is reduced, and the impurities such as ions and molecules are introduced from the inside of the spacer to the liquid crystal layer. The amount eluted into it is also reduced. Therefore, the contrast is increased, the roughness is reduced, and the display quality is expected to be improved.

The liquid crystal display panel of the present invention comprises, for example, a first electrode substrate, a second electrode substrate, a liquid crystal display plate spacer, a sealant and a liquid crystal. The first electrode substrate has a first substrate and a first electrode formed on the surface of the first substrate.
The second electrode substrate has a second substrate and a second electrode formed on the surface of the second substrate, and faces the first electrode substrate.
The liquid crystal display plate spacer is interposed between the first electrode substrate and the second electrode substrate and is the liquid crystal display plate spacer of the present invention. The sealing material bonds the first electrode substrate and the second electrode substrate at the peripheral portion. The liquid crystal is filled in the space surrounded by the first electrode substrate, the second electrode substrate, and the sealing material.

For the liquid crystal display panel of the present invention, those other than the spacer, such as the electrode substrate, the sealant, and the liquid crystal, can be used in the same manner as the conventional ones. The electrode substrate has a substrate such as a glass substrate or a film substrate, and an electrode formed on the surface of the substrate, and if necessary, an alignment film formed so as to cover the electrode on the surface of the electrode substrate. Have more. An epoxy resin adhesive sealing material or the like is used as the sealing material. As the liquid crystal, those which have been conventionally used may be used, for example, biphenyl-based, phenylcyclohexane-based, Schiff base-based, azo-based, azoxy-based, benzoic acid ester-based, terphenyl-based, cyclohexylcarboxylic acid ester-based, biphenylcyclohexane. A liquid crystal of a system, a pyrimidine system, a dioxane system, a cyclohexylcyclohexane ester system, a cyclohexylethane system, a cyclohexene system, a fluorine system, or the like can be used.

As a method for producing the liquid crystal display panel of the present invention, for example, the spacer of the present invention is used as an in-plane spacer and uniformly dispersed on one of the two electrode substrates by a wet method or a dry method. After the spacer of the present invention is dispersed in an adhesive seal material such as an epoxy resin as a seal part spacer, the adhesive seal part of the other electrode substrate is coated with a material applied by means of screen printing or the like, and an appropriate pressure is applied. And heating at a temperature of 100 to 180 ° C. for 1 to 60 minutes, or an irradiation dose of 40 to 300
A method of obtaining a liquid crystal display plate by heating and curing the adhesive sealing material with ultraviolet irradiation of mJ / cm ² and then injecting liquid crystal and sealing the injection part can be mentioned. The invention is not limited by the method. As the in-plane spacer, among the spacers for a liquid crystal display panel of the present invention, the colored first spacer for a liquid crystal display panel is preferable because light leakage does not easily occur, and the second spacer for a liquid crystal display panel is a substrate. It is more preferable because the second spacer for the second liquid crystal display plate that is colored is less likely to cause light leakage and is less likely to be fixed and move to the substrate.

The liquid crystal display panel of the present invention is used for the same purpose as that of the conventional liquid crystal display panel, for example, as an image display device for televisions, personal computers, word processors and the like.

[0111]

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 liquid crystal display panel in the following examples was produced by the following method. As shown in Fig. 1, first, 300 mm x 34
After forming an electrode (for example, a transparent electrode) 5 and a polyimide alignment film 4 on a lower glass substrate 11 having a size of 5 mm × 1.1 mm, rubbing was performed to obtain a lower electrode substrate 110. On the lower electrode substrate 110, 1% by weight of the spacer for liquid crystal display panel (in this case, in-plane spacer) 8 of the present invention is added to a mixed solvent of 30 parts by volume of methanol, 20 parts by volume of isopropanol, and 50 parts by volume of water. The material thus uniformly dispersed was sprayed for 1 to 10 seconds.

On the other hand, an electrode (for example, a transparent electrode) 5 is formed on the upper glass substrate 12 of 300 mm × 345 mm × 1.1 mm.
After forming the polyimide alignment film 4 and rubbing, the upper electrode substrate 120 was obtained. Then, the liquid crystal display panel spacers (in this case, the spacer spacers) 3 of the present invention dispersed in the epoxy resin adhesive seal material 2 so as to be 30% by volume are used for the adhesive seal portion of the upper electrode substrate 120. Screen printed.

Finally, the upper and lower electrode substrates 120 and 110
Are bonded via the spacer 8 of the present invention so that the electrode 5 and the alignment film 4 face each other, a pressure of 4 kg / cm ² is applied, and the adhesive sealing material 2 is heated at a temperature of 150 ° C. for 30 minutes. Heat cured. After that, the two electrode substrates 1
The gap between 20, 110 is evacuated and then returned to the atmospheric pressure, thereby injecting the liquid crystal 7 in which a liquid crystal substance such as biphenyl-based or phenylcyclohexane-based is mixed depending on the type of liquid crystal display panel to be manufactured, and the injection part Sealed. And
A PVA (polyvinyl alcohol) -based polarizing film 6 was attached to the outside of the upper and lower glass substrates 12 and 11 to form a liquid crystal display plate.

As shown in FIG. 2, the spacer 8 may be composed of uncolored organic-inorganic composite particles 31 of the present invention. At this time, the electrode substrate is less likely to be physically damaged by the press during manufacturing, and low-temperature foaming and image unevenness are less likely to occur. Moreover, since the number of spacers can be reduced as compared with the conventional spacers made of polymer particles, the area of a portion where an image is not formed is reduced and the amount of impurities eluted into the liquid crystal is also reduced. For this reason,
The display quality can be improved by improving the contrast.

As shown in FIG. 3, the spacer 8 may be composed of colored organic-inorganic composite particles 32 of the present invention. At this time, light leakage due to the spacers 8 is less likely to occur, so that the bright spots are less noticeable and the display quality is further improved. As shown in FIG. 4, the spacer 8 may include an uncolored organic-inorganic composite particle 31 of the present invention and an adhesive layer 33 formed on the surface of the particle 31. At this time, the spacers are less likely to move, so that the alignment film is prevented from being damaged and the display quality can be further improved.

As shown in FIG. 5, the spacer 8 may include a colored organic-inorganic composite particle 32 of the present invention and an adhesive layer 33 formed on the surface of the particle 32. At this time, since light leakage by the spacer 8 is less likely to occur, the bright spots are less noticeable and the display quality is further improved, and since the spacer is less likely to move, damage to the alignment film is prevented and the display quality is improved. The further advantage is obtained.

As shown in FIG. 6, the conductive particles of the present invention are the organic-inorganic composite particles 34 of the present invention and the particles 3 thereof.
4 and the conductor layer 35 formed on the surface. Conductor layer 35
Is, for example, a metal coating formed by electroless plating, and may be one layer or two or more layers. Regarding the evaluation method of the obtained liquid crystal display panel, the low-temperature foaming is -4.
The presence / absence of image display after holding at 5 ° C. for 1000 hours was visually observed for image unevenness and pixel defects at room temperature (25 ° C.).

[Example 1] A 25% aqueous ammonia solution of 2.9 was placed in a four-necked flask equipped with a cooling tube, a thermometer, and a dropping port.
g, methanol 10.1 g, water 141.1 g mixed solution (solution A), and maintained at 25 ± 2 ° C., while stirring the solution, γ-methacryloxypropyltrimethoxysilane 27 g, methanol 54 g Then, a solution (solution B) in which 0.14 g of 2,2′-azobis- (2.4-dimethylvaleronitrile) was mixed as a radical polymerization initiator was added from a dropping port to obtain γ-methacryloxypropyltrimethoxysilane. Hydrolysis and condensation were performed. After 20 minutes while continuing stirring, the mixture was heated to 70 ± 5 ° C. in a N ₂ atmosphere to carry out radical polymerization.

After continuing heating for 2 hours, cooling 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 to 3 times.
The procedure was repeated, and the obtained polymer particles were vacuum dried in a vacuum dryer at 200 ° C. for 2 hours to obtain composite particles (1). The obtained composite particles (1) had an average particle diameter of 4.24.
μm, coefficient of variation 3.8%, amount of SiO ₂ constituting polysiloxane skeleton 34.7 wt%, 10% compressive elastic modulus 48
The residual displacement after deformation of 0 kg / mm ² , 10% was 2.2%, and the breaking strength was 2.4 g. Regarding the composite particles (1),
The FT-IR analysis, the organic polymer backbone -CH ₂ -
CH ₂ - spectra attributed to (650～800C
m ⁻¹ ) and the spectrum (1) assigned to —Si—CH ₂ —
150-1300 cm ^-1 ) was confirmed.

From these results, the composite particles (1) are
It can be seen that the organic-inorganic composite particles include an organic polymer skeleton and a polysiloxane skeleton having an organic silicon in which a silicon atom is directly chemically bonded to at least one carbon atom in the organic polymer skeleton. Using this composite particle (1), an STN type liquid crystal display plate of B plate size was produced by a known method. As a result, the number of sprayed particles can be reduced by 10% or more with respect to the existing organic particle spacer (Nippon Shokubai Co., Ltd. Eposter GP-H), and the particles can be calcined silica or unsintered silica particles by the sol-gel method. No low-temperature bubbling or image unevenness occurred when the above was used.

Example 2 In Example 1, the composition of solution B was changed to γ-methacryloxypropyltrimethoxysilane 1
9.2 g, methanol 51 g, 2,2'-azobis-
(2,4-dimethylvaleronitrile) 0.10 g, 2 to 5-mer of tetraethoxysilane (Tama Chemical Co., Ltd. "Silicate 40" 40 wt% as SiO ₂₎ 4.2
The procedure of Example 1 was repeated except that the amount was changed to g to obtain composite particles (2).

The obtained composite particles (2) had an average particle diameter of 2.02 μm, a coefficient of variation of 7.4%, an amount of SiO ₂ constituting the polysiloxane skeleton of 42.7% by weight, and a compressive elastic modulus of 720 kg / 10%. mm ² , 10% residual displacement after deformation 3.
The strength was 6% and the breaking strength was 1.0 g. About the composite particle (2), in the same manner as in Example 1, a spectrum (650 to 800 cm ⁻¹ ) assigned to —CH ₂ —CH ₂ — and —Si were obtained.
Spectra belonging to —CH ₂ — (1150 to 130
0 cm ^-1 ) was confirmed.

Using this composite particle (2), a B5 plate size ferroelectric liquid crystal display panel was produced by a known method, and the same results as in Example 1 were obtained. [Example 3] In Example 1, the composition of the liquid B was changed to γ-methacryloxypropyltrimethoxysilane 40.5 g, methanol 50.6 g, 2,2'-azobis- (4-methoxy-2,4-dimethylvalero). Nitrile) 0.20 g,
Divinylbenzene was changed to 4.5 g, solution A was kept at 50 ± 5 ° C., and solution B was added dropwise over 20 minutes while stirring in N ₂ atmosphere, and radical polymerization was performed while hydrolysis / condensation was performed. The procedure of Example 1 was repeated to obtain composite particles (3).

The obtained composite particles (3) had an average particle size of 8.91 μm, a coefficient of variation of 4.8%, an amount of SiO ₂ constituting the polysiloxane skeleton of 29.5 wt%, and a 10% compression elastic modulus of 370 kg / mm ² , 10% residual displacement after deformation 2.
The strength was 8% and the breaking strength was 9.7 g. About the composite particle (3), in the same manner as in Example 1, a spectrum (650 to 800 cm ⁻¹ ) assigned to —CH ₂ —CH ₂ — and —Si.
Spectra belonging to —CH ₂ — (1150 to 130
0 cm ^-1 ) was confirmed.

Using this composite particle (3), a TN type liquid crystal display panel of B5 size was prepared by a known method.
The same result as in Example 1 was obtained. Example 4 In Example 1, vinyltrimethoxysilane was used instead of γ-methacryloxypropyltrimethoxysilane, and vacuum drying was performed at 200 ° C. for 2 hours, and then N
_The procedure of Example 1 was repeated except that firing was performed at 600 ° C. for 2 hours in ₂ atmospheres to obtain composite particles (4).

The obtained composite particles (4) had an average particle size of 4.18 μm, a coefficient of variation of 7.2%, an amount of SiO ₂ constituting the polysiloxane skeleton of 40.9 wt%, and a 10% compression elastic modulus of 1050 kg / mm ² , the residual displacement after 10% deformation was 3.2%, and the fracture strength was 1.9 g. Regarding the composite particles (4), in the same manner as in Example 1, —CH ₂ —C.
Spectra assigned to H ₂ − (650 to 800 cm ⁻¹ ).
And a spectrum assigned to —Si—CH ₂ — (1150
.About.1300 cm ^-1 ).

Using this composite particle (4), a STN type liquid crystal display plate of B5 size was prepared by a known method, and the same results as in Example 1 were obtained. Example 5 In Example 1, the solution A was mixed with silica sol (“Snowtex-XS” SiO ₂ 2 manufactured by Nissan Chemical Industries, Ltd.).
The operation of Example 1 was repeated except that 15 g of 0 wt% and a particle diameter of 4 to 6 nm) was added to obtain composite particles (5).

The obtained composite particles (5) had an average particle size of 4.77 μm, a coefficient of variation of 4.0%, an amount of SiO ₂ constituting the polysiloxane skeleton of 42.0 wt%, and a 10% compression elastic modulus of 1130 kg /. mm ² , the residual displacement after 10% deformation was 2.5%, and the fracture strength was 3.8 g. Regarding the composite particles (5), in the same manner as in Example 1, —CH ₂ —C.
Spectra assigned to H ₂ − (650 to 800 cm ⁻¹ ).
And a spectrum assigned to —Si—CH ₂ — (1150
.About.1300 cm ^-1 ).

Using this composite particle (5), a B5-size TFT type liquid crystal display panel was prepared by a known method, and the same results as in Example 1 were obtained. [Examples 6 to 9] Example 5 except that the type and amount of silica sol in Example 5 were changed as shown in Table 1.
The above operation was repeated to obtain composite particles (6) to (9).

The composite particles (6) to (9) thus obtained have an average particle diameter, a coefficient of variation, and S that constitutes the polysiloxane skeleton.
The amount of iO ₂ , 10% compressive elastic modulus, residual displacement after 10% deformation, and fracture strength are shown in Table 1. Composite particles (6)
For (9), in the same manner as in Example 1, —CH ₂ —C.
Spectra assigned to H ₂ − (650 to 800 cm ⁻¹ ).
And a spectrum assigned to —Si—CH ₂ — (1150
.About.1300 cm ^-1 ).

When a STN type liquid crystal display plate of B5 size was prepared by a known method using the composite particles (6) to (9), the same results as in Example 1 were obtained. [Example 10] The composite particles (8) obtained in Example 8 were further heat-treated at 400 ° C for 2 hours in a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen to obtain composite particles (10). It was

Average particle size of the obtained composite particles (10)
Diameter, coefficient of variation, SiO constituting the polysiloxane skeleton₂
Amount, 10% compressive modulus, 10% residual displacement after deformation, fracture
The breaking strength is shown in Table 1. Regarding the composite particles (10),
In the same manner as in Example 1, -CH₂-CH₂Belonged to
Spectrum (650-800 cm^-1) And -Si-CH ₂
Spectra assigned to − (1150 to 1300 cm^-1)
And confirmed.

A B5 plate-sized STN type liquid crystal display panel was produced by a known method using the composite particles (10).
In all cases, the same results as in Example 1 were obtained.

[0134]

[Table 1]

Example 11 Acid dye Kayac
yl Sky Blue R (manufactured by Nippon Kayaku Co., Ltd.) 5
g was dissolved in 100 g of water, and a dispersion liquid obtained by dispersing 10 g of the composite particles (8) obtained in Example 8 in 500 g of water was mixed and heated under pressure at 150 ° C. for 1 hour in an autoclave. . After the treatment, the particles colored in deep blue were collected by filtration, further washed with water 3 times, and then vacuum dried at 200 ° C. to obtain complex particles (11) colored in deep blue.

The obtained composite particles (11) are average particles.
Diameter 4.26 μm, coefficient of variation 6.3%, polysiloxane bone
SiO forming the case₂Amount of 40.0wt%, 10% compression
Elastic modulus 920 kg / mm²Residual displacement after 10% deformation
The strength was 3.0% and the breaking strength was 3.0 g. Composite particles (1
For 1), in the same manner as in Example 1, -CH₂-CH
₂-Spectra assigned to (650-800 cm^-1)When
-Si-CH₂Spectrum assigned to − (1150 to
1300 cm^-1) And confirmed.

Using this composite particle (11), a STN type liquid crystal display plate of B5 size was produced by a known method. The same results as in Example 8 were obtained, and the bright spot (light leakage) was obtained. There were few. Example 12 Kayacryl B which is a basic dye
5 g of rack NP200 (manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 300 g of water, pH was adjusted to 4 with acetic acid, 10 g of the composite particles (8) obtained in Example 8 was added, and the mixture was well stirred at 95 ° C. After heating for 8 hours, composite particles (12) colored in black were obtained.

The obtained composite particles (12) are average particles.
Diameter 4.41 μm, coefficient of variation 5.7%, polysiloxane bone
SiO forming the case₂Amount of 40.2wt%, 10% compression
Elastic modulus 920 kg / mm²Residual displacement after 10% deformation
The breaking strength was 2.8% and the breaking strength was 3.4 g. Composite particles (1
For 2), in the same manner as in Example 1, -CH₂-CH
₂-Spectra assigned to (650-800 cm^-1)When
-Si-CH₂Spectrum assigned to − (1150 to
1300 cm^-1) And confirmed.

Using this composite particle (12), a STN type liquid crystal display plate of B5 size was prepared by a known method, and the same results as in Example 11 were obtained. [Example 13] A composite colored in black by repeating the procedure of Example 8 except that 1 g of the basic dye Kayacryl Black NP200 (manufactured by Nippon Kayaku Co., Ltd.) was added to the liquid A. Particles (13) were obtained.

The composite particles (13) obtained are average particles.
Diameter 4.53 μm, coefficient of variation 5.1%, polysiloxane bone
SiO forming the case₂Amount of 40.4wt%, 10% compression
Elastic modulus 970 kg / mm²Residual displacement after 10% deformation
The breaking strength was 2.5% and the breaking strength was 3.6 g. Composite particles (1
For 3), in the same manner as in Example 1, -CH₂-CH
₂-Spectra assigned to (650-800 cm^-1)When
-Si-CH₂Spectrum assigned to − (1150 to
1300 cm^-1) And confirmed.

Using this composite particle (13), a STN type liquid crystal display panel of B5 size was prepared by a known method, and the same results as in Example 11 were obtained. [Example 14] Composite particles (8) 3 obtained in Example 8
0 g and thermoplastic resin particles (methyl methacrylate 84w
Copolymer of t% and 16 wt% of n-butyl acrylate, glass transition temperature 70 ° C., average particle size 0.3 μm) 2
and a composite particle (14) having an adhesive layer on the surface by coating the surface of the composite particle (8) with a thermoplastic resin by using a hybridization system NHS-O type manufactured by Nara Machinery Co., Ltd. Got When the obtained composite particles (14) having an adhesive layer were observed by SEM,
The surface of the composite particles (8) was completely covered with the thermoplastic resin, and the cross section thereof was observed by TEM. As a result, the thickness of the coating layer was 0.2 μm.

When a STN type liquid crystal display panel of B5 size was prepared by a known method using the composite particles (14) having the adhesive layer, the same results as in Example 1 were obtained.
Further, when the obtained liquid crystal display plate was similarly displayed before and after vibrating using a vibrator, there was no change at all. [Example 15] The composite particles (8) of Example 14 were used.
The procedure of Example 14 was repeated except that the black-colored composite particles (13) obtained in Example 13 were used in place of, to obtain black-colored composite particles having an adhesive layer on the surface. (15) was obtained. When the obtained black colored composite particles (15) having an adhesive layer were observed by SEM, the surface of the composite particles (13) was completely covered with a thermoplastic resin, and its cross section was TEM. The thickness of the coating layer was 0.2 μm.

Using the composite particles (15) colored in black having this adhesive layer, the S of B5 plate size was prepared by a known method.
When a TN type liquid crystal display panel was produced, the same results as in Example 14 were obtained. [Example 16] The composite particles (8) obtained in Example 8 were subjected to electroless Ni plating to obtain conductive particles (16).
The obtained conductive particles (16) had an average particle size of 4.92μ.
m, the coefficient of variation was 5.4%. When the obtained conductive particles (16) were observed with SEM and XMA, the surface of the conductive particles (16) was completely plated with Ni, and when the cross section was observed with TEM, the thickness of the coating layer was found. Was 0.3 μm.

Example 17 The composite particles (8) obtained in Example 8 were electrolessly Ni-plated and then electrolessly gold-plated to obtain conductive particles (17). The obtained conductive particles (17) had an average particle size of 5.05 μm and a coefficient of variation of 5.5%. When the obtained conductive particles (17) were observed by SEM and XMA, the conductive particles (17)
The surface of was completely plated with Ni, and the surface thereof was coated with Au. When the cross section was observed with a TEM, the thickness of the coating layer was 0.5 μm.

Example 18 The suspension of polymer particles (1) obtained in Example 1 was subjected to solid-liquid separation by decantation, and the obtained cake was dried overnight at room temperature. 5 g of this dried product was sampled, ultrasonically dispersed in 200 g of isopropyl alcohol, 0.5 g of dibutyltin dilaurate was added to this dispersion, and the mixture was heated at 80 ° C. for 2 hours while stirring. Thus, a suspension of recondensed particles (18) was obtained, and solid-liquid separation, washing, and drying were carried out in the same manner as in Example 1 to obtain composite particles (18).

The obtained composite particles (18) are average particles.
Diameter 4.20 μm, coefficient of variation 3.9%, polysiloxane bone
SiO forming the case₂Amount of 35.1wt%, 10% compression
Elastic modulus 950 kg / mm²Residual displacement after 10% deformation
The strength was 1.8% and the breaking strength was 3.0 g. Composite particles (1
For 8), in the same manner as in Example 1, -CH₂-CH
₂-Spectra assigned to (650-800 cm^-1)When
-Si-CH₂Spectrum assigned to − (1150 to
1300 cm^-1) And confirmed.

Using this composite particle (18), an STN type liquid crystal display plate of B5 size was produced by a known method, and the same results as in Example 1 were obtained. [Example 19] A four-necked flask equipped with a cooling tube, a thermometer and a dropping port was charged with a solution prepared by mixing 1.8 g of a 25% aqueous ammonia solution and 154.8 g of water in an N ₂ atmosphere.
While maintaining at ± 2 ° C. and stirring, 29 g of p-trimethoxysilylstyrene, 70 g of methanol and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) as a radical polymerization initiator were added to the solution. A solution obtained by mixing 0.12 g was added through a dropping port to hydrolyze and condense p-trimethoxysilylstyrene. After 7 minutes while continuing stirring, the mixture was heated to 55 ± 5 ° C. in an N ₂ atmosphere to carry out radical polymerization.

After continuing heating for 15 minutes, cool 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 to 3 times.
Repeated times, the obtained polymer particles were heated in an N ₂ atmosphere at 350 ° C. for 2 hours to obtain composite particles (19). The obtained composite particles (19) had an average particle diameter of 2.6.
0 μm, coefficient of variation 6.9%, amount of SiO ₂ constituting polysiloxane skeleton 36.7 wt%, 10% compressive elastic modulus 7
45 kg / mm ² , residual displacement after 10% deformation 1.8%,
The breaking strength was 1.2 g. Regarding the composite particles (19), in the same manner as in Example 1, —CH of the organic polymer skeleton was used.
_The spectrum assigned to _2- CH2- (650-800
cm ^-1) and -Si-C ₆ H ₄ - spectra attributed to (1400~1450cm ^-1, it was confirmed 700~710cm ^-1) and.

From these results, composite particles (19)
Is an organic-inorganic composite particle containing an organic polymer skeleton and a polysiloxane skeleton having 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. Using this composite particle (19), a B5 size ferroelectric liquid crystal display panel was produced by a known method, and the same results as in Example 1 were obtained.

Example 20 500 g of γ-glycidoxypropyltrimethoxysilane was added to 500 g of Raven 1255 (Colombian Carbon Japan Co., Ltd.), which is carbon black, and the mixture was heated on a hot roll at 80 to 90 ° C. three times. The procedure of Example 1 was repeated except that 13 g of the kneaded product was dispersed in Solution B in Example 1 as Solution B, and black colored composite particles (20) were obtained.
I got

The obtained composite particles (20) had an average particle diameter of 3.92 μm, a coefficient of variation of 3.2%, an amount of SiO ₂ constituting the polysiloxane skeleton of 27.8 wt%, and a 10% compression elastic modulus of 837 kg /. mm ² , the residual displacement after 10% deformation was 2.3%, and the breaking strength was 2.5 g. Composite particles (2
For (0), in the same manner as in Example 1, a spectrum assigned to —CH ₂ —CH ₂ — of the organic polymer skeleton (65
0 to 800 cm ⁻¹ ) and a spectrum (1150 to 1300 cm ⁻¹ ) assigned to —Si—CH ₂ — were confirmed.

From these results, the composite particles (20)
Is an organic-inorganic composite particle containing an organic polymer skeleton and a polysiloxane skeleton having 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. Using this composite particle (20), a B5 plate size T
When an FT type liquid crystal display panel was produced, the same results as in Example 1 were obtained.

Comparative Example 1 The composite particles (1) obtained in Example 1 were further heat-treated at 950 ° C. for 2 hours to obtain particles. SiO ₂ constituting the polysiloxane skeleton of these particles
Was 99.8 wt%, and it was found from the FT-IR analysis results that the silica particles were silica particles in which the organic polymer skeleton was decomposed and burned. The 10% compression elastic modulus of the obtained particles was 3250 kg / mm ² , and the residual displacement after 10% deformation was 6.2%. A B5 plate size TFT type liquid crystal display panel was prepared by using these particles by a known method. As a result, a pixel defect due to the disconnection of the TFT on the electrode substrate occurred, and
Since the mechanical recovery of the particles is not sufficient, the image becomes uneven.

The number of spacers of the present invention dispersed in the surface of the liquid crystal display panel obtained in the above-mentioned embodiment was such that
The number of spacers of the present invention in an arbitrary 1 mm ² in each of the nine areas divided into three equal parts in the horizontal direction was counted by an optical microscope, and the average value of the number of the nine areas in total was calculated.
The number of sprays was used. The results were as follows. Example 1 ... 73 sprays / mm ² Example 10 ... 63 sprays / mm ² Example 2 ... 70 sprays / mm ² Example 11 ... 70 sprays / mm ² Example 3 ... Sprays 69 pieces / mm ² Example 12 ... spraying number 69 pieces / mm ² Example 4 ... spraying number 68 pieces / mm ² Example 13 ... spraying number 71 pieces / mm ² Example 5 ... spraying number 69 pieces / mm ² Example 14: 69 sprayed / mm ² Example 6: 66 sprayed / mm ² Example 15: 70 sprayed / mm ² Example 7: 64 sprayed / mm ² Example 18: 65 sprayed No./mm ² Example 8 ... spraying number 68 / mm ² Example 19 ... spraying number 75 / mm ² Example 9 ... spraying number 52 / mm ² Example 20 ... spraying number 63 / mm ² [Comparison Example 2] Using the existing organic particle spacer described in Example 1, a STN type liquid crystal display panel of B5 size was prepared by a known method. La markedly appeared and could not be used as a liquid crystal display panel. At this time, the number of scattered spacers was 66 / mm ² according to the above counting method.

(Comparative Example 3) In a 2 liter glass reactor equipped with a stirrer, a dropping port and a thermometer, 307 parts by weight of methanol, 6 parts by weight of 25% aqueous ammonia and 122 parts of water were added.
5 parts by weight were mixed uniformly. 20 ± 0.5 of this mixture
60 parts by weight of methyltrimethoxysilane was added dropwise from the dropping port over 6 hours while the temperature was adjusted to 0 ° C. and the mixture was uniformly stirred at 100 rpm. Even after the dropping, the mixture was uniformly stirred for 1 hour to carry out hydrolysis and condensation to obtain a suspension of fine particles of hydrated condensate of methyltrimethoxysilane. This suspension was subjected to solid-liquid separation by filtration, and the cake thus obtained was washed with methanol 3 times.
The solid content powder thus obtained was dried repeatedly at 200 ° C. for 3 hours in a vacuum drier, and the average particle size was 2.04 μm.
m, the organic-inorganic composite particles having a coefficient of variation of 7.6% were obtained.
The 10% compression modulus of the obtained composite particles is 370 kg / mm.
² , the residual displacement after 10% deformation was 2.7%, and the fracture strength was 0.2 g. Using the composite particles as a spacer for a liquid crystal display plate, a B5 plate-sized ferroelectric liquid crystal display plate was produced by a known method. However, the composite particles were destroyed, and image unevenness remarkably appeared. It was not usable as a display board. At this time, the number of spacers scattered was 95 / mm ² according to the above counting method.

[0156]

The organic-inorganic composite particles of the present invention are
At least one of organic polymer skeleton and organic polymer skeleton
Organosilicon in which a silicon atom is directly chemically bonded to the carbon atom of
And a polysiloxane skeleton having
SiO constituting the roxane skeleton ₂Is over 25wt%
Since the average particle size is 0.5 μm or more,
Set the gap distance between a pair of members that should be
With the mechanical resilience and the small number required to maintain
The hardness required to keep the gap distance constant and
It has a breaking strength and is physically
Hard to damage.

The organic-inorganic composite particles of the present invention are 10
% Compressive elastic modulus is 350 to 3000 kg / mm ² , residual displacement after 10% deformation is 0 to 5%, and average particle size is 0.5 to 50 μ.
When the coefficient of variation of m and the particle diameter is 20% or less, the particle diameters are very uniform and there is an advantage that the spacer is useful as a spacer for a liquid crystal display plate capable of producing a liquid crystal display plate with high image quality.

When the organic-inorganic composite particles of the present invention are colored by containing at least one selected from the group consisting of dyes and pigments, light leakage is less likely to occur, and a liquid crystal display panel with few bright spots is produced. It further has an advantage that it is useful as a spacer for a liquid crystal display panel. The method for producing organic-inorganic composite particles of the present invention comprises a condensation step of hydrolyzing and condensing using a hydrolyzable / condensable radically polymerizable group-containing first silicon compound,
Since the method includes a polymerization step in which a radical polymerizable group undergoes a radical polymerization reaction during and / or after the condensation step, and a heat treatment step of drying and firing the polymer particles produced in the polymerization step at a temperature of 800 ° C. or less, The polymer skeleton and the polysiloxane skeleton chemically bonded to the polymer skeleton are evenly distributed inside and on the surface of the particle, and the gap distance between a pair of members which should be arranged at a precise interval is kept constant. An organic-inorganic composite particle that has mechanical resilience necessary for it and has hardness and breaking strength necessary to keep the gap distance constant with a small number and that does not easily give physical damage to the member. It can be easily made.

The production method of the present invention comprises a condensation step of 0.4
When further using the inorganic fine particles having an average particle diameter of μm or less, the obtained composite particles have further advantages that the hardness is higher and the breaking strength is higher. When silica having an average particle diameter of 0.1 μm or less is used as the inorganic fine particles, the polysiloxane skeleton is introduced into the composite particles in a more quantitative manner, so that higher hardness and greater breaking strength are easily exhibited. It also has the advantage of producing body particles.

In the manufacturing method of the present invention, when the heat treatment step is performed in an atmosphere having an oxygen concentration of 10% by volume or less,
Since the decomposition of the organic polymer skeleton is suppressed and the dehydration condensation of the silanol groups is promoted, it further has an advantage that composite particles having necessary hardness, mechanical restoring property and breaking strength are more easily generated. When the production method of the present invention further includes a coloring step of coloring the produced particles during and / or after at least one step selected from the condensation step, the polymerization step and the heat treatment step, light emission is less likely to occur, and thus a bright spot It further has an advantage that colored organic-inorganic composite particles are produced, which are useful as spacers for liquid crystal display panels, which can make less liquid crystal display panels.

The manufacturing method of the present invention further comprises a recondensation step of condensing the polymer particles produced in the polymerization step between the polymerization step and the heat treatment step, and the heat treatment step comprises adding 800 to the condensed polymer particles. The process of drying and firing at a temperature of ℃ or less further has the advantage of producing organic-inorganic composite particles having further improved hardness, mechanical resilience, and breaking strength.

The production method of the present invention further comprises a recondensation step, and a coloring step of coloring the produced particles during and / or after at least one step selected from the condensation step, the polymerization step, the recondensation step and the heat treatment step. When it further contains, hardness, mechanical resilience and fracture strength are further improved,
It further has an advantage that colored organic-inorganic composite particles are produced which are useful as a spacer for a liquid crystal display panel, which can produce a liquid crystal display panel having a small number of bright spots because light leakage is unlikely to occur.

Since the conductive particles of the present invention have the organic / inorganic composite particles of the present invention and the conductor layer formed on the surface of the organic / inorganic composite particles, the conductive particles between the pair of electrodes electrically connected to each other. It is easy to keep the gap distance constant and less likely to cause poor contact. For this reason, good electrical connection can be performed while maintaining a constant gap distance between the electrode substrates, which is useful as a mounting material for electronics.

Since the spacer for a liquid crystal display panel of the present invention is composed of the organic-inorganic composite particles of the present invention, it is necessary to maintain a constant gap distance between a pair of electrode substrates which should be arranged at precise intervals. It has sufficient mechanical resilience and hardness and breaking strength necessary to keep the gap distance constant with a small number, and it is hard to give physical damage to the electrode substrate.

In the liquid crystal display panel of the present invention, since the spacer for liquid crystal display panel of the present invention is used as the spacer interposed between the electrode substrates, physical damage of the electrode substrate due to the press during manufacturing is unlikely to occur. The image quality has improved.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view showing an embodiment of a liquid crystal display panel of the present invention.

FIG. 2 is a cross-sectional view showing an example of a spacer for a liquid crystal display panel of the present invention.

FIG. 3 is a cross-sectional view showing an example of a spacer for a liquid crystal display panel of the present invention.

FIG. 4 is a cross-sectional view showing an example of a spacer for a liquid crystal display panel of the present invention.

FIG. 5 is a cross-sectional view showing an example of a spacer for a liquid crystal display panel of the present invention.

FIG. 6 is a cross-sectional view showing an example of the conductive particles of the present invention.

[Explanation of symbols]

 2 Adhesive Sealing Material 3 Seal Spacer 4 Alignment Film 5 Electrode 6 Polarizing Film 7 Liquid Crystal 8 In-plane Spacer 11 Lower Glass Substrate 12 Upper Glass Substrate 31 Organic / Inorganic Composite Particles 32 Organic / Inorganic Composite Particles 33 Adhesive Layer 34 Organic / Inorganic Composite particle 35 Conductor layer 110 Lower electrode substrate 120 Upper electrode substrate

Claims (14)

[Claims] 1. A polysiloxane skeleton comprising an organic polymer skeleton and a polysiloxane skeleton having in its molecule an organosilicon in which a silicon atom is directly chemically bonded to at least one carbon atom in the organic polymer skeleton. Do Si
Organic-inorganic composite particles having an O ₂ amount of 25 wt% or more and an average particle size of 0.5 μm or more. 2. The following equation: (Where G is the breaking strength [kg]; Y is the particle size [m
m] is shown), The organic-inorganic composite particles according to claim 1, further having a breaking strength satisfying the above condition. 3. A 10% compression modulus of 350-3000 kg /
mm ² , the residual displacement after 10% deformation is 0 to 5%, the average particle diameter is 0.5 to 50 μm, and the variation coefficient of the particle diameter is 20% or less, and the organic-inorganic composite according to claim 1. particle. 4. The organic-inorganic composite particle according to claim 1, which is colored by containing at least one selected from the group consisting of dyes and pigments. 5. The following general formula 1: (Here, R ¹ represents a hydrogen atom or a methyl group; R ²
Represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent; R ³ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. And at least one monovalent group selected from the group consisting of (Here, R ⁴ represents a hydrogen atom or a methyl group; R ⁵
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), and the following general formula 3: 3] (Here, R ⁶ represents a hydrogen atom or a methyl group; R ⁷
Represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent; R ⁸ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. And at least one monovalent group selected from the group consisting of a group) and at least one selected from the group consisting of compounds represented by the general formula selected from the group consisting of
And a condensation step of hydrolyzing and condensing using a radically polymerizable group-containing first silicon compound; a polymerization step of causing a radical polymerizable group to undergo a radical polymerization reaction during and / or after the condensation step; A method for producing organic-inorganic composite particles, which comprises a heat treatment step of drying and firing the polymer particles generated in the step at a temperature of 800 ° C. or lower. 6. The production method according to claim 5, wherein the condensation step is a step of hydrolyzing and condensing by further using inorganic fine particles having an average particle diameter of 0.4 μm or less. 7. The method according to claim 6, wherein the inorganic fine particles are silica having an average particle diameter of 0.1 μm or less. 8. The manufacturing method according to claim 5, wherein the heat treatment step is performed in an atmosphere having an oxygen concentration of 10% by volume or less. 9. At least one step selected from the condensation step, the polymerization step and the heat treatment step and / or
Alternatively, the production method according to any one of claims 5 to 8, further comprising a coloring step of coloring the produced particles later. 10. A recondensation step of condensing the polymer particles produced in the polymerization step between the polymerization step and the heat treatment step, wherein the heat treatment step comprises recondensing the polymer particles. The manufacturing method according to claim 5, which is a step of drying and firing at a temperature of 800 ° C. or lower. 11. At least one selected from the condensation step, the polymerization step, the recondensation step and the heat treatment step.
The manufacturing method according to claim 10, further comprising a coloring step of coloring the produced particles during and / or after one step. 12. A conductive particle comprising the organic-inorganic composite particle according to any one of claims 1 to 4 and a conductor layer formed on the surface of the organic-inorganic composite particle. 13. A spacer for a liquid crystal display panel, which comprises the organic-inorganic composite particles according to any one of claims 1 to 4. 14. A liquid crystal display panel using the spacer for a liquid crystal display panel according to claim 13 as a spacer interposed between electrode substrates.