JP7547527B2 - Silicone particles, method for producing silicone particles, sealant for liquid crystal dropping method, and liquid crystal display element - Google Patents

Description

The present invention relates to silicone particles and a method for producing silicone particles. The present invention also relates to a sealant for liquid crystal dropping method using the silicone particles and a liquid crystal display element.

Anisotropic conductive materials such as anisotropic conductive pastes and anisotropic conductive films are widely known. In the anisotropic conductive materials, conductive particles are dispersed in a binder resin. The anisotropic conductive materials are used to electrically connect the electrodes of various connection target components such as flexible printed circuit boards (FPCs), glass boards, glass epoxy boards, and semiconductor chips, to obtain connection structures. In addition, as the conductive particles, conductive particles having a base particle and a conductive layer disposed on the surface of the base particle may be used.

Liquid crystal display elements are constructed by disposing liquid crystal between two glass substrates. In liquid crystal display elements, spacers are used as gap control materials to keep the distance (gap) between the two glass substrates uniform and constant.

The following Patent Document 1 describes the use of rubber powder such as silicone rubber powder as the spacer for the liquid crystal display element.

In addition, the following Patent Document 2 discloses particles that have two or more types of polyorganosiloxanes with different organic groups, and whose composition changes stepwise or continuously from the center of the particle toward the surface.

The following Patent Document 3 discloses particles obtained by hydrolyzing and polycondensing a polyfunctional silane compound having a polymerizable unsaturated group in the presence of a surfactant. In Patent Document 3, the polyfunctional silane compound is a first silicon compound containing at least one radical polymerizable group selected from compounds represented by a specific formula and derivatives thereof.

JP 2009-139922 A JP 2010-229303 A JP 2000-204119 A

Particles such as those described in Patent Documents 1 to 3 may have low chemical resistance or high moisture permeability.

For example, if a typical silicone rubber powder such as that described in Patent Document 1 is used as a spacer for a liquid crystal display element, the silicone rubber powder may cause contamination of the liquid crystal. In addition, due to the characteristics of the silicone material, it has high moisture permeability, which may cause unevenness in the liquid crystal display.

On the other hand, in recent years, electronic components such as pressure sensors, acceleration sensors, CMOS sensor elements, and CCD sensor elements that are placed in ceramic packages are required to have highly accurate sensing capabilities even under harsh conditions such as high temperature and high pressure. For this reason, improving the moisture permeability at the joint between two ceramic members in the above electronic components has become an important issue.

The object of the present invention is to provide silicone particles that can enhance chemical resistance and reduce moisture permeability, and a method for producing silicone particles. It is also an object of the present invention to provide a sealant for liquid crystal dropping method and a liquid crystal display element that use the silicone particles.

According to a broad aspect of the present invention, there is provided silicone particles having a particle diameter of 0.1 μm or more and 500 μm or less, and the silicone particles are silicone particles (first silicone particles) having a siloxane bond, a radical polymerizable group, and a hydrophobic group having 5 or more carbon atoms, silicone particles (second silicone particles) obtained by reacting a silane compound having a radical polymerizable group with a silane compound having a hydrophobic group having 5 or more carbon atoms to form a siloxane bond, or silicone particles (third silicone particles) obtained by reacting a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms to form a siloxane bond.

In a specific aspect of the silicone particles according to the present invention, the silicone particles are silicone particles (first silicone particles) having a siloxane bond, a radically polymerizable group at the end of the siloxane bond, and a hydrophobic group having 5 or more carbon atoms in the side chain of the siloxane bond, or silicone particles (second silicone particles) obtained by reacting a silane compound having a radically polymerizable group with a silane compound having a hydrophobic group having 5 or more carbon atoms to form a siloxane bond, or silicone particles (third silicone particles) obtained by reacting a silane compound having a radically polymerizable group and a hydrophobic group having 5 or more carbon atoms to form a siloxane bond.

In a specific aspect of the silicone particles according to the present invention, the silicone particles are silicone particles (first silicone particles) having a siloxane bond, a radically polymerizable group bonded to a silicon atom at the end of the siloxane bond, and a hydrophobic group having 5 or more carbon atoms bonded to a silicon atom in a side chain of the siloxane bond, or silicone particles (second silicone particles) obtained by reacting a silane compound having a radically polymerizable group bonded to a silicon atom with a silane compound having a hydrophobic group having 5 or more carbon atoms bonded to a silicon atom to form a siloxane bond, or silicone particles (third silicone particles) obtained by reacting a silane compound having a radically polymerizable group bonded to a silicon atom and a hydrophobic group having 5 or more carbon atoms bonded to a silicon atom to form a siloxane bond.

In a particular aspect of the silicone particles according to the present invention, the silicone particles have a dimethylsiloxane skeleton in which two methyl groups are bonded to one silicon atom.

In a specific aspect of the silicone particles according to the present invention, the silicone particles have a compressive modulus of elasticity of 500 N/mm2 or ^less when compressed by 30%.

In a particular aspect of the silicone particles according to the present invention, the silicone particles are silicone particles that do not contain a metal catalyst or contain 100 ppm or less of a metal catalyst.

In a particular aspect of the silicone particles according to the present invention, the silicone particles contain a light blocking agent.

In a particular aspect of the silicone particles according to the present invention, the silicone particles are silicone particles used as a sealant for liquid crystal dropping method.

The silicone particles according to the present invention are preferably silicone particles (first silicone particles) having a siloxane bond, a radically polymerizable group, and a hydrophobic group having 5 or more carbon atoms.

The silicone particles according to the present invention are preferably silicone particles (second silicone particles) obtained by reacting a silane compound having a radical polymerizable group with a silane compound having a hydrophobic group with 5 or more carbon atoms to form a siloxane bond, or silicone particles (third silicone particles) obtained by reacting a silane compound having a radical polymerizable group and a hydrophobic group with 5 or more carbon atoms to form a siloxane bond.

In a particular aspect of the silicone particles according to the present invention, the silicone particles are silicone particles (second silicone particles) obtained by reacting a silane compound having a radical polymerizable group with a silane compound having a hydrophobic group with 5 or more carbon atoms using a radical polymerization initiator, or silicone particles (third silicone particles) obtained by reacting a silane compound having a radical polymerizable group and a hydrophobic group with 5 or more carbon atoms using a radical polymerization initiator.

According to a broad aspect of the present invention, there is provided a method for producing silicone particles as described above, which comprises a step of obtaining silicone particles (second silicone particles) by reacting a silane compound having a radical polymerizable group with a silane compound having a hydrophobic group with 5 or more carbon atoms, or obtaining silicone particles (third silicone particles) by reacting a silane compound having a radical polymerizable group and a hydrophobic group with 5 or more carbon atoms.

In a specific aspect of the method for producing silicone particles according to the present invention, a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group with 5 or more carbon atoms are reacted with a radical polymerization initiator to obtain silicone particles (second silicone particles), or a silane compound having a radical polymerizable group and a hydrophobic group with 5 or more carbon atoms is reacted with a radical polymerization initiator to obtain silicone particles (third silicone particles).

According to a broad aspect of the present invention, there is provided a sealant for liquid crystal dropping method, comprising a thermosetting component and the above-mentioned silicone particles.

According to a broad aspect of the present invention, there is provided a liquid crystal display element comprising a first liquid crystal display element member, a second liquid crystal display element member, a seal portion that seals the outer periphery of the first liquid crystal display element member and the second liquid crystal display element member while the first liquid crystal display element member and the second liquid crystal display element member are facing each other, and liquid crystal disposed inside the seal portion between the first liquid crystal display element member and the second liquid crystal display element member, the seal portion being formed by thermally curing a sealant for the liquid crystal dripping method, and the sealant for the liquid crystal dripping method containing a thermosetting component and the above-mentioned silicone particles.

The silicone particles according to the present invention are silicone particles having a particle diameter of 0.1 μm or more and 500 μm or less, and the silicone particles are silicone particles having a siloxane bond, a radically polymerizable group, and a hydrophobic group having 5 or more carbon atoms, or silicone particles obtained by reacting a silane compound having a radically polymerizable group with a silane compound having a hydrophobic group having 5 or more carbon atoms to form a siloxane bond, or silicone particles obtained by reacting a silane compound having a radically polymerizable group and a hydrophobic group having 5 or more carbon atoms to form a siloxane bond, and therefore can have high chemical resistance and low moisture permeability.

FIG. 1 is a cross-sectional view that illustrates an example of a liquid crystal display device that uses silicone particles. FIG. 2 is a front cross-sectional view that illustrates an example of a connection structure using conductive particles. FIG. 3 is a cross-sectional view that illustrates an example of an electronic component device that uses silicone particles. FIG. 4 is an enlarged cross-sectional view showing a joint portion of the electronic component device shown in FIG.

The present invention is described in detail below.

(Silicone particles)
The silicone particles according to the present invention are silicone particles having a particle size of 0.1 μm or more and 500 μm or less.

In the silicone particles having a particle diameter of 0.1 μm or more and 500 μm or less, the present invention has the following configuration. The silicone particles according to the present invention are (Configuration 1) silicone particles (first silicone particles) having a siloxane bond, a radical polymerizable group, and a hydrophobic group having 5 or more carbon atoms, (Configuration 2) silicone particles (second silicone particles) obtained by reacting a silane compound having a radical polymerizable group with a silane compound having a hydrophobic group having 5 or more carbon atoms to form a siloxane bond, or (Configuration 3) silicone particles (third silicone particles) obtained by reacting a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms to form a siloxane bond.

The second silicone particles are silicone particles having siloxane bonds, which are a reaction product of a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group with 5 or more carbon atoms. The third silicone particles are silicone particles having siloxane bonds, which are a reaction product of a silane compound having a radical polymerizable group and a hydrophobic group with 5 or more carbon atoms.

The present invention employs the above-mentioned configuration, which makes it possible to increase the chemical resistance of the silicone particles according to the present invention, reduce their moisture permeability, and increase their moisture resistance.

In addition, in a connection structure in which conductive particles are obtained by forming a conductive portion on the surface of the silicone particles according to the present invention, and a conductive connection is made using a conductive material containing the obtained conductive particles, in a liquid crystal display element using a sealant for liquid crystal dropping method containing the silicone particles according to the present invention, and in an electronic component device (electronic device, etc.) in which two ceramic members are joined using the silicone particles according to the present invention as a gap adjustment material, it is possible to increase chemical resistance and reduce moisture permeability, thereby improving reliability under high humidity conditions.

For example, in the above connection structure, the moisture permeability of the connection portion connecting the two connection target components can be reduced, and as a result, the connection resistance can be maintained low. For example, in the above liquid crystal display element, the moisture permeability of the seal portion can be reduced, and as a result, the infiltration of moisture into the liquid crystal can be suppressed, and unevenness in the liquid crystal display can be prevented. For example, in the above electronic component element, the moisture permeability of the joint between the two ceramic members can be reduced, and deterioration of electronic components such as pressure sensors, acceleration sensors, CMOS sensor elements, and CCD sensor elements arranged in the ceramic package can be suppressed, and the reliability of the electronic components can be improved.

The presence of siloxane bonds, radically polymerizable groups, and hydrophobic groups with 5 or more carbon atoms can be measured by NMR, etc.

Since the silicone particles according to the present invention can effectively increase chemical resistance and effectively decrease moisture permeability, it is preferable that the silicone particles according to the present invention are (Structure 1') silicone particles having a siloxane bond, a radical polymerizable group at the end of the siloxane bond, and a hydrophobic group having 5 or more carbon atoms in the side chain of the siloxane bond (first silicone particles), (Structure 2) silicone particles obtained by reacting a silane compound having a radical polymerizable group with a silane compound having a hydrophobic group having 5 or more carbon atoms to form a siloxane bond (second silicone particles), or (Structure 3) silicone particles obtained by reacting a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms to form a siloxane bond (third silicone particles).

The radically polymerizable group at the end of the siloxane bond has the effect of relatively increasing the molecular weight of the polymer of the siloxane compound, and the radically polymerizable group makes it possible to easily achieve the desired particle size of the silicone particles of the present invention and further increase the chemical resistance. Examples of the radically polymerizable group include vinyl groups, (meth)acryloyl groups, and styryl groups. From the viewpoint of increasing flexibility, vinyl groups are preferred.

The hydrophobic group having 5 or more carbon atoms in the side chain of the siloxane bond has the effect of effectively reducing the moisture permeability of the polymer of the siloxane compound, and can increase the chemical resistance. Examples of the hydrophobic group having 5 or more carbon atoms include a linear alkyl group having 5 to 30 carbon atoms, a cyclic alkyl group having 5 to 30 carbon atoms, and an aromatic group having 5 to 30 carbon atoms. From the viewpoint of increasing moisture resistance, an aromatic group having 5 to 30 carbon atoms is preferable, and a phenyl group is more preferable. The hydrophobic group having 5 or more carbon atoms is preferably a hydrocarbon group having 5 or more carbon atoms. The number of carbon atoms of the hydrophobic group is preferably 6 or more.

In the above configurations 1, 1', 2, and 3, the radical polymerizable group is preferably bonded to a silicon atom.

In the above configurations 1, 1', 1'', 2, and 3, it is preferable that the hydrophobic group having 5 or more carbon atoms is bonded to a silicon atom, since this effectively increases chemical resistance and effectively reduces moisture permeability.

In a preferred embodiment of the silicone particles according to the present invention, the silicone particles are (Structure 1'') silicone particles having a siloxane bond, a vinyl group bonded to a silicon atom at the end of the siloxane bond, and a phenyl group bonded to a silicon atom at the side chain of the siloxane bond (first silicone particles); (Structure 2') silicone particles obtained by reacting a silane compound having a vinyl group bonded to a silicon atom at the end with a silane compound having a phenyl group bonded to a silicon atom at the side chain to form a siloxane bond (second silicone particles); or (Structure 3') silicone particles obtained by reacting a silane compound having a vinyl group bonded to a silicon atom at the end and a phenyl group bonded to a silicon atom at the side chain to form a siloxane bond (third silicone particles).

The silicone particles according to the present invention preferably have the above-mentioned configuration 1, more preferably have the above-mentioned configuration 1', and even more preferably have the above-mentioned configuration 1''. The silicone particles according to the present invention preferably have the above-mentioned configuration 2, and more preferably have the above-mentioned configuration 2'. The silicone particles according to the present invention preferably have the above-mentioned configuration 3, and more preferably have the above-mentioned configuration 3'. The silicone particles according to the present invention preferably have the above-mentioned configuration 2 or the above-mentioned configuration 3, and more preferably have the above-mentioned configuration 2' or the above-mentioned configuration 3'. The silicone particles according to the present invention preferably have the above-mentioned configuration 1 and the above-mentioned configuration 2 or the above-mentioned configuration 3, and more preferably have the above-mentioned configuration 1' and the above-mentioned configuration 2 or the above-mentioned configuration 3, and even more preferably have the above-mentioned configuration 1'' and the above-mentioned configuration 2' or the above-mentioned configuration 3'.

From the viewpoint of increasing the gap control effect, further effectively increasing the chemical resistance, and effectively decreasing the moisture permeability, the compressive elastic modulus when the silicone particles are compressed by 30% (30% K value) is preferably 1000 N/ ^mm2 or less, more preferably 500 N/ ^mm2 or less, and even more preferably 300 N/mm2 or ^less . The 30% K value may be greater than 1 N/ ^mm2 , may be greater than 50 N/ ^mm2 , or may be greater than 100 N/ ^mm2 .

The compressive elastic modulus (30% K value) of the silicone particles can be measured as follows:

Using a micro-compression tester, one silicone particle is compressed with the smooth end face of a cylindrical indenter (diameter 100 μm, made of diamond) under conditions of 25°C, a compression speed of 0.3 mN/sec, and a maximum test load of 20 mN. The load value (N) and compression displacement (mm) at this time are measured. From the obtained measured values, the above-mentioned compression elastic modulus can be calculated using the following formula. As the above-mentioned micro-compression tester, for example, the "Fisherscope H-100" manufactured by Fischer is used.

30% K value (N/mm ² ) = (3/2 ^1/2 )·F·S ^-3/2 ·R ^-1/2
F: Load value (N) when the silicone particles are compressed and deformed by 30%
S: Compressive displacement (mm) when the silicone particles are compressed and deformed by 30%
R: Radius of silicone particle (mm)

The particle diameter of the silicone particles is 0.1 μm or more and 500 μm or less. When the particle diameter of the silicone particles is equal to or more than the above lower limit and equal to or less than the above upper limit, the silicone particles can be suitably used as a sealant for liquid crystal dropping method. The particle diameter of the silicone particles is preferably 1 μm or more, more preferably 5 μm or more, and preferably 300 μm or less, more preferably 200 μm or less, even more preferably 100 μm or less, and particularly preferably 50 μm or less. When the particle diameter of the silicone particles is equal to or more than the above lower limit and equal to or less than the above upper limit, the distance between the liquid crystal display element components becomes appropriate, the shock absorption is increased, and aggregated silicone particles are less likely to be formed. In addition, silicone particles having a particle diameter equal to or more than the above lower limit and equal to or less than the above upper limit can be easily obtained by using the silane compound of the above configuration 2 and the above configuration 2'.

The particle size above indicates the maximum diameter. Therefore, if the silicone particles are spherical, the particle size above indicates the diameter, and if the silicone particles are other than spherical, the particle size above indicates the maximum diameter.

From the viewpoint of controlling the distance between two liquid crystal display element components with high precision, the CV value of the particle diameter of the silicone particles is preferably 40% or less.

The aspect ratio of the silicone particles is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1.2 or less. The aspect ratio indicates the major axis/minor axis.

The silicone particles preferably do not contain a metal catalyst or contain a metal catalyst at 100 ppm or less. The metal catalyst is a catalyst containing metal atoms. When a metal catalyst is used, the lower the content of the metal catalyst, the better. If the content of the metal catalyst is high, the anti-fouling properties tend to decrease. The content of the metal catalyst is more preferably 80 ppm or less, even more preferably 60 ppm or less, even more preferably 50 ppm or less, even more preferably 40 ppm or less, particularly preferably 30 ppm or less, and particularly preferably 20 ppm or less, and most preferably 10 ppm or less.

Generally, silicone particles are often obtained by polymerizing monomers using a metal catalyst. Such silicone particles contain metal catalysts inside even after washing, and the metal catalyst content may exceed 100 ppm. In contrast, silicone particles obtained without using a metal catalyst generally do not contain metal catalysts. The above-mentioned metal catalyst refers to a curing catalyst such as platinum or tin.

There is no particular limitation on the method for reducing the metal catalyst to 100 ppm or less, but examples include a method of condensing by adding a crosslinkable silane compound, and a method of introducing a polymerizable functional group into a silicone compound and polymerizing it with a polymerization initiator.

The content of the metal catalyst can be measured, for example, using an inductively coupled plasma emission spectrometer.

The use of the silicone particles is not particularly limited. The silicone particles are preferably used to obtain conductive particles having a conductive layer formed on the surface thereof, or as spacers for liquid crystal display elements. The silicone particles are preferably used to obtain conductive particles having a conductive layer formed on the surface thereof. The silicone particles are preferably used to obtain conductive particles having a conductive layer formed on the surface thereof. The silicone particles are preferably used as spacers for liquid crystal display elements.

Furthermore, the silicone particles can be suitably used to bond two ceramic members together to obtain electronic component devices (electronic devices, etc.).

Furthermore, the silicone particles can be suitably used as a filler, shock absorber, or vibration absorber. For example, the silicone particles can be used as a substitute for rubber or springs, etc.

Further details about silicone particles are described below.

Silicone Particles Details:
The material of the silicone particles is preferably a silane compound having a radical polymerizable group and a silane compound having a hydrophobic group having 5 or more carbon atoms, or a silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms. The silicone particles can be obtained through a process of obtaining silicone particles by reacting the above-mentioned silane compound and forming a siloxane bond. When these materials are reacted, a siloxane bond is formed. In the obtained silicone particles, the radical polymerizable group and the hydrophobic group having 5 or more carbon atoms generally remain. By using such a material, silicone particles having a particle size of 0.1 μm or more and 500 μm or less can be easily obtained, and the chemical resistance of the silicone particles can be increased and the moisture permeability can be reduced.

In the above-mentioned silane compound having a radical polymerizable group, it is preferable that the radical polymerizable group is directly bonded to a silicon atom. Only one type of the above-mentioned silane compound having a radical polymerizable group may be used, or two or more types may be used in combination.

The silane compound having the radical polymerizable group is preferably an alkoxysilane compound. Examples of the silane compound having the radical polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, divinylmethoxyvinylsilane, divinylethoxyvinylsilane, divinyldimethoxysilane, divinyldiethoxysilane, and 1,3-divinyltetramethyldisiloxane.

In the above-mentioned silane compound having a hydrophobic group having 5 or more carbon atoms, it is preferable that the hydrophobic group having 5 or more carbon atoms is directly bonded to a silicon atom. Only one type of the above-mentioned silane compound having a hydrophobic group having 5 or more carbon atoms may be used, or two or more types may be used in combination.

The silane compound having a hydrophobic group with 5 or more carbon atoms is preferably an alkoxysilane compound. Examples of the silane compound having a hydrophobic group with 5 or more carbon atoms include phenyltrimethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, dimethylmethoxyphenylsilane, dimethylethoxyphenylsilane, hexaphenyldisiloxane, 1,3,3,5-tetramethyl-1,1,5,5-tetraphenyltrisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, hexaphenylcyclotrisiloxane, phenyltris(trimethylsiloxy)silane, and octaphenylcyclotetrasiloxane.

In the above silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms, the radical polymerizable group is preferably directly bonded to a silicon atom, and the hydrophobic group having 5 or more carbon atoms is preferably directly bonded to a silicon atom. The above silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms may be used alone or in combination of two or more.

Examples of silane compounds having the above radical polymerizable group and a hydrophobic group having 5 or more carbon atoms include phenylvinyldimethoxysilane, phenylvinyldiethoxysilane, phenylmethylvinylmethoxysilane, phenylmethylvinylethoxysilane, diphenylvinylmethoxysilane, diphenylvinylethoxysilane, phenyldivinylmethoxysilane, phenyldivinylethoxysilane, and 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane.

When using the silane compound having the radical polymerizable group and the silane compound having the hydrophobic group having 5 or more carbon atoms to obtain silicone particles, the silane compound having the radical polymerizable group and the silane compound having the hydrophobic group having 5 or more carbon atoms are preferably used in a weight ratio of 1:1 to 1:20, and more preferably 1:5 to 1:15. In the silicone particles, the skeleton derived from the silane compound having the radical polymerizable group and the skeleton derived from the silane compound having the hydrophobic group having 5 or more carbon atoms are preferably used in a weight ratio of 1:1 to 1:20, and more preferably 1:5 to 1:15.

In the entire silane compound used to obtain silicone particles, the ratio of the number of radically polymerizable groups to the number of hydrophobic groups having 5 or more carbon atoms is preferably 1:0.5 to 1:20, and more preferably 1:1 to 1:15.

From the viewpoint of effectively increasing chemical resistance, effectively decreasing moisture permeability, and controlling the 30% K value within a suitable range, it is preferable that the silicone particles have a dimethylsiloxane skeleton in which two methyl groups are bonded to one silicon atom, and it is preferable that the material of the silicone particles contains a silane compound in which two methyl groups are bonded to one silicon atom.

From the viewpoint of effectively increasing the chemical resistance, effectively decreasing the moisture permeability, and controlling the 30% K value to a suitable range, it is preferable that the silicone particles are obtained by reacting the above-mentioned silane compound with a radical polymerization initiator to form a siloxane bond. The silicone particles are preferably a radical polymerization reaction product of the above-mentioned silane compound. The silicone particles can be obtained through a process of obtaining silicone particles by reacting the above-mentioned silane compound with a radical polymerization initiator and forming a siloxane bond. In general, it is difficult to obtain silicone particles having a particle diameter of 0.1 μm or more and 500 μm or less using a radical polymerization initiator, and it is particularly difficult to obtain silicone particles having a particle diameter of 100 μm or less. On the other hand, even when a radical polymerization initiator is used, it is possible to obtain silicone particles having a particle diameter of 0.1 μm or more and 500 μm or less by using the silane compound of the above configuration 2 and the above configuration 2', and it is also possible to obtain silicone particles having a particle diameter of 100 μm or less.

To obtain the above silicone particles, it is not necessary to use a silane compound having a hydrogen atom bonded to a silicon atom. In this case, the silane compound can be polymerized using a radical polymerization initiator without using a metal catalyst. As a result, it is possible to prevent the silicone particles from containing a metal catalyst, reduce the content of the metal catalyst in the silicone particles, and further effectively increase the chemical resistance, effectively reduce the moisture permeability, and control the 30% K value within a suitable range.

Specific methods for producing the silicone particle body include a method of producing silicone particles by carrying out a polymerization reaction of a silane compound by a suspension polymerization method, a dispersion polymerization method, a mini-emulsion polymerization method, an emulsion polymerization method, or the like. After the polymerization of the silane compound is advanced to obtain an oligomer, the silicone particles may be produced by carrying out a polymerization reaction of the silane compound, which is a polymer (oligomer, etc.), by a suspension polymerization method, a dispersion polymerization method, a mini-emulsion polymerization method, an emulsion polymerization method, or the like. For example, a silane compound having a vinyl group may be polymerized to obtain a silane compound having a vinyl group bonded to a silicon atom at the end as a polymer (oligomer, etc.). A silane compound having a phenyl group may be polymerized to obtain a silane compound having a phenyl group bonded to a silicon atom at the side chain as a polymer (oligomer, etc.). A silane compound having a vinyl group and a silane compound having a phenyl group may be polymerized to obtain a silane compound having a vinyl group bonded to a silicon atom at the end as a polymer (oligomer, etc.).

The silicone particles may have a plurality of particles on the outer surface. In this case, the silicone particles include a silicone particle body and a plurality of particles arranged on the surface of the silicone particle body, and the silicone particle body includes the above-mentioned configuration 1, the above-mentioned configuration 1', the above-mentioned configuration 1'', the above-mentioned configuration 2, the above-mentioned configuration 2', the above-mentioned configuration 3, or the above-mentioned configuration 3'. Examples of the above-mentioned plurality of particles include silicone particles and spherical silica. The presence of the above-mentioned plurality of particles can suppress the aggregation of the silicone particles.

The silicone particles may contain a light-shielding agent. By using the light-shielding agent, the sealant for liquid crystal display elements containing the silicone particles can be suitably used as a light-shielding sealant.

Examples of the light-shielding agent include polypyrrole, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Titanium black is preferred. The light-shielding agent may be present inside the silicone particles or on the outer surface.

(Sealants for liquid crystal display elements and liquid crystal dripping method)
The sealant for liquid crystal display elements is preferably a sealant for the liquid crystal dropping method. The silicone particles can be suitably used for the sealant for the liquid crystal dropping method.

The above-mentioned sealing agent for the liquid crystal dropping method (hereinafter sometimes abbreviated as sealing agent) is preferably cured by heating. The above-mentioned sealing agent preferably contains a thermosetting component and the above-mentioned silicone particles. The above-mentioned sealing agent may or may not contain a photocurable component. The above-mentioned sealing agent may or may not be irradiated with light for curing. Note that if the above-mentioned sealing agent does not contain a photocurable component, it may be stored under irradiation with light.

The thermosetting component preferably contains a thermosetting compound and a polymerization initiator or a thermosetting agent. In this case, a polymerization initiator and a thermosetting agent may be used in combination.

The content of the silicone particles is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, and preferably 70 parts by weight or less, more preferably 50 parts by weight or less, relative to 100 parts by weight of the thermosetting compound. When the content of the silicone particles is equal to or more than the lower limit and equal to or less than the upper limit, the adhesiveness of the resulting sealant for the liquid crystal dropping method becomes even better.

The above-mentioned thermosetting compounds include oxetane compounds, epoxy compounds, episulfide compounds, (meth)acrylic compounds, phenol compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds. Only one type of the above-mentioned thermosetting compounds may be used, or two or more types may be used in combination.

From the viewpoint of further improving adhesion and long-term reliability, the thermosetting compound preferably contains a (meth)acrylic compound, and more preferably contains an epoxy (meth)acrylate. The "(meth)acrylic compound" means a compound having a (meth)acryloyl group. The "epoxy (meth)acrylate" means a compound in which all epoxy groups in an epoxy compound are reacted with (meth)acrylic acid. Note that "(meth)acrylic" means one or both of "acrylic" and "methacrylic", "(meth)acryloyl" means one or both of "acryloyl" and "methacryloyl", and "(meth)acrylate" means one or both of "acrylate" and "methacrylate".

Epoxy compounds that are raw materials for synthesizing the above epoxy (meth)acrylates include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, 2,2'-diallyl bisphenol A type epoxy resins, hydrogenated bisphenol type epoxy resins, propylene oxide-added bisphenol A type epoxy resins, resorcinol type epoxy resins, biphenyl type epoxy resins, sulfide type epoxy resins, diphenyl ether type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, naphthalene phenol novolac type epoxy resins, glycidylamine type epoxy resins, alkyl polyol type epoxy resins, rubber modified type epoxy resins, glycidyl ester compounds, and bisphenol A type episulfide resins.

Commercially available bisphenol A epoxy resins include, for example, jER828EL, jER1001, and jER1004 (all manufactured by Mitsubishi Chemical Corporation); Epiclon 850-S (manufactured by DIC Corporation); and the like.

Commercially available examples of the above bisphenol F type epoxy resin include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).

Commercially available bisphenol S type epoxy resins include, for example, Epiclon EXA1514 (manufactured by DIC Corporation).

Commercially available products of the above 2,2'-diallyl bisphenol A type epoxy resin include, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).

Commercially available hydrogenated bisphenol epoxy resins include, for example, Epiclon EXA7015 (manufactured by DIC Corporation).

Commercially available products of the above propylene oxide-added bisphenol A type epoxy resin include, for example, EP-4000S (manufactured by ADEKA Corporation).

Commercially available resorcinol-type epoxy resins include, for example, EX-201 (manufactured by Nagase ChemteX Corporation).

Commercially available biphenyl-type epoxy resins include, for example, jERYX-4000H (manufactured by Mitsubishi Chemical Corporation).

Commercially available sulfide-type epoxy resins include, for example, YSLV-50TE (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.).

Commercially available diphenyl ether type epoxy resins include, for example, YSLV-80DE (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.).

Commercially available dicyclopentadiene epoxy resins include, for example, EP-4088S (manufactured by ADEKA Corporation).

Commercially available naphthalene-type epoxy resins include, for example, Epicron HP4032 and Epicron EXA-4700 (both manufactured by DIC Corporation).

Commercially available phenol novolac epoxy resins include, for example, Epiclon N-770 (manufactured by DIC Corporation).

Commercially available ortho-cresol novolac epoxy resins include, for example, Epiclon N-670-EXP-S (manufactured by DIC Corporation).

Commercially available dicyclopentadiene novolac epoxy resins include, for example, Epiclon HP7200 (manufactured by DIC Corporation).

Commercially available biphenyl novolac epoxy resins include, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).

An example of a commercially available product of the above naphthalene phenol novolac type epoxy resin is ESN-165S (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.).

Commercially available examples of the above glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Company, Inc.).

Commercially available alkyl polyol epoxy resins include, for example, ZX-1542 (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); Epiclon 726 (manufactured by DIC Corporation); Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.); and Denacol EX-611 (manufactured by Nagase ChemteX Corporation).

Commercially available rubber-modified epoxy resins include, for example, YR-450 and YR-207 (both manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); Epolead PB (manufactured by Daicel Corporation); and the like.

Commercially available products of the above glycidyl ester compounds include, for example, Denacol EX-147 (manufactured by Nagase Chemtex Corporation).

Commercially available examples of the above bisphenol A episulfide resin include jERYL-7000 (manufactured by Mitsubishi Chemical Corporation).

Other commercially available products of the above epoxy resins include, for example, YDC-1312, YSLV-80XY, and YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); XAC4151 (manufactured by Asahi Kasei Corporation); jER1031 and jER1032 (both manufactured by Mitsubishi Chemical Corporation); EXA-7120 (manufactured by DIC Corporation); and TEPIC (manufactured by Nissan Chemical Co., Ltd.).

Commercially available products of the above epoxy (meth)acrylates include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, and EBECRYLRDX63182 (all manufactured by Daicel-Allnex Co., Ltd.); EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.); Examples of such acrylates include Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, and Epoxy Ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.); Denacol Acrylate DA-141, Denacol Acrylate DA-314, and Denacol Acrylate DA-911 (all manufactured by Nagase ChemteX Corporation).

Examples of (meth)acrylic compounds other than the above epoxy (meth)acrylates include ester compounds obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, and urethane (meth)acrylates obtained by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group.

As the ester compound obtained by reacting the above (meth)acrylic acid with a compound having a hydroxyl group, any of monofunctional ester compounds, bifunctional ester compounds, and trifunctional or higher ester compounds may be used.

Examples of the monofunctional ester compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, imido (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isononyl (meth)acrylate, isomyristyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2 -phenoxyethyl (meth)acrylate, bicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth)acrylate, and 2-(meth)acryloyloxyethyl phosphate.

Examples of the bifunctional ester compounds include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and propylene oxide di(meth)acrylate. Examples of such di(meth)acrylates include bisphenol A di(meth)acrylate with ethylene oxide, bisphenol A di(meth)acrylate with ethylene oxide, bisphenol F di(meth)acrylate with ethylene oxide, dimethylol dicyclopentadienyl di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, and polybutadiene diol di(meth)acrylate.

Examples of the trifunctional or higher ester compounds include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, and tris(meth)acryloyloxyethyl phosphate.

The urethane (meth)acrylate can be obtained, for example, by reacting one equivalent of an isocyanate compound having two isocyanate groups with two equivalents of a (meth)acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin compound. An isocyanate compound having two or more isocyanate groups may also be used.

Examples of isocyanate compounds that are raw materials for the above urethane (meth)acrylates include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, tetramethylxylene diisocyanate, and 1,6,10-undecane triisocyanate.

As the isocyanate compound that is the raw material of the above urethane (meth)acrylate, for example, a chain-extended isocyanate compound obtained by reacting a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol, polyether diol, polyester diol, or polycaprolactone diol with an excess of isocyanate can also be used.

Examples of (meth)acrylic acid derivatives having a hydroxyl group, which are raw materials for the above urethane (meth)acrylates, include commercially available products such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate; mono(meth)acrylates of dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol; mono(meth)acrylates and di(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin; and epoxy (meth)acrylates such as bisphenol A type epoxy acrylate.

Commercially available products of the above urethane (meth)acrylates include, for example, M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei Co., Ltd.); EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, and EBECRYL1290. , EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, and EBECRYL2220 (all manufactured by Daicel Allnex Co., Ltd.); Art Resin UN-9000H, Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-1255, Art Resin UN-2220, Art Resin UN-2220 (all manufactured by Daicel Allnex Co., Ltd.); Toresin UN-3320HB, Art Resin UN-1200TPK, and Art Resin SH-500B (all manufactured by Negami Chemical Industries, Ltd.); U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA -4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, and UA-4000 (all manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, and UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.).

From the viewpoint of suppressing adverse effects on liquid crystals, the (meth)acrylic compound preferably has a hydrogen-bonding unit such as an --OH group, an --NH-- group, or an _--NH2 group.

From the viewpoint of increasing reactivity, it is preferable that the (meth)acrylic compound has two or three (meth)acryloyl groups.

From the viewpoint of improving the adhesiveness of the sealant for liquid crystal display elements, the above-mentioned thermosetting compound may contain an epoxy compound.

Examples of the epoxy compound include epoxy compounds that are raw materials for synthesizing the epoxy (meth)acrylates, partially (meth)acrylic modified epoxy compounds, etc.

The partially (meth)acrylic modified epoxy compound means a compound having one or more epoxy groups and one or more (meth)acryloyl groups. The partially (meth)acrylic modified epoxy compound can be obtained, for example, by reacting a part of the two or more epoxy groups in a compound having two or more epoxy groups with (meth)acrylic acid.

Commercially available products of the partially (meth)acrylic modified epoxy compounds include, for example, KRM8287 (manufactured by Daicel Allnex Corporation).

When the (meth)acrylic compound and the epoxy compound are used as the thermosetting compound, the epoxy group is preferably 20 mol % or more and preferably 50 mol % or less out of a total of 100 mol % of the (meth)acryloyl group and the epoxy group in the entire thermosetting compound. When the epoxy group is below the upper limit, the solubility of the sealant for liquid crystal display elements in liquid crystal is reduced, making it even more difficult for liquid crystal contamination to occur, and the display performance of the liquid crystal display element is even better.

The polymerization initiator may be a radical polymerization initiator, a cationic polymerization initiator, or the like. Only one type of the polymerization initiator may be used, or two or more types may be used in combination.

The above radical polymerization initiators include photoradical polymerization initiators that generate radicals upon irradiation with light, and thermal radical polymerization initiators that generate radicals upon heating.

The above radical polymerization initiator has a much faster curing speed than a heat curing agent. Therefore, by using a radical polymerization initiator, it is possible to suppress the occurrence of seal breaks and liquid crystal contamination, and also to suppress springback that is likely to occur due to the above silicone particles.

Examples of the photoradical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and thioxanthone.

Commercially available examples of the photoradical polymerization initiator include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucirin TPO (all manufactured by BASF Japan); benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.).

Examples of the thermal radical polymerization initiator include azo compounds and organic peroxides. Azo compounds are preferred, and polymeric azo initiators that are polymeric azo compounds are more preferred.

A polymeric azo compound means a compound that has an azo group, generates radicals that can harden (meth)acryloyloxy groups by heat, and has a number average molecular weight of 300 or more.

The number average molecular weight of the polymeric azo initiator is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more, and is preferably 300,000 or less, more preferably 100,000 or less, and even more preferably 90,000 or less. When the number average molecular weight of the polymeric azo initiator is equal to or greater than the lower limit, the polymeric azo initiator is less likely to adversely affect the liquid crystal. When the number average molecular weight of the polymeric azo initiator is equal to or less than the upper limit, it is easy to mix it into the thermosetting compound.

The number average molecular weight is a value determined by measuring using gel permeation chromatography (GPC) and converting it into polystyrene equivalent. Examples of columns used for GPC measurements include Shodex LF-804 (manufactured by Showa Denko KK).

The above-mentioned polymeric azo initiator may, for example, be a polymeric azo initiator having a structure in which multiple units such as polyalkylene oxide or polydimethylsiloxane are bonded via azo groups.

The polymeric azo initiator having a structure in which multiple units such as polyalkylene oxide are bonded via the azo group preferably has a polyethylene oxide structure. Examples of such polymeric azo initiators include polycondensates of 4,4'-azobis(4-cyanopentanoic acid) and polyalkylene glycol, and polycondensates of 4,4'-azobis(4-cyanopentanoic acid) and polydimethylsiloxane having a terminal amino group. Specific examples include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.).

Examples of the organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxy esters, diacyl peroxides, and peroxydicarbonates.

As the cationic polymerization initiator, a photocationic polymerization initiator can be suitably used. The photocationic polymerization initiator generates a protonic acid or a Lewis acid upon irradiation with light. The type of the photocationic polymerization initiator is not particularly limited, and may be an ionic photoacid generating type or a nonionic photoacid generating type.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts; iron-allene complexes; titanocene complexes; and organometallic complexes such as arylsilanol-aluminum complexes.

Commercially available examples of the above-mentioned cationic photopolymerization initiator include Adeka Optomer SP-150 and Adeka Optomer SP-170 (both manufactured by ADEKA Corporation).

The content of the polymerization initiator is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and preferably 30 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less, relative to 100 parts by weight of the thermosetting compound. When the content of the polymerization initiator is equal to or more than the lower limit, the sealant for liquid crystal display elements can be sufficiently cured. When the content of the polymerization initiator is equal to or less than the upper limit, the storage stability of the sealant for liquid crystal display elements is increased.

The above-mentioned heat curing agents include, for example, organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, and acid anhydrides. Organic acid hydrazides that are solid at 23°C are preferably used. Only one type of the above-mentioned heat curing agents may be used, or two or more types may be used in combination.

Examples of the organic acid hydrazides that are solid at 23°C include 1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide.

Commercially available organic acid hydrazides that are solid at 23°C include, for example, Amicure VDH and Amicure UDH (both manufactured by Ajinomoto Fine-Techno Co., Ltd.); SDH, IDH, ADH, and MDH (all manufactured by Otsuka Chemical Co., Ltd.).

The content of the heat curing agent is preferably 1 part by weight or more, preferably 50 parts by weight or less, and more preferably 30 parts by weight or less, relative to 100 parts by weight of the heat curing compound. When the content of the heat curing agent is equal to or more than the lower limit, the sealant for liquid crystal display elements can be sufficiently heat cured. When the content of the heat curing agent is equal to or less than the upper limit, the viscosity of the sealant for liquid crystal display elements does not become too high, and the applicability is good.

The above-mentioned sealant for liquid crystal display elements preferably contains a curing accelerator. By using the above-mentioned curing accelerator, the sealant can be cured sufficiently without heating at a high temperature.

Examples of the curing accelerator include polycarboxylic acids having an isocyanuric ring structure and epoxy resin amine adducts, and specific examples include tris(2-carboxymethyl)isocyanurate, tris(2-carboxyethyl)isocyanurate, tris(3-carboxypropyl)isocyanurate, and bis(2-carboxyethyl)isocyanurate.

The content of the curing accelerator is preferably 0.1 parts by weight or more, and preferably 10 parts by weight or less, per 100 parts by weight of the thermosetting compound. When the content of the curing accelerator is equal to or more than the lower limit, the sealant for liquid crystal display elements is sufficiently cured, and high temperature heating is not required for curing. When the content of the curing accelerator is equal to or less than the upper limit, the adhesiveness of the sealant for liquid crystal display elements is increased.

The above-mentioned sealant for liquid crystal display elements preferably contains a filler for the purposes of improving viscosity, improving adhesion through stress dispersion effects, improving the linear expansion coefficient, and improving the moisture resistance of the cured product.

Examples of the fillers include inorganic fillers such as talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, and aluminum nitride, and organic fillers such as polyester particles, polyurethane particles, vinyl polymer particles, acrylic polymer particles, and core-shell acrylate copolymer particles. Only one type of the above fillers may be used, or two or more types may be used in combination.

In 100% by weight of the sealant for liquid crystal display elements, the content of the filler is preferably 10% by weight or more, more preferably 20% by weight or more, and preferably 70% by weight or less, more preferably 60% by weight or less. When the content of the filler is equal to or greater than the lower limit, the effect of improving adhesion and the like is fully exerted. When the content of the filler is equal to or less than the upper limit, the viscosity of the sealant for liquid crystal display elements does not become too high, and the coatability is good.

The above-mentioned sealant for liquid crystal display elements preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly serves as an adhesive aid for favorably adhering the sealant to a substrate or the like. Only one type of silane coupling agent may be used, or two or more types may be used in combination.

The above-mentioned silane coupling agents are excellent in improving adhesion to the substrate, etc., and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin. For example, N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc. are preferred.

In 100% by weight of the sealant for liquid crystal display elements, the content of the silane coupling agent is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and preferably 20% by weight or less, more preferably 10% by weight or less. When the content of the silane coupling agent is equal to or more than the lower limit, the effect of blending the silane coupling agent is fully exerted. When the content of the silane coupling agent is equal to or less than the upper limit, contamination of the liquid crystal by the sealant for liquid crystal display elements is further suppressed.

The above-mentioned sealant for liquid crystal display elements may contain a light-shielding agent. By using the above-mentioned light-shielding agent, the sealant for liquid crystal display elements can be suitably used as a light-shielding sealant.

Examples of the light-blocking agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Titanium black is preferred.

Liquid crystal display elements manufactured using a sealant for liquid crystal display elements containing a light-blocking agent have sufficient light-blocking properties, making it possible to realize liquid crystal display elements with no light leakage, high contrast, and excellent image display quality.

The above-mentioned titanium black is a substance that has a higher transmittance for light near the ultraviolet region, particularly light with wavelengths of 370 to 450 nm, compared to the average transmittance for light with wavelengths of 300 to 800 nm. The above-mentioned titanium black has the property of imparting light-blocking properties to the sealant for liquid crystal display elements by sufficiently blocking light with wavelengths in the visible light region, while allowing light with wavelengths near the ultraviolet region to pass through. It is preferable that the light-blocking agent contained in the sealant for liquid crystal display elements has high insulating properties, and titanium black is a suitable light-blocking agent with high insulating properties.

The optical density (OD value) per 1 μm of the titanium black is preferably 3 or more, and more preferably 4 or more. The higher the light blocking ability of the titanium black, the better. There is no particular upper limit to the OD value of the titanium black, but the OD value is usually 5 or less.

The above titanium black and carbon black are sufficiently effective even without surface treatment. Surface-treated titanium black can also be used, such as titanium black whose surface has been treated with an organic component such as a coupling agent, or titanium black coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide. Titanium black treated with an organic component is preferred, as it can enhance insulation.

Commercially available titanium black products include, for example, 12S, 13M, 13M-C, 13R-N, and 14M-C (all manufactured by Mitsubishi Materials Corporation); Tilac D (manufactured by Ako Kasei Co., Ltd.), etc.

The specific surface area of the titanium black is preferably 13 m ² /g or more, more preferably 15 m ² /g or more, and is preferably 30 m ² /g or less, more preferably 25 m ² /g or less.

The volume resistivity of the titanium black is preferably 0.5 Ω·cm or more, more preferably 1 Ω·cm or more, and is preferably 3 Ω·cm or less, more preferably 2.5 Ω·cm or less.

The primary particle diameter of the light-shielding agent affects the distance between two liquid crystal display element members. The primary particle diameter of the light-shielding agent is preferably 1 nm or more, more preferably 5 nm or more, even more preferably 10 nm or more, and is preferably 5 μm or less, more preferably 200 nm or less, even more preferably 100 nm or less. If the primary particle diameter of the light-shielding agent is equal to or greater than the lower limit, the viscosity and thixotropy of the sealant for liquid crystal display elements are unlikely to increase significantly, and workability is improved. If the primary particle diameter of the light-shielding agent is equal to or less than the upper limit, the coatability of the sealant for liquid crystal display elements is improved.

The content of the light-shielding agent is preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 30% by weight or more, and preferably 80% by weight or less, more preferably 70% by weight or less, and even more preferably 60% by weight or less, based on 100 parts by weight of the thermosetting compound. When the content of the light-shielding agent is equal to or greater than the lower limit, sufficient light-shielding properties are obtained. When the content of the light-shielding agent is equal to or less than the upper limit, the adhesion and post-curing strength of the sealant for liquid crystal display elements are improved, and the drawability is further improved.

The above-mentioned sealant for liquid crystal display elements may contain, as necessary, a stress relaxation agent, a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other additives.

The method for producing the above-mentioned sealant for liquid crystal display elements is not particularly limited, and examples include a method in which a thermosetting compound, a polymerization initiator or a thermosetting agent, silicone particles, and additives such as a silane coupling agent, which are added as necessary, are mixed using a mixer such as a homodisper, homomixer, universal mixer, planetary mixer, kneader, or three-roll mixer.

The viscosity of the sealant for liquid crystal display elements at 25°C and 1 rpm is preferably 50,000 Pa·s or more, preferably 500,000 Pa·s or less, and more preferably 400,000 Pa·s or less. If the viscosity is equal to or greater than the lower limit and equal to or less than the upper limit, the applicability of the sealant for liquid crystal display elements is good. The viscosity is measured using an E-type viscometer.

(Liquid crystal display element)
A liquid crystal display element can be obtained by using the sealant for liquid crystal display elements. The liquid crystal display element includes a first member for liquid crystal display elements, a second member for liquid crystal display elements, a seal portion that seals the outer periphery of the first member for liquid crystal display elements and the second member for liquid crystal display elements in a state in which the first member for liquid crystal display elements and the second member for liquid crystal display elements face each other, and liquid crystal disposed inside the seal portion between the first member for liquid crystal display elements and the second member for liquid crystal display elements. In this liquid crystal display element, a liquid crystal dropping method is applied, and the seal portion is formed by thermally curing a sealant for the liquid crystal dropping method. The seal portion is a thermoset product of the sealant for the liquid crystal dropping method.

Figure 1 is a cross-sectional view showing a schematic example of a liquid crystal display element using silicone particles.

A liquid crystal display element 1 shown in FIG. 1 has a pair of transparent glass substrates 2. The transparent glass substrates 2 have insulating films (not shown) on opposing surfaces. Examples of materials for the insulating films include _SiO2 and the like. A transparent electrode 3 is formed on the insulating film on the transparent glass substrate 2. Examples of materials for the transparent electrode 3 include ITO and the like. The transparent electrode 3 can be formed, for example, by patterning using photolithography. An alignment film 4 is formed on the transparent electrode 3 on the surface of the transparent glass substrate 2. Examples of materials for the alignment film 4 include polyimide and the like.

A liquid crystal 5 is sealed between the pair of transparent glass substrates 2. A plurality of spacer particles 7 are arranged between the pair of transparent glass substrates 2. The plurality of spacer particles 7 regulate the distance between the pair of transparent glass substrates 2. A seal portion 6 is arranged between the peripheral edges of the pair of transparent glass substrates 2. The seal portion 6 prevents the liquid crystal 5 from leaking out. The seal portion 6 contains silicone particles 6A. In the liquid crystal display element 1, the member located above the liquid crystal 5 is the first liquid crystal display element member, and the member located below the liquid crystal is the second liquid crystal display element member.

Note that the liquid crystal display element shown in FIG. 1 is just one example, and the structure of the liquid crystal display element can be modified as appropriate.

(Connection structure)
The silicone particles have a conductive layer formed on the surface thereof, and are used to obtain conductive particles having the conductive layer. The conductive particles or the conductive material containing the conductive particles and the binder resin described above can be used to connect the connection target members to obtain a connection structure.

The connection structure preferably includes a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member, and the connection portion is formed from the conductive particles described above, or is formed from a conductive material containing the conductive particles and a binder resin described above. When the conductive particles are used alone, the connection portion itself is a conductive particle. In other words, the first and second connection target members are connected by the conductive particles. The conductive material used to obtain the connection structure is preferably an anisotropic conductive material.

The first connection target member preferably has a first electrode on its surface. The second connection target member preferably has a second electrode on its surface. The first electrode and the second electrode are preferably electrically connected by the conductive particles.

Figure 2 is a schematic front cross-sectional view of an example of a connection structure using conductive particles.

The connection structure 51 shown in FIG. 2 includes a first connection target member 52, a second connection target member 53, and a connection portion 54 connecting the first connection target member 52 and the second connection target member 53. The connection portion 54 is formed of a conductive material including conductive particles 54A and a binder resin. The connection portion 54 includes conductive particles 54A. The conductive particles 54A include silicone particles and a conductive layer disposed on the surface of the silicone particles. In FIG. 2, the conductive particles 54A are shown diagrammatically for convenience of illustration.

The first connection target member 52 has a plurality of first electrodes 52a on its surface (upper surface). The second connection target member 53 has a plurality of second electrodes 53a on its surface (lower surface). The first electrode 52a and the second electrode 53a are electrically connected by one or more conductive particles 1. Therefore, the first and second connection target members 52, 53 are electrically connected by the conductive particles 1.

The method for producing the connection structure is not particularly limited. One example of the method for producing the connection structure is to place the conductive material between a first connection target member and a second connection target member, obtain a laminate, and then heat and press the laminate. The pressure of the pressurization is about 9.8×10 ⁴ to 4.9×10 ⁶ Pa. The heating temperature is about 120 to 220° C. The pressure of the pressurization for connecting the electrodes of the flexible printed circuit board, the electrodes arranged on the resin film, and the electrodes of the touch panel is about 9.8×10 ⁴ to 1.0×10 ⁶ Pa.

Specific examples of the connection target components include electronic components such as semiconductor chips, capacitors, and diodes, as well as circuit boards such as printed circuit boards, flexible printed circuit boards, glass epoxy boards, and glass boards. The conductive material is preferably a conductive material for connecting electronic components. The conductive paste is preferably a conductive material in a paste form, and is preferably applied in a paste form to the connection target components.

The conductive particles and conductive materials are also suitable for use in touch panels. Therefore, the connection target member is preferably a flexible substrate, or a connection target member having electrodes arranged on the surface of a resin film. The connection target member is preferably a flexible substrate, and is preferably a connection target member having electrodes arranged on the surface of a resin film. When the flexible substrate is a flexible printed circuit board or the like, the flexible substrate generally has electrodes on its surface.

The electrodes provided on the connection target members include metal electrodes such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, copper electrodes, silver electrodes, molybdenum electrodes, and tungsten electrodes. When the connection target members are flexible substrates, the electrodes are preferably gold electrodes, nickel electrodes, tin electrodes, or copper electrodes. When the connection target members are glass substrates, the electrodes are preferably aluminum electrodes, copper electrodes, molybdenum electrodes, or tungsten electrodes. When the electrodes are aluminum electrodes, they may be electrodes made of aluminum only, or may be electrodes in which an aluminum layer is laminated on the surface of a metal oxide layer. Examples of materials for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.

(Electronic component device)
The silicone particles can be disposed between the first ceramic member and the second ceramic member on the outer periphery of the first ceramic member and the second ceramic member, and can also be used as a gap control material.

Figure 3 is a cross-sectional view showing a schematic example of an electronic component device using silicone particles. Figure 4 is a cross-sectional view showing an enlarged view of a joint portion (the area surrounded by the dashed line in Figure 3) in the electronic component device shown in Figure 3.

The electronic component device 71 shown in Figures 3 and 4 includes a first ceramic member 72, a second ceramic member 73, a joint 74, an electronic component 75, and a lead frame 76.

The first and second ceramic members 72 and 73 are each formed of a ceramic material. The first and second ceramic members 72 and 73 are, for example, a housing. The first ceramic member 72 is, for example, a substrate. The second ceramic member 73 is, for example, a lid. The first ceramic member 72 has a convex portion protruding toward the second ceramic member 73 side (upper side) on the outer periphery. The first ceramic member 72 has a concave portion on the second ceramic member 73 side (upper side) that forms an internal space R for storing an electronic component 75. The first ceramic member 72 does not have to have a convex portion. The second ceramic member 73 has a convex portion protruding toward the first ceramic member 72 side (lower side) on the outer periphery. The second ceramic member 73 has a concave portion on the first ceramic member 72 side (lower side) that forms an internal space R for storing an electronic component 75. The second ceramic member 73 does not have to have a convex portion.

The joint 74 joins the outer periphery of the first ceramic member 72 to the outer periphery of the second ceramic member 73. Specifically, the joint 74 joins the convex portion of the outer periphery of the first ceramic member 72 to the convex portion of the outer periphery of the second ceramic member 73.

A package is formed by first and second ceramic members 72, 73 joined by a joint 74. The package forms an internal space R. The joint 74 seals the internal space R liquid-tightly and air-tightly. The joint 74 is a sealing part.

The electronic components 75 are disposed within the internal space R of the package. Specifically, the electronic components 75 are disposed on the first ceramic member 72. In this embodiment, two electronic components 75 are used.

The bonding portion 74 includes a plurality of silicone particles 74A and glass 74B. The bonding portion 74 is formed using a bonding material that includes a plurality of particles 74A that are different from glass particles and glass 74B. This bonding material is a bonding material for ceramic packages.

The bonding material may contain a solvent or may contain a resin. At the bonding portion 74, glass 74B such as glass particles is melted and bonded, and then solidified.

The electronic components include sensor elements, MEMS, and bare chips. The sensor elements include pressure sensor elements, acceleration sensor elements, CMOS sensor elements, and CCD sensor elements.

The lead frame 76 is disposed between the outer periphery of the first ceramic member 72 and the outer periphery of the second ceramic member 73. The lead frame 76 extends to the internal space R side and the external space side of the package. The terminals of the electronic component 75 and the lead frame 76 are electrically connected via wires.

The joint 74 partially directly joins the outer periphery of the first ceramic member 72 and the outer periphery of the second ceramic member 73, and partially indirectly joins them. Specifically, the joint 74 indirectly joins the outer periphery of the first ceramic member 72 and the outer periphery of the second ceramic member 73 via the lead frame 76 in the portion where the lead frame 76 is located between the outer periphery of the first ceramic member 72 and the outer periphery of the second ceramic member 73. In the portion where the lead frame 76 is located between the outer periphery of the first ceramic member 72 and the outer periphery of the second ceramic member 73, the first ceramic member 72 is in contact with the lead frame 76, the lead frame 76 is in contact with the first ceramic member 72 and the joint 74, the joint 74 is in contact with the lead frame 76 and the second ceramic member 73, and the second ceramic member 73 is in contact with the joint 74. The joint 74 directly joins the outer periphery of the first ceramic member 72 to the outer periphery of the second ceramic member 73 in a portion where there is no lead frame 76 between the outer periphery of the first ceramic member 72 and the outer periphery of the second ceramic member 73. The joint 74 contacts the first ceramic member 72 and the second ceramic member 73 in a portion where there is no lead frame 76 between the outer periphery of the first ceramic member 72 and the outer periphery of the second ceramic member 73.

In the portion where the lead frame 76 is located between the outer periphery of the first ceramic member 72 and the outer periphery of the second ceramic member 73, the gap distance between the outer periphery of the first ceramic member 72 and the outer periphery of the second ceramic member 73 is controlled by a plurality of particles 74A contained in the joint 74.

The joint may be any joint that directly or indirectly joins the outer periphery of the first ceramic member to the outer periphery of the second ceramic member. Note that electrical connection methods other than the lead frame may also be used.

Like electronic component device 71, the electronic component device includes, for example, a first ceramic member formed of a ceramic material, a second ceramic member formed of a ceramic material, a joint, and an electronic component, the joint directly or indirectly joining the outer periphery of the first ceramic member to the outer periphery of the second ceramic member, a package is formed by the first and second ceramic members joined by the joint, the electronic component is disposed within the internal space of the package, and the joint includes a plurality of silicone particles and glass.

Furthermore, like the bonding material used in the electronic component device 71, the ceramic package bonding material is used to form the bonding portion in the electronic component device, and contains silicone particles and glass.
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

( Reference Example 1)
(1) Preparation of Silicone Oligomer 1 part by weight of 1,3-divinyltetramethyldisiloxane and 20 parts by weight of 0.5% by weight p-toluenesulfonic acid aqueous solution were placed in a 100 ml separable flask placed in a warm bath. After stirring at 40°C for 1 hour, 0.05 parts by weight of sodium bicarbonate was added. Then, 10 parts by weight of dimethoxymethylphenylsilane, 49 parts by weight of dimethyldimethoxysilane, 0.6 parts by weight of trimethylmethoxysilane, and 3.6 parts by weight of methyltrimethoxysilane were added and stirred for 1 hour. Then, 1.9 parts by weight of 10% by weight potassium hydroxide aqueous solution was added, and the temperature was raised to 85°C, and the mixture was stirred and reacted for 10 hours while reducing the pressure with an aspirator. After the reaction was completed, the pressure was returned to normal pressure and cooled to 40°C, 0.2 parts by weight of acetic acid was added, and the mixture was left to stand in a separatory funnel for 12 hours or more. The lower layer after the two-layer separation was taken out and purified with an evaporator to obtain a silicone oligomer.

(2) Preparation of Silicone Particles (Containing Organic Polymer) 0.5 parts by weight of tert-butyl-2-ethylperoxyhexanoate (polymerization initiator, NOF Corp.'s "Perbutyl O") was dissolved in 30 parts by weight of the obtained silicone oligomer to prepare a solution A. In addition, 0.8 parts by weight of polyoxyethylene alkylphenyl ether (emulsifier) and 80 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol (polymerization degree: about 2000, saponification degree: 86.5 to 89 mol%, Nippon Synthetic Chemical Industry Co., Ltd.'s "GOHSENOL GH-20") were mixed with 150 parts by weight of ion-exchanged water to prepare an aqueous solution B.

The above-mentioned solution A was placed in a separable flask placed in a warm bath, and then the above-mentioned aqueous solution B was added. Then, emulsification was performed using a Shirasu Porous Glass (SPG) membrane (average pore size: approximately 5 μm). The temperature was then raised to 85°C, and polymerization was performed for 9 hours. After the entire amount of particles after polymerization was washed with water by centrifugation, the particles were dispersed again in 100 parts by weight of ion-exchanged water to obtain a dispersion liquid. Next, 0.7 parts by weight of colloidal silica (Nissan Chemical Industries, Ltd.'s "MP-2040") was added to the dispersion liquid, which was then freeze-dried to obtain base particles. The obtained base particles were classified to obtain silicone particles with an average particle size of 6.8 μm.

( Reference Example 2)
Silicone particles were obtained in the same manner as in Reference Example 1, except that 49 parts by weight of dimethyldimethoxysilane was changed to 49 parts by weight of a reactive silicone oil modified with carbinol at both ends ("KF-6001" manufactured by Shin-Etsu Chemical Co., Ltd.).

( Reference Example 3)
Silicone particles were obtained in the same manner as in Reference Example 1, except that 3.6 parts by weight of methyltrimethoxysilane was changed to 3.6 parts by weight of tetraethoxysilane.

( Reference Example 4)
Silicone particles were obtained in the same manner as in Reference Example 1, except that 3.6 parts by weight of methyltrimethoxysilane was changed to 3.6 parts by weight of phenyltrimethoxysilane.

( Reference Example 5)
Silicone particles were obtained in the same manner as in Reference Example 1, except that 1 part by weight of 1,3-divinyltetramethyldisiloxane was replaced with 1.2 parts by weight of 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane.

( Reference Example 6)
Silicone particles were obtained in the same manner as in Reference Example 1, except that the Shirasu Porous Glass (SPG) membrane (average pore size: about 5 μm) was changed to a membrane with an average pore size of 1 μm.

( Reference Example 7)
A solution A was prepared by dissolving 0.5 parts by weight of tert-butyl-2-ethylperoxyhexanoate (polymerization initiator, NOF Corp.'s "Perbutyl O") in 20 parts by weight of both-end acrylic silicone oil and 10 parts by weight of p-styryltrimethoxysilane. In addition, 0.8 parts by weight of a 40% by weight aqueous solution of triethanolamine lauryl sulfate (emulsifier) and 80 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol (polymerization degree: about 2000, saponification degree: 86.5 to 89 mol%, Nippon Synthetic Chemical Industry Co., Ltd.'s "Gosenol GH-20") were mixed with 150 parts by weight of ion-exchanged water to prepare an aqueous solution B. The above-mentioned solution A was placed in a separable flask placed in a warm bath, and then the above-mentioned aqueous solution B was added. Thereafter, emulsification was performed using a Shirasu Porous Glass (SPG) membrane (average pore size about 20 μm). The temperature was then raised to 85° C., and polymerization was carried out for 9 hours. After polymerization, the entire amount of particles was washed with water by centrifugation, and then classified to obtain silicone particles A.

6.5 parts by weight of the obtained silicone particles A, 0.6 parts by weight of hexadecyltrimethylammonium bromide, 240 parts by weight of distilled water, and 120 parts by weight of methanol were placed in a 500 ml separable flask placed in a warm bath. After stirring at 40°C for 1 hour, 3.0 parts by weight of divinylbenzene and 0.5 parts by weight of styrene were added, the temperature was raised to 75°C, and stirring was continued for 0.5 hours. After that, 0.4 parts by weight of 2,2'-azobis(isobutyrate)dimethyl was added and the reaction was continued with stirring for 8 hours. The entire amount of particles after polymerization was washed with water by centrifugation to obtain silicone particles.

(Comparative Example 1)
Silicone particles were obtained in the same manner as in Reference Example 1, except that 10 parts by weight of methoxymethylphenylsilane was not added.

(Comparative Example 2)
Silicone particles were synthesized in the same manner as in Reference Example 1, except that 1,3-divinyltetramethyldisiloxane, p-toluenesulfonic acid, and tert-butyl-2-ethylperoxyhexanoate were not added, and the resulting particles were in a gel state.

(Comparative Example 3)
A mixed solution of 150 parts by weight of ion-exchanged water, 0.8 parts by weight of polyoxyethylene alkylphenyl ether, and 80 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol (degree of polymerization: about 2000, degree of saponification: 86.5 to 89 mol%, "GOHSENOL GH-20" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was prepared.

40 parts by weight of dimethyldimethoxysilane, 10 parts by weight of dimethylphenylmethoxysilane, and 2 parts by weight of methylhydrogensiloxane were mixed at room temperature, and the entire amount of the above mixture was added. Then, emulsification was performed using a Shirasu Porous Glass (SPG) membrane (average pore size: approximately 5 μm). This was transferred to a separable flask and cooled to 15°C while stirring, after which 0.1 parts by weight of a toluene solution of chloroplatinic acid-olefin complex was added and stirred for 12 hours to obtain silicone particles.

(evaluation)
(1) Particle Size of Silicone Particles The particle sizes of the obtained silicone particles were measured using a laser diffraction particle size distribution measuring device (Malvern Instruments "Mastersizer 2000"), and the average value was calculated.

(2) Compressive elastic modulus of silicone particles (30% K value)
The compressive elastic modulus (30% K value) of the resulting silicone particles was measured at 23° C. by the method described above using a microcompression tester (Fisherscope H-100, manufactured by Fischer).

(3) Liquid crystal contamination prevention properties Preparation of sealant for liquid crystal dropping method:
50 parts by weight of bisphenol A type epoxy methacrylate (thermosetting compound, Daicel-Allnex Corporation's "KRM7985"), 20 parts by weight of caprolactone-modified bisphenol A type epoxy acrylate (thermosetting compound, Daicel-Allnex Corporation's "EBECRYL3708"), 30 parts by weight of partially acrylic-modified bisphenol E type epoxy resin (thermosetting compound, Daicel-Allnex Corporation's "KRM8276"), and 2,2-dimethoxy-2-phenylacetophenone (photoradical polymerization initiator, BASF A mixture of 2 parts by weight of malonic acid dihydrazide (thermosetting agent, "MDH" manufactured by Otsuka Chemical Co., Ltd.), 30 parts by weight of the obtained silicone particles, 20 parts by weight of silica (filler, "Admafine SO-C2" manufactured by Admatechs Co., Ltd.), 2 parts by weight of 3-glycidoxypropyltrimethoxysilane (silane coupling agent, "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.), and core-shell acrylate copolymer fine particles (stress relaxation agent, "F351" manufactured by Zeon Kasei Co., Ltd.) was mixed and stirred with a planetary mixer ("Awatori Rentaro" manufactured by Thinky Corporation), and then uniformly mixed with a ceramic triple roll to obtain a sealant for liquid crystal display elements.

Preparation of liquid crystal display element:
One part by weight of spacer particles ("Micropearl SP-2050" manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 5 μm was uniformly dispersed in 100 parts by weight of each of the obtained sealants for liquid crystal display elements using a planetary stirring device, and the obtained spacer-containing sealant was filled into a dispenser syringe ("PSY-10E" manufactured by Musashi Engineering Co., Ltd.) and degassed. After that, the sealant was applied to a transparent electrode substrate with an ITO thin film using a dispenser ("SHOTMASTER300" manufactured by Musashi Engineering Co., Ltd.) so as to draw a rectangular frame. Next, minute droplets of TN liquid crystal ("JC-5001LA" manufactured by Chisso Corporation) were dropped and applied using a liquid crystal dropping device, and the other transparent substrate was attached under a vacuum of 5 Pa using a vacuum attachment device. The laminated cell was irradiated with ultraviolet light of 100 mW/cm ² using a metal halide lamp for 30 seconds, and then heated at 120° C. for 1 hour to thermally cure the sealant, thereby obtaining a liquid crystal display element (cell gap 5 μm).

Evaluation method for preventing liquid crystal contamination:
The obtained liquid crystal display element was visually observed for display unevenness occurring in the liquid crystal around the sealed portion (particularly in the corner portion), and the liquid crystal contamination prevention property was judged according to the following criteria.

[Criteria for determining anti-contamination properties of liquid crystal]
○: No display unevenness at all ○: Very slight display unevenness △: Noticeable display unevenness ×: Severe display unevenness

(4) Low moisture permeability (evaluation of color unevenness of a liquid crystal display element after storage under high temperature and high humidity conditions)
The liquid crystal display element obtained in the above evaluation (3) was prepared.

Evaluation method for low moisture permeability:
The obtained liquid crystal display element was stored for 72 hours under an environment of a temperature of 80° C. and a humidity of 90% RH, and then driven with a voltage of AC 3.5 V, and the periphery of the intermediate tone sealant was visually observed. The low moisture permeability was evaluated according to the following criteria.

[Criteria for determining low moisture permeability]
○: No color unevenness around the seal ○: Very slight color unevenness △: Noticeable color unevenness ×: Severe color unevenness

(5) Chemical resistance 10 parts by weight of the obtained silicone particles were weighed into a glass bottle, and 100 parts by weight of various solvents were added thereto and shaken in a bath at 30°C for 24 hours. After 24 hours, the silicone particles were removed by filtration and freeze-dried for 72 hours. The weight of the sample after drying was measured to evaluate the weight loss.

The results are shown in Table 1 below.

REFERENCE SIGNS LIST 1 liquid crystal display element 2 transparent glass substrate 3 transparent electrode 4 alignment film 5 liquid crystal 6 sealing portion 6A silicone particles 7 spacer particles 51 connection structure 52 first connection target member 52a first electrode 53 second connection target member 53a second electrode 54 connection portion 54A conductive particles 71 electronic component device 72 first ceramic member 73 second ceramic member 74 joint portion 74A silicone particles 74B glass 75 electronic component 76 lead frame R internal space

Claims (7)

Silicone particles having a particle diameter of 0.1 μm or more and 500 μm or less and containing a light-shielding agent,
The silicone particles are silicone particles obtained by reacting a silane compound having a radically polymerizable group bonded to a silicon atom with a silane compound having a hydrophobic group having 5 or more carbon atoms bonded to a silicon atom to form a siloxane bond, and then subjecting the radically polymerizable group to a radical polymerization reaction using a radical polymerization initiator, or by reacting a silane compound having a radically polymerizable group bonded to a silicon atom and a hydrophobic group having 5 or more carbon atoms bonded to the silicon atom to form a siloxane bond, and then subjecting the radically polymerizable group to a radical polymerization reaction using a radical polymerization initiator. 2. The silicone particle according to claim 1 , which is a silicone particle having a dimethylsiloxane skeleton in which two methyl groups are bonded to one silicon atom. 3. The silicone particles according to claim 1 or 2 , which have a compressive modulus of elasticity of 500 N/mm2 ^or less when compressed by 30% at 23°C. 4. The silicone particles according to claim 1, which are silicone particles containing no metal catalyst or no more than 100 ppm of a metal catalyst. A method for producing the silicone particles according to any one of claims 1 to 4 , comprising the steps of:
A method for producing silicone particles, comprising the steps of: reacting a silane compound having a radically polymerizable group bonded to a silicon atom with a silane compound having a hydrophobic group having 5 or more carbon atoms bonded to a silicon atom to form a siloxane bond, and then subjecting the radically polymerizable group to a radical polymerization reaction using a radical polymerization initiator, thereby obtaining silicone particles; or reacting a silane compound having a radically polymerizable group bonded to a silicon atom and a hydrophobic group having 5 or more carbon atoms bonded to the silicon atom to form a siloxane bond, and then subjecting the radically polymerizable group to a radical polymerization reaction using a radical polymerization initiator, thereby obtaining silicone particles. A thermosetting component;
A sealant for a liquid crystal dropping method, comprising the silicone particles according to any one of claims 1 to 4 . A first liquid crystal display member;
A second liquid crystal display member;
a seal portion that seals the outer periphery of the first liquid crystal display member and the second liquid crystal display member in a state in which the first liquid crystal display member and the second liquid crystal display member face each other;
a liquid crystal disposed between the first liquid crystal display member and the second liquid crystal display member on the inner side of the seal portion,
The sealing portion is formed by thermally curing a sealing agent for a liquid crystal dropping method,
A liquid crystal display element, wherein the sealing agent for the liquid crystal dropping method comprises a thermosetting component and the silicone particle according to any one of claims 1 to 4 .

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