WO2014087984A1

WO2014087984A1 - Organic-inorganic hybrid particles, conductive particles, conductive material and connection structure

Info

Publication number: WO2014087984A1
Application number: PCT/JP2013/082422
Authority: WO
Inventors: 恭幸山田
Original assignee: 積水化学工業株式会社
Priority date: 2012-12-06
Filing date: 2013-12-03
Publication date: 2014-06-12
Also published as: JP5699230B2; TWI506076B; JPWO2014087984A1; TW201434898A; KR20150023064A; KR101538904B1; CN104718241B; CN104718241A

Abstract

Provided are organic-inorganic hybrid particles which have high breaking load when compressed and have good compressive deformation characteristics. Organic-inorganic hybrid particles of the present invention are obtained using a plurality of inorganic particles, each of which has a first reactive functional group on the surface, and an alkoxy group-containing organopolysiloxane, which has a second reactive functional group that is reactive with the first reactive functional group. The organic-inorganic hybrid particles are aggregates of the inorganic particles.

Description

Organic-inorganic hybrid particles, conductive particles, conductive materials, and connection structures

The present invention relates to an organic-inorganic hybrid particle that is an aggregate of a plurality of inorganic particles. The present invention also relates to conductive particles, conductive materials and connection structures using the organic-inorganic hybrid particles.

Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known. In the anisotropic conductive material, conductive particles are dispersed in a binder resin. The anisotropic conductive material is used to electrically connect electrodes of various connection target members such as a flexible printed circuit (FPC), a glass substrate, and a semiconductor chip to obtain a connection structure. In addition, conductive particles having resin particles and a conductive layer disposed on the surface of the resin particles may be used as the conductive particles.

As an example of the resin particles used for the conductive particles, the following Patent Document 1 discloses polymer particles having a breaking point load of 9.8 mN or less. In Patent Document 1, as a preferred embodiment of the polymer particles, (a) inorganic particles formed of metal oxides such as silica, alumina, and titania, metal nitrides, metal sulfides, metal carbides, etc. (B) (b) an aspect in which a metalloxane chain (a molecular chain containing a “metal-oxygen-metal” bond) such as (organo) polysiloxane and polytitanoxane is combined with an organic molecule at a molecular level; c) The aspect etc. which are organic inorganic polymer particles containing a vinyl polymer frame | skeleton and a polysiloxane skeleton are mentioned.

Further, the liquid crystal display element is configured by arranging liquid crystal between two glass substrates. In the liquid crystal display element, a spacer is used as a gap control material in order to keep the distance (gap) between two glass substrates uniform and constant. As the spacer, resin particles are generally used.

As an example of the resin particles used for the conductive particles or the liquid crystal display element spacers, Patent Document 2 listed below contains a polyfunctional silane compound having a polymerizable unsaturated group in the presence of a surfactant. Organic-inorganic hybrid particles obtained by decomposition and polycondensation are disclosed. In Patent Document 2, the polyfunctional silane compound is at least one radical polymerizable group-containing first silicon compound selected from a compound represented by the following formula (X) and a derivative thereof.

In the above formula (X), R1 represents a hydrogen atom or a methyl group, R2 represents an optionally substituted divalent organic group having 1 to 20 carbon atoms, and R3 represents a carbon atom having 1 to 5 carbon atoms. R 4 represents an alkyl group or a phenyl group, and R 4 represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.

WO2012 / 020799A1 JP 2000-204119 A

In conventional organic-inorganic hybrid particles as described in

Patent Documents

1 and 2, the breaking load during compression may be low.

For this reason, when the organic-inorganic hybrid particles are used as spacers for liquid crystal display elements and placed between substrates, or a conductive layer is formed on the surface and used as conductive particles to electrically connect electrodes. When an impact is applied to the liquid crystal display element using the liquid crystal display element spacer and the connection structure using the conductive particles, the liquid crystal display element spacer or the conductive particles may be cracked or damaged. .

An object of the present invention is to provide an organic-inorganic hybrid particle having a high compressive load and a good compressive deformation characteristic, and conductive particles, a conductive material, and a connection structure using the organic-inorganic hybrid particle. is there.

According to a wide aspect of the present invention, a plurality of inorganic particles having a first reactive functional group on the surface, and an alkoxy group containing a second reactive functional group capable of reacting with the first reactive functional group Organic-inorganic hybrid particles that are obtained using organopolysiloxane and are aggregates of the inorganic particles are provided.

In a specific aspect of the organic-inorganic hybrid particle according to the present invention, the first reactive functional group is a hydroxyl group.

In a specific aspect of the organic-inorganic hybrid particle according to the present invention, the alkoxy group-containing organopolysiloxane has an epoxy group or a (meth) acryloyl group as the second reactive functional group.

In a specific aspect of the organic-inorganic hybrid particle according to the present invention, the alkoxy group-containing organopolysiloxane has an epoxy group as the second reactive functional group.

In a specific aspect of the organic-inorganic hybrid particle according to the present invention, a plurality of the inorganic particles are integrated through a structure derived from the alkoxy group-containing organopolysiloxane to obtain an aggregate of the inorganic particles. ing.

In a specific aspect of the organic-inorganic hybrid particle according to the present invention, the alkoxy group-containing organopolysiloxane has a methoxy group as the second reactive functional group.

In a specific aspect of the organic-inorganic hybrid particle according to the present invention, the alkoxy group-containing organopolysiloxane has an alkyl group directly bonded to a silicon atom.

The organic-inorganic hybrid particles according to the present invention are preferably used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer, or used as spacers for liquid crystal display elements.

According to a wide aspect of the present invention, there is provided conductive particles comprising the organic-inorganic hybrid particles described above and a conductive layer disposed on the surface of the organic-inorganic hybrid particles.

According to a wide aspect of the present invention, the conductive particles include a binder resin, and the conductive particles include the organic-inorganic hybrid particles described above, and a conductive layer disposed on the surface of the organic-inorganic hybrid particles. A conductive material is provided.

According to a wide aspect of the present invention, a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, and the A connection portion connecting the second connection target member, and the connection portion is formed of conductive particles or formed of a conductive material including the conductive particles and a binder resin. The conductive particles include the organic-inorganic hybrid particles described above and a conductive layer disposed on the surface of the organic-inorganic hybrid particles, and the first electrode and the second electrode are the conductive particles. To provide a connection structure that is electrically connected.

The organic-inorganic hybrid particle according to the present invention includes a plurality of inorganic particles having a first reactive functional group on the surface, and an alkoxy group having a second reactive functional group capable of reacting with the first reactive functional group. Since it is an aggregate of the inorganic particles obtained using the organopolysiloxane, the organic-inorganic hybrid particles have high compressive deformation characteristics due to high breaking load during compression.

FIG. 1 is a cross-sectional view schematically showing organic-inorganic hybrid particles according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing conductive particles using the organic-inorganic hybrid particles shown in FIG. FIG. 3 is a cross-sectional view schematically showing a modification of the conductive particles using the organic-inorganic hybrid particles shown in FIG. FIG. 4 is a cross-sectional view schematically showing a connection structure using the conductive particles shown in FIG. FIG. 5 is a cross-sectional view schematically showing a liquid crystal display element using the organic-inorganic hybrid particles shown in FIG. 1 as a spacer for a liquid crystal display element.

Hereinafter, the present invention will be described in detail.

(Organic inorganic hybrid particles)
The organic-inorganic hybrid particle according to the present invention includes a plurality of inorganic particles having a first reactive functional group on the surface, and an alkoxy group having a second reactive functional group capable of reacting with the first reactive functional group. It is obtained using the containing organopolysiloxane. The organic-inorganic hybrid particle according to the present invention is an aggregate of the inorganic particles.

Since the organic-inorganic hybrid particles according to the present invention have the above-described configuration, organic-inorganic hybrid particles having a high breaking load during compression can be obtained. Since the organic-inorganic hybrid particles have a high breaking load during compression, the organic-inorganic hybrid particles have good compression deformation characteristics. In order to obtain the organic-inorganic hybrid particles according to the present invention, the breaking load is effectively increased by using the alkoxy group-containing organopolysiloxane separately from the inorganic particles. For this reason, when the organic-inorganic hybrid particles are used as spacers for liquid crystal display elements and placed between substrates, or a conductive layer is formed on the surface and used as conductive particles to electrically connect electrodes. When an impact is applied to the liquid crystal display element using the liquid crystal display element spacer and the connection structure using the conductive particles, the liquid crystal display element spacer or the conductive particles are hardly cracked or damaged.

Hereinafter, the present invention will be clarified by describing specific embodiments of the present invention with reference to the drawings.

FIG. 1 is a cross-sectional view schematically showing organic-inorganic hybrid particles according to the first embodiment of the present invention.

The organic-inorganic hybrid particle 1 shown in FIG. 1 has a plurality of inorganic particles 11 and a structure portion 12 derived from an alkoxy group-containing organopolysiloxane. The organic-inorganic hybrid particle 1 is an aggregate of inorganic particles 11. The structure part 12 is a substance different from the inorganic particles 11.

In order to obtain the inorganic particles 11, inorganic particles having a first reactive functional group on the surface are used. In order to obtain the structure portion 12, an alkoxy group-containing organopolysiloxane having a second reactive functional group capable of reacting with the first reactive functional group is used. The organic-inorganic hybrid particle 1 includes an inorganic particle having a first reactive functional group on its surface, an alkoxy group-containing organopolysiloxane having a second reactive functional group capable of reacting with the first reactive functional group, and Is obtained.

The structural portion 12 is disposed on the surface of the inorganic particles 11. The structure part 12 exists between the plurality of inorganic particles 11. The plurality of inorganic particles 11 are preferably integrated via a structure (structure part 12) derived from an alkoxy group-containing organopolysiloxane. It is preferable that the aggregate | assembly of the inorganic particle 11 is obtained by integrating the some inorganic particle 11 via the structure (structure part 12) derived from an alkoxy group containing organopolysiloxane. The structure part 12 preferably binds a plurality of inorganic particles 11.

Examples of the inorganic particles include particles formed of metal oxides, metal nitrides, metal sulfides, metal carbides, and composites thereof. Examples of the metal oxide include silica, alumina, and titania. Especially, it is preferable that the said inorganic particle is a silica particle.

The main component of the inorganic particles is an inorganic substance. If the said inorganic particle is a small quantity, it may contain the carbon atom. The content of carbon atoms in 100% by weight of the inorganic particles is preferably 20% by weight or less, more preferably 10% by weight or less. Particles containing a small amount of carbon atoms are also included in the inorganic particles.

Examples of the first reactive functional group include a hydroxyl group, an alkoxy group, an epoxy group, a (meth) acryloyl group, an amino group, a mercapto group, and an isocyanate group. Among these, a hydroxyl group is preferable because functional groups can be easily and massively introduced onto the surface of the inorganic particles.

The inorganic particles preferably contain a polysiloxane skeleton. The inorganic particles are preferably obtained by hydrolyzing and condensing a silane compound. The silane compound may have an organic group such as an alkyl group and a vinyl group. Particles obtained using such a silane compound having an organic group are also called inorganic particles if the main component is an inorganic substance. The inorganic particles may be formed using organopolysiloxane.

Examples of the silane compound include a compound represented by the following formula (1) (hereinafter sometimes referred to as compound (1)) and a compound represented by the following formula (2) (hereinafter referred to as compound (2)). And a compound represented by the following formula (3) (hereinafter, a compound represented by the compound (3), etc.) As the silane compound, the compound (1), the compound (2) and the compound It is preferable to use at least one selected from the group consisting of (3) If such a compound is used, the resulting inorganic particles have silanol groups on the surface, so that they have hydroxyl groups.

In the above formula (1), Ra represents a (meth) acryloyl group, Rb represents an optionally substituted divalent organic group having 1 to 20 carbon atoms, and R1 and R2 each represents a hydrogen atom. Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 2 to 5 carbon atoms, and Z represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. To express.

In the above formula (2), R1, R2 and R3 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acyl group having 2 to 5 carbon atoms.

In the above formula (3), Ra represents a methyl group or an ethyl group, and R1, R2, and R3 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acyl group having 2 to 5 carbon atoms.

The compound (1) has a Ra—O—Rb— group. This group has a Ra group as a group containing a polymerizable unsaturated group. By subjecting the polymerizable unsaturated group in the compound (1) to a radical polymerization reaction, an organic polymer skeleton having high flexibility is formed. On the other hand, when only the compound (2) is used without using the compound (1), an organic polymer skeleton having sufficiently high flexibility is not formed.

Ra in the above formula (1) represents a (meth) acryloyl group.

In the above formula (1), Rb represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent. Due to the presence of such an organic group, an organic polymer skeleton having high flexibility is formed.

Examples of the divalent organic group having 1 to 20 carbon atoms in Rb include alkylene groups such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, and a group in which a substituent is bonded to the alkylene group. And a phenylene group and a group in which a substituent is bonded to the phenylene group, a group in which an alkylene group is bonded through an ether bond, a group in which a phenylene group is bonded through an ether bond, and the like. Of these, a propylene group or a phenylene group is preferable, and a propylene group is more preferable.

In the above formula (1), Z represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Since the number of reactive base points increases, Z in the above formula (1) is preferably an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and is an alkoxy group having 1 to 5 carbon atoms. It may be an alkyl group having 1 to 3 carbon atoms. When Z in the formula (1) is an alkoxy group, Z is more preferably an alkoxy group having 1 or 2 carbon atoms. When Z in the formula (1) is an alkyl group, Z is more preferably an alkyl group having 1 or 2 carbon atoms, and further preferably a methyl group.

In the above formula (3), Ra represents a methyl group or an ethyl group. Ra in the formula (3) is preferably a methyl group.

In the above formulas (1), (2) and (3), R1, R2 and R3 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acyl group having 2 to 5 carbon atoms. These groups are hydrolyzable groups. Since the hydrolysis rate is moderately high, R1, R2 and R3 in the above formulas (1), (2) and (3) are each an alkyl group having 1 to 3 carbon atoms or an acyl group having 2 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably a methyl group.

Examples of the compound (1) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropyltriethoxysilane. Examples include acryloxypropyltriethoxysilane. As for the above-mentioned compound (1), only 1 type may be used and 2 or more types may be used together.

Examples of the compound (2) include vinyltrimethoxysilane and vinyltriethoxysilane. As for the said compound (2), only 1 type may be used and 2 or more types may be used together.

Examples of the compound (3) include methyltrimethoxysilane and ethyltrimethoxysilane. As for the said compound (3), only 1 type may be used and 2 or more types may be used together.

The alkoxy group-containing organopolysiloxane has a second reactive functional group capable of reacting with the first reactive functional group. The second reactive functional group is appropriately selected according to the type of the first reactive functional group. Examples of the second reactive functional group include a hydroxyl group, an alkoxy group, an epoxy group, a (meth) acryloyl group, an amino group, a mercapto group, and an isocyanate group. For example, when the first reactive functional group is a hydroxyl group, the hydroxyl group reacts with an alkoxy group, and therefore the alkoxy group in the alkoxy group-containing organopolysiloxane corresponds to the second reactive functional group. Among them, an epoxy group, a (meth) acryloyl group, a mercapto group, or an alkoxy group is preferable because the reaction with the first reactive functional group in the inorganic particles easily proceeds, and an epoxy group, a (meth) acryloyl group, or An alkoxy group is more preferable. The alkoxy group-containing organopolysiloxane preferably has an epoxy group, a (meth) acryloyl group or a mercapto group as the second reactive functional group, and more preferably has an epoxy group or a (meth) acryloyl group. More preferably an epoxy group or a mercapto group, still more preferably an epoxy group, even more preferably a (meth) acryloyl group, further preferably an alkoxy group, an epoxy group, ) It is more preferred to have an acryloyl group or mercapto group and an alkoxy group, more preferably an epoxy group or mercapto group and an alkoxy group, and particularly preferably an epoxy group and an alkoxy group. The alkoxy group is preferably a methoxy group or an ethoxy group.

The alkoxy group-containing organopolysiloxane preferably has an epoxy group, a methoxy group, or an ethoxy group as the second reactive functional group, because much better compression deformation characteristics can be obtained.

Examples of the alkoxy-containing organopolysiloxane include alkoxy oligomers and the like, and X-41-1053, X-41-1059A (having epoxy groups, methoxy groups, and ethoxy groups) manufactured by Shin-Etsu Chemical Co., Ltd., X-41-1056 (having epoxy group, methoxy group), X-41-1805 (having mercapto group, methoxy group, ethoxy group), X-41-1818 (having mercapto group, ethoxy group), X- 41-1810 (having a mercapto group and a methoxy group), X-41-2651 (having an amino group and a methoxy group), X-40-2655A (having a methacryloyl group and a methoxy group), KR-513 (acryloyl group, Having methoxy group), KC-89S, KR-500, X-40-9225, X-40-9 46, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308 (and above, having a methoxy group), X-40-9238 (having an ethoxy group) and the like. As for the said alkoxy containing organopolysiloxane, only 1 type may be used and 2 or more types may be used together.

The alkoxy group-containing organopolysiloxane may be a reaction product of a cyclic siloxane and the silane compound having the second reactive functional group. In the reaction product, the cyclic siloxane is preferably opened. The silane compound having the second reactive functional group may be a silane coupling agent.

The alkoxy group-containing organopolysiloxane preferably has an alkyl group directly bonded to a silicon atom. The alkyl group is an organic functional group.

More preferably, the inorganic particles have an epoxy group and an alkoxy group as the second reactive functional group. More preferably, the inorganic particles have an epoxy group, a (meth) acryloyl group or a mercapto group, an alkoxy group, and an alkyl group directly bonded to a silicon atom, and an epoxy group or a (meth) acryloyl group, an alkoxy group, and a silicon atom. It is particularly preferable to have an alkyl group directly bonded to the alkyl group, and it is most preferable to have an epoxy group, an alkoxy group, and an alkyl group directly bonded to a silicon atom. Even better compression deformation properties are obtained by the presence of these preferred second reactive functional groups and by the presence of these preferred second reactive functional groups and organic functional groups.

The weight average molecular weight of the alkoxy group-containing organopolysiloxane is preferably 500 or more, more preferably 1000 or more, preferably 10,000 or less, more preferably 7000 or less. The said weight average molecular weight shows the weight average molecular weight in polystyrene conversion calculated | required by a gel permeation chromatography (GPC) measurement.

It is preferable that the organic-inorganic hybrid particles are obtained by reacting the first reactive functional group and the second reactive functional group, because much better compression deformation characteristics can be obtained.

In the organic-inorganic hybrid particles, it is preferable that a plurality of the inorganic particles are integrated through a structure derived from the alkoxy group-containing organopolysiloxane because more excellent compression deformation characteristics can be obtained.

The organic-inorganic hybrid particle is an aggregate of a plurality of the inorganic particles. In the organic-inorganic hybrid particles, the number of inorganic particles in the aggregate is 2 or more, preferably 5 or more, more preferably 10 or more. In the examples described later, the number of inorganic particles in the aggregate is 10 or more. The upper limit of the number of inorganic particles in the aggregate is not particularly limited.

In the organic-inorganic hybrid particles, the particle diameter of each inorganic particle in the aggregate is preferably 0.1 nm or more, more preferably 1 nm or more, still more preferably 3 nm or more, preferably 1000 nm or less, more preferably 500 nm or less, still more preferably. Is 200 nm or less, particularly preferably 100 nm or less. If the particle size of the inorganic particles in the aggregate is not less than the above lower limit, it is difficult to be brittle because there are few grain boundaries, and if it is not more than the above upper limit, it becomes brittle because there are few voids in the organic-inorganic hybrid particles. There is a tendency to become difficult.

From the viewpoint of further suppressing damage to the organic / inorganic hybrid particles, the breaking load of the organic / inorganic hybrid particles is preferably 5 mN or more, more preferably 10 mN or more, and even more preferably 11 mN or more. When the breaking load is equal to or more than the lower limit, the organic-inorganic hybrid particles are hardly cracked or damaged during compression.

The breaking load can be measured as follows, for example. Using a micro-compression tester, organic-inorganic hybrid particles are compressed on a smooth indenter end face of a cylinder (diameter 100 μm, made of diamond) under the conditions of 25 ° C., compression speed of 0.3 mN / second, and maximum test load of 20 mN. The load value (N) and compression displacement (mm) at this time are measured. From the measured value obtained, the compression elastic modulus can be obtained by the following formula. As the micro compression tester, for example, “Fischer Scope H-100” manufactured by Fischer is used.

The above breaking load represents the load value when the bending point is confirmed in the measurement curve of the load value and the compression displacement.

The compression recovery rate of the organic / inorganic hybrid particles is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more. When the compression recovery rate is equal to or higher than the lower limit, the organic / inorganic hybrid particles are less likely to be damaged, and the organic / inorganic hybrid particles easily follow and deform in response to fluctuations in the distance between substrates or electrodes. . For this reason, it becomes difficult to produce the connection failure between board | substrates or between electrodes.

The compression recovery rate can be measured as follows, for example. Spread organic-inorganic hybrid particles on the sample stage. With respect to one dispersed organic-inorganic hybrid particle, a load (reversal load value) is applied to the center direction of the organic-inorganic hybrid particle until the organic-inorganic hybrid particle is 30% compressed and deformed using a micro compression tester. Thereafter, unloading is performed up to the origin load value (0.40 mN). The load-compression displacement during this period is measured, and the compression recovery rate can be obtained from the following equation. The load speed is 0.33 mN / sec. As the micro compression tester, for example, “Fischer Scope H-100” manufactured by Fischer is used. *

Compression recovery rate (%) = [(L1−L2) / L1] × 100 L1: Compression displacement from the load value for the origin when applying the load to the reverse load value L2: Inversion when releasing the load Unloading displacement from the load value to the load value for origin

The particle diameter of the organic-inorganic hybrid particles is preferably 0.1 μm or more, more preferably 1 μm or more, still more preferably 1.5 μm or more, particularly preferably 2 μm or more, preferably 1000 μm or less, more preferably 500 μm or less, even more. It is preferably 300 μm or less, more preferably 50 μm or less, particularly preferably 30 μm or less, and most preferably 5 μm or less. When the particle diameter of the organic / inorganic hybrid particles is not less than the lower limit and not more than the upper limit, the organic / inorganic hybrid particles can be suitably used for electronic parts. The particle diameter of the organic-inorganic hybrid particles indicates the maximum diameter.

In order to measure the particle diameter of the organic-inorganic hybrid particles, for example, a particle size distribution measuring machine using principles such as laser light scattering, electric resistance value change, and image analysis after imaging can be used.

(Method for producing organic-inorganic hybrid particles)

The method for producing the organic / inorganic hybrid particles is not particularly limited. The method for producing the organic-inorganic hybrid particles preferably includes a hydrolysis and condensation step of hydrolyzing and condensing the silane compound to obtain inorganic particles. According to this method, organic-inorganic hybrid particles having a uniform particle diameter and even better compression deformation characteristics can be obtained. In the hydrolysis and condensation step, hydrolysis and condensation reactions occur at the contact interface between the silane compound and the aqueous solvent, a polysiloxane skeleton is formed, and inorganic particles are obtained.

In the hydrolysis and condensation step, a catalyst is generally used. The silane compound is reacted in the presence of a catalyst. Specifically, in the hydrolysis and condensation step, for example, water and an acidic catalyst or a basic catalyst are used. As for the said catalyst, only 1 type may be used and 2 or more types may be used together.

Examples of the acidic catalyst include inorganic acids, organic acids, acid anhydrides of inorganic acids and derivatives thereof, and acid anhydrides of organic acids and derivatives thereof.

In the hydrolysis and condensation step, an appropriate organic solvent may be used in addition to water. Specific examples of the organic solvent include alcohols, ketones, esters, (cyclo) paraffins, ethers and aromatic hydrocarbons. As for the said organic solvent, only 1 type may be used and 2 or more types may be used together.

Although the reaction temperature in the said hydrolysis and condensation process is not specifically limited, Preferably it is 0 degreeC or more, Preferably it is 100 degrees C or less, More preferably, it is 70 degrees C or less. The reaction time in the hydrolysis and condensation step is not particularly limited, but is preferably 30 minutes or more, and preferably 100 hours or less.

The method for producing the organic-inorganic hybrid particle includes a plurality of inorganic particles having a first reactive functional group on the surface, and an alkoxy group having a second reactive functional group capable of reacting with the first reactive functional group. It is preferable to provide a step of reacting the containing organopolysiloxane to obtain an aggregate of the inorganic particles. In this step, it is preferable to integrate a plurality of the inorganic particles through a structure derived from the alkoxy group-containing organopolysiloxane. It is preferable to obtain an aggregate of inorganic particles by integrating a plurality of inorganic particles via a structure (structure part) derived from an alkoxy group-containing organopolysiloxane.

For example, in a state where water and the silane compound layer containing the alkoxy group-containing organopolysiloxane are separated in a container, or a layer containing water and the silane compound and a layer containing the alkoxy group-containing organopolysiloxane; In the separated state, the silane compound is hydrolyzed and condensed to obtain inorganic particles, and the alkoxy group-containing organopolysiloxane is deposited and deposited on the surface of the obtained inorganic particles to obtain the first reactivity. Aggregates of the inorganic particles obtained by reacting a plurality of inorganic particles having a functional group on the surface with an alkoxy group-containing organopolysiloxane having a second reactive functional group capable of reacting with the first reactive functional group. You may get

(Use of organic-inorganic hybrid particles)
The use of the organic-inorganic hybrid particles is not particularly limited. The organic-inorganic hybrid particles are suitably used for various applications that require a high breaking load. The organic-inorganic hybrid particles are preferably used for electronic parts. The organic-inorganic hybrid particles are preferably organic-inorganic hybrid particles for electronic parts.

The organic / inorganic hybrid particles are preferably used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer, or used as spacers for liquid crystal display elements. The organic-inorganic hybrid particles are preferably used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer. The organic / inorganic hybrid particles are preferably used as spacers for liquid crystal display elements. Since the organic-inorganic hybrid particles have a high breaking load, the organic-inorganic hybrid particles are used as spacers for liquid crystal display elements and disposed between the substrates, or a conductive layer is formed on the surface to be used as conductive particles between the electrodes. When electrically connected, the spacer for liquid crystal display element or the conductive particles are not easily broken and damaged. In particular, when an impact is applied to the liquid crystal display element using the liquid crystal display element spacer and the connection structure using the conductive particles, the liquid crystal display element spacer and the conductive particles are difficult to break and damage. .

Furthermore, the organic-inorganic hybrid particles are also suitably used as a shock absorber or a vibration absorber. For example, the organic-inorganic hybrid particles can be used as an alternative such as rubber or spring.

FIG. 2 is a cross-sectional view schematically showing conductive particles using the organic-inorganic hybrid particles shown in FIG.

2 has the organic-inorganic hybrid particle 1 and the conductive layer 31A disposed on the surface of the organic-inorganic hybrid particle 1. The conductive particle 21 shown in FIG.

The conductive layer 31 </ b> A covers the surface of the organic-inorganic hybrid particle 1. The conductive particles 21 are coated particles in which the surface of the organic-inorganic hybrid particle 1 is coated with a conductive layer 31A.

FIG. 3 schematically shows a modification of the conductive particles using the organic-inorganic hybrid particles shown in FIG. 1 in a cross-sectional view.

3 includes the organic-inorganic hybrid particle 1, the conductive layer 31B, a plurality of core substances 32, and a plurality of insulating substances 33. The conductive particles 22 shown in FIG.

The conductive layer 31 </ b> B is disposed on the surface of the organic-inorganic hybrid particle 1. The conductive layer 31B includes a first conductive layer 31Ba that is an inner layer and a second conductive layer 31Bb that is an outer layer. On the surface of the organic-inorganic hybrid particle 1, the first conductive layer 31Ba is disposed. A second conductive layer 31Bb is arranged on the surface of the first conductive layer 31Ba.

The conductive particles 22 have a plurality of protrusions on the conductive surface. The conductive layer 31B and the second conductive layer 31Bb have a plurality of protrusions on the outer surface. As described above, the conductive particles may have protrusions on the conductive surface of the conductive particles, or may have protrusions on the outer surfaces of the conductive layer and the second conductive layer. A plurality of core substances 32 are arranged on the surface of the organic-inorganic hybrid particle 1. The plurality of core materials 32 are embedded in the conductive layer 31B. The core substance 32 is disposed inside the protrusions in the conductive particles 22 and the conductive layer 31B. The conductive layer 31 </ b> B covers a plurality of core materials 32. The outer surface of the conductive layer 31B is raised by the plurality of core materials 32, and protrusions are formed.

The conductive particles 22 have an insulating material 33 disposed on the outer surface of the conductive layer 31B. At least a part of the outer surface of the conductive layer 31 </ b> B is covered with the insulating material 33. The insulating substance 33 is made of an insulating material and is an insulating particle. Thus, the said electroconductive particle may have the insulating substance arrange | positioned on the outer surface of a conductive layer.

The metal for forming the conductive layer is not particularly limited. Examples of the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, and these. And the like. Examples of the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes can be made still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable.

Like the conductive particles 21, the conductive layer may be formed of a single layer. Like the conductive particles 22, the conductive layer may be formed of a plurality of layers. That is, the conductive layer may have a stacked structure of two or more layers. When the conductive layer is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and is a gold layer. Is more preferable. When the outermost layer is these preferred conductive layers, the connection resistance between the electrodes is further reduced. Moreover, when the outermost layer is a gold layer, the corrosion resistance is further enhanced.

The method for forming a conductive layer on the surface of the organic-inorganic hybrid particles is not particularly limited. As a method for forming the conductive layer, for example, a method using electroless plating, a method using electroplating, a method using physical vapor deposition, and a metal powder or a paste containing a metal powder and a binder are coated on the surface of the organic-inorganic hybrid particles. Methods and the like. Especially, since formation of a conductive layer is simple, the method by electroless plating is preferable. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.

The particle diameter of the conductive particles is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, preferably 520 μm or less, more preferably 500 μm or less, still more preferably 100 μm or less, and even more preferably. Is 50 μm or less, particularly preferably 20 μm or less. When the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrode becomes sufficiently large when the electrodes are connected using the conductive particles, and the conductive layer When forming the conductive particles, it becomes difficult to form aggregated conductive particles. Moreover, the space | interval between the electrodes connected via the electroconductive particle does not become large too much, and it becomes difficult for a conductive layer to peel from the surface of an organic inorganic hybrid particle. Further, when the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be suitably used for the use of the conductive material.

The particle diameter of the conductive particles means a diameter when the conductive particles are true spherical, and means a maximum diameter when the conductive particles have a shape other than the true spherical shape.

The thickness of the conductive layer (when the conductive layer is a multilayer, the total thickness of the conductive layer) is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 10 μm or less, more preferably 1 μm or less, Preferably it is 0.3 micrometer or less. When the thickness of the conductive layer is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed when connecting the electrodes. .

When the conductive layer is formed of a plurality of layers, the thickness of the outermost conductive layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, preferably 0.5 μm or less, more preferably 0. .1 μm or less. When the thickness of the outermost conductive layer is not less than the above lower limit and not more than the above upper limit, the coating with the outermost conductive layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection resistance between the electrodes is further increased. Lower. Further, the thinner the gold layer when the outermost layer is a gold layer, the lower the cost.

The thickness of the conductive layer can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).

The conductive particles may have protrusions on the outer surface of the conductive layer. It is preferable that there are a plurality of the protrusions. An oxide film is often formed on the surface of the electrode connected by the conductive particles. When conductive particles having protrusions are used, the oxide film is effectively eliminated by the protrusions by placing the conductive particles between the electrodes and pressing them. For this reason, an electrode and the conductive layer of electroconductive particle can be contacted still more reliably, and the connection resistance between electrodes can be made low. Furthermore, when the conductive particles are provided with an insulating material on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the conductive particles and the electrodes are separated by protrusions of the conductive particles. Insulating substances or binder resins in between can be effectively eliminated. For this reason, the conduction | electrical_connection reliability between electrodes can be improved.

As a method of forming protrusions on the surface of the conductive particles, a method of forming a conductive layer by electroless plating after attaching a core substance to the surface of the organic-inorganic hybrid particles, and a method of forming no protrusion on the surface of the organic-inorganic hybrid particles. Examples include a method of forming a conductive layer by electrolytic plating, attaching a core substance, and further forming a conductive layer by electroless plating. In addition, the core material may not be used to form the protrusion.

The conductive particles may include an insulating material disposed on the outer surface of the conductive layer. In this case, when the conductive particles are used for connection between the electrodes, a short circuit between adjacent electrodes can be prevented. Specifically, when a plurality of conductive particles are in contact with each other, an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between electrodes adjacent in the lateral direction instead of between the upper and lower electrodes. In addition, the insulating substance between the conductive layer of an electroconductive particle and an electrode can be easily excluded by pressurizing electroconductive particle with two electrodes in the case of the connection between electrodes. When the conductive particles have protrusions on the surface of the conductive layer, the insulating substance between the conductive layer of the conductive particles and the electrode can be more easily eliminated. The insulating substance is preferably an insulating resin layer or insulating particles, and more preferably insulating particles. The insulating particles are preferably insulating resin particles.

(Conductive material)
The conductive material includes the conductive particles described above and a binder resin. The conductive particles are preferably dispersed in a binder resin and used as a conductive material. The conductive material is preferably an anisotropic conductive material. The conductive material is preferably a conductive material for circuit connection.

The binder resin is not particularly limited. As the binder resin, a known insulating resin is used. Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for the said binder resin, only 1 type may be used and 2 or more types may be used together.

Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin. Examples of the thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin. Examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin. The curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin. The curable resin may be used in combination with a curing agent. Examples of the thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogenated products of styrene block copolymers. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

In addition to the conductive particles and the binder resin, the conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer. Various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.

The method for dispersing the conductive particles in the binder resin is not particularly limited, and a conventionally known dispersion method can be used. Examples of a method for dispersing the conductive particles in the binder resin include a method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. The conductive particles are dispersed in water. Alternatively, after uniformly dispersing in an organic solvent using a homogenizer or the like, it is added to the binder resin and kneaded with a planetary mixer or the like, and the binder resin is diluted with water or an organic solvent. Then, the method of adding the said electroconductive particle, kneading with a planetary mixer etc. and disperse | distributing is mentioned.

The conductive material can be used as a conductive paste and a conductive film. When the conductive material according to the present invention is used as a conductive film, a film not including conductive particles may be laminated on the conductive film including the conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.

In 100% by weight of the conductive material, the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably 99.% or more. It is 99 weight% or less, More preferably, it is 99.9 weight% or less. When the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further increased.

In 100% by weight of the conductive material, the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 40% by weight or less, more preferably 20% by weight or less, More preferably, it is 10 weight% or less. When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.

(Connection structure and liquid crystal display element)
A connection structure can be obtained by connecting the connection target members using the conductive particles described above or using a conductive material including the conductive particles described above and a binder resin.

The connection structure 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 preferably formed of the above-described conductive particles, or a connection structure formed of a conductive material containing the above-described conductive particles and a binder resin. When the conductive particles are used alone, the connection part itself is the conductive particles. That is, the first and second connection target members are connected by the conductive particles. The conductive material used for obtaining the connection structure is preferably an anisotropic conductive material.

The first connection object member preferably has a first electrode on the surface. The second connection target member preferably has a second electrode on the surface. It is preferable that the first electrode and the second electrode are electrically connected by the conductive particles.

FIG. 4 is a cross-sectional view schematically showing a connection structure using the conductive particles 21 shown in FIG.

The connection structure 51 shown in FIG. 4 is a connection that connects the first connection target member 52, the second connection target member 53, and the first connection target member 52 and the second connection target member 53. Part 54. The connection part 54 is formed of a conductive material including the conductive particles 21 and a binder resin. In FIG. 4, the conductive particles 21 are schematically illustrated for convenience of illustration. Instead of the conductive particles 21, other conductive particles such as the conductive particles 22 may be used.

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

connection target members

52 and 53 are electrically connected by the conductive particles 21.

The manufacturing method of the connection structure is not particularly limited. As an example of a method of manufacturing a connection structure, a method of placing the conductive material between a first connection target member and a second connection target member to obtain a laminate, and then heating and pressurizing the laminate Etc. The pressurizing pressure is about 9.8 × 10 ⁴ to 4.9 × 10 ⁶ Pa. The heating temperature is about 120 to 220 ° C. The pressure applied to connect the electrode of the flexible printed board, the electrode disposed on the resin film, and the electrode of the touch panel is about 9.8 × 10 ⁴ to 1.0 × 10 ⁶ Pa.

Specific examples of the connection target member include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed boards, flexible printed boards, glass epoxy boards, and glass boards. The conductive material is preferably a conductive material for connecting electronic components. The conductive paste is a paste-like conductive material, and is preferably applied on the connection target member in a paste-like state.

The conductive particles and the conductive material are also suitably used for touch panels. Therefore, the connection target member is preferably a flexible printed circuit board or a connection target member in which an electrode is disposed on the surface of a resin film. The connection target member is preferably a flexible printed board, and is preferably a connection target member in which an electrode is disposed on the surface of the resin film. The flexible printed board generally has electrodes on the surface.

Examples of the electrode provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode. When the connection object member is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. In addition, when the said electrode is an aluminum electrode, the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated | stacked on the surface of the metal oxide layer may be sufficient. Examples of the material 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.

The organic-inorganic hybrid particles are preferably used as a spacer for a liquid crystal display element. That is, the organic / inorganic hybrid particle includes a pair of substrates constituting a liquid crystal cell, a liquid crystal sealed between the pair of substrates, and a liquid crystal display element spacer disposed between the pair of substrates. It is suitably used for obtaining an element.

FIG. 5 is a cross-sectional view of a liquid crystal display element using organic / inorganic hybrid particles according to an embodiment of the present invention as a spacer for a liquid crystal display element.

A liquid crystal display element 81 shown in FIG. 5 has a pair of transparent glass substrates 82. The transparent glass substrate 82 has an insulating film (not shown) on the opposing surface. Examples of the material for the insulating film include SiO ₂ . A transparent electrode 83 is formed on the insulating film in the transparent glass substrate 82. Examples of the material of the transparent electrode 83 include ITO. The transparent electrode 83 can be formed by patterning, for example, by photolithography. An alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82. Examples of the material of the alignment film 84 include polyimide.

A liquid crystal 85 is sealed between the pair of transparent glass substrates 82. A plurality of organic-inorganic hybrid particles 1 are disposed between the pair of transparent glass substrates 82. The organic-inorganic hybrid particle 1 is used as a spacer for a liquid crystal display element. The space between the pair of transparent glass substrates 82 is regulated by the plurality of organic-inorganic hybrid particles 1. A sealing agent 86 is disposed between the edges of the pair of transparent glass substrates 82. Outflow of the liquid crystal 85 to the outside is prevented by the sealing agent 86. In FIG. 5, the organic-inorganic hybrid particle 1 is schematically shown for convenience of illustration. Instead of the organic / inorganic hybrid particles 1, other organic / inorganic hybrid particles may be used.

In the liquid crystal display element, the arrangement density of spacers for liquid crystal display elements per 1 mm ² is preferably 10 pieces / mm ² or more, and preferably 1000 pieces / mm ² or less. When the arrangement density is 10 pieces / mm ² or more, the cell gap becomes even more uniform. When the arrangement density is 1000 / mm ² or less, the contrast of the liquid crystal display element is further improved.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited only to the following examples.

(Example 1)
In a 500 mL reaction vessel equipped with a stirrer and a thermometer, 300 g of a 0.13% by weight aqueous ammonia solution was placed. Next, 4.1 g of methyltrimethoxysilane, 19.2 g of vinyltrimethoxysilane, silicone alkoxy oligomer (“X-41-1053” manufactured by Shin-Etsu Chemical Co., Ltd., methoxy group, A mixture of 0.7 g of weight average molecular weight (about 1600) having an ethoxy group, an epoxy group and an alkyl group directly bonded to a silicon atom was slowly added. After the hydrolysis and condensation reaction proceeded with stirring, 2.4 mL of a 25 wt% aqueous ammonia solution was added, and then the particles were isolated from the aqueous ammonia solution, and the resulting particles were subjected to an oxygen partial pressure of 10 ⁻¹⁷ atm, Firing at 400 ° C. for 2 hours gave organic-inorganic hybrid particles. The particle diameters of the obtained organic-inorganic hybrid particles are shown in Table 1 below.

(Example 2)
Silicone alkoxy oligomer (“X-41-1053” manufactured by Shin-Etsu Chemical Co., Ltd.), alkoxy oligomer (“KR-500” manufactured by Shin-Etsu Chemical Co., Ltd.), having a methoxy group and an alkyl group directly bonded to a silicon atom, weight average Organic-inorganic hybrid particles were obtained in the same manner as in Example 1 except that the molecular weight was changed to 3000 to 10,000.

(Example 3)
Silicone alkoxy oligomer (“X-41-1053” manufactured by Shin-Etsu Chemical Co., Ltd.), silicone oligomer (“X-41-1805” manufactured by Shin-Etsu Chemical Co., Ltd.), weight average molecular weight having methoxy group, ethoxy group and mercapto group : About 1800), except that the organic-inorganic hybrid particles were obtained in the same manner as in Example 1.

Example 4
In a 500 mL reaction vessel equipped with a stirrer and a thermometer, 300 g of a 0.13% by weight aqueous ammonia solution was placed. Next, a mixture of 4.1 g of methyltrimethoxysilane and 19.2 g of vinyltrimethoxysilane was slowly stirred into the aqueous ammonia solution in the reaction vessel. After the hydrolysis and condensation reaction proceeds with stirring, a silicone alkoxy oligomer (“X-41-1053” manufactured by Shin-Etsu Chemical Co., Ltd., having an alkyl group directly bonded to a methoxy group, an ethoxy group, an epoxy group, and a silicon atom) ) 0.7g was added and stirred slowly. After the disappearance of the silicone alkoxy oligomer, 2.4 mL of 25 wt% aqueous ammonia solution was added, and then the particles were isolated from the aqueous ammonia solution, and the obtained particles were calcined at 400 ° C. for 2 hours at an oxygen partial pressure of 10 ⁻¹⁷ atm. Organic / inorganic hybrid particles were obtained.

(Example 5)
In a 500 mL reaction vessel equipped with a stirrer and a thermometer, 300 g of a 0.13% by weight aqueous ammonia solution was placed. Next, 1.9 g of 3-methacryloxypropyltrimethoxysilane, 4.1 g of methyltrimethoxysilane, 17.3 g of vinyltrimethoxysilane, silicone alkoxy oligomer (Shin-Etsu Chemical Co., Ltd.) were added to the aqueous ammonia solution in the reaction vessel. A mixture of 0.7 g of “X-41-1053” (having a methoxy group, an ethoxy group, an epoxy group, and an alkyl group directly bonded to a silicon atom) was slowly added. After the hydrolysis and condensation reaction proceeded with stirring, 2.4 mL of a 25 wt% aqueous ammonia solution was added, and then the particles were isolated from the aqueous ammonia solution, and the resulting particles were subjected to an oxygen partial pressure of 10 ⁻¹⁷ atm, Firing at 400 ° C. for 2 hours gave organic-inorganic hybrid particles.

(Example 6)
Cyclopentasiloxane (“KF-995” manufactured by Shin-Etsu Chemical Co., Ltd.), a cyclic siloxane, and 3-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.), an epoxy silane coupling agent, To obtain an alkoxy group-containing organopolysiloxane A (having an epoxy group and an alkoxy group, and a weight average molecular weight of about 1500).

Organic-inorganic hybrid particles were obtained in the same manner as in Example 4 except that the silicone alkoxy oligomer (“X-41-1053” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to an alkoxy group-containing organopolysiloxane A.

(Example 7)
Cyclopentasiloxane (“KF-995” manufactured by Shin-Etsu Chemical Co., Ltd.), which is a cyclic siloxane, and 3-acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silane coupling agent having an acryloyl group. ) To obtain an alkoxy group-containing organopolysiloxane B (having an acryloyl group and an alkoxy group, weight average molecular weight: about 1300).

Organic-inorganic hybrid particles were obtained in the same manner as in Example 4 except that the silicone alkoxy oligomer (“X-41-1053” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to an alkoxy group-containing organopolysiloxane B.

(Example 8)
Cyclopentasiloxane (“KF-995” manufactured by Shin-Etsu Chemical Co., Ltd.), which is a cyclic siloxane, and 3-methacryloxypropyltrimethoxysilane (“KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silane coupling agent having a methacryloyl group. And methacryloxy group-containing organopolysiloxane C (having a methacryloyl group and an alkoxy group, weight average molecular weight: about 2000).

Organic-inorganic hybrid particles were obtained in the same manner as in Example 4 except that the silicone alkoxy oligomer (“X-41-1053” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to an alkoxy group-containing organopolysiloxane C.

Example 9
(1) Palladium adhesion process The organic-inorganic hybrid particles obtained in Example 4 were prepared. The organic / inorganic hybrid particles were etched and washed with water. Next, organic-inorganic hybrid particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash | cleaned. Organic / inorganic hybrid particles were added to 0.5 wt% dimethylamine borane solution at pH 6 to obtain organic / inorganic hybrid particles to which palladium was attached.

(2) Core substance adhering step The organic-inorganic hybrid particles to which palladium was attached were stirred and dispersed in 300 mL of ion-exchanged water for 3 minutes to obtain a dispersion. Next, 1 g of metallic nickel particle slurry (average particle size 100 nm) was added to the dispersion over 3 minutes to obtain organic-inorganic hybrid particles to which the core material was adhered.

(3) Electroless nickel plating process By the electroless plating method, the nickel layer was formed on the surface of the organic inorganic hybrid particle to which the core substance was adhered, and the electroconductive particle was produced. The nickel layer had a thickness of 0.1 μm.

(Example 10)
(1) Preparation of insulating particles Into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.

The insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.

(2) Production of conductive particles with insulating particles 10 g of the conductive particles obtained in Example 9 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. . After filtration through a 3 μm mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.

When observed with a scanning electron microscope (SEM), only one coating layer of insulating particles was formed on the surface of the conductive particles. The coverage of the insulating particles with respect to the area of 2.5 μm from the center of the conductive particles by image analysis (that is, the projected area of the particle diameter of the insulating particles) was calculated to be 30%.

(Comparative Example 1)
Organic-inorganic hybrid particles were obtained in the same manner as in Example 1 except that the silicone alkoxy oligomer (“X-41-1053” manufactured by Shin-Etsu Chemical Co., Ltd.) was not used.

(Comparative Example 2)
Example 1 except that the silicone alkoxy oligomer (“X-41-1053” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to a non-reactive methylphenyl silicone oil (“KF-56A” manufactured by Shin-Etsu Chemical Co., Ltd.) In the same manner, organic-inorganic hybrid particles were obtained.

(Evaluation)
(1) Particle size of organic-inorganic hybrid particles Regarding the particle size of the obtained organic-inorganic hybrid particles, about 10,000 organic-inorganic hybrid particle particles were measured using a particle size distribution measuring device ("Multisizer 3" manufactured by Beckman Coulter, Inc.). The diameter was measured. The average value of the measured particle diameters was determined and used as the particle diameter of the organic / inorganic hybrid particles.

(2) Breaking Load of Organic / Inorganic Hybrid Particles The breaking load of the obtained organic / inorganic hybrid particles was measured by the above-described method using “Fischer Scope H-100” manufactured by Fisher.

(3) Particle diameter of each inorganic particle (per inorganic particle) in the aggregate In the obtained organic-inorganic hybrid particle, the particle diameter of each inorganic particle in the aggregate is X-ray small angle scattering (Powder X, manufactured by Rigaku Corporation). Measurement was performed by a transmission method using a line diffractometer SmartLab (parallel beam method). The average size obtained using the analysis software NANO-Solver was adopted. In the model of the analysis software NANO-Solver, the scatterer model was a sphere, the particles were SiO ₂ , and the matrix was Air.

In the obtained organic-inorganic hybrid particles, the particle diameter of each inorganic particle in the aggregate was 1 to 500 nm.

(4) Connection resistance Production of conductive particles:
The organic / inorganic hybrid particles obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were washed and dried. Then, the nickel layer was formed on the surface of the obtained organic-inorganic hybrid particle | grains by the electroless-plating method, and the electroconductive particle was produced. The nickel layer had a thickness of 0.1 μm. In Examples 9 and 10, the obtained conductive particles were used as they were.

Fabrication of connection structure:
10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and a microcapsule type curing agent (Asahi Kasei E-material) 50 parts by weight of “HX3941HP” manufactured by KK And dispersed to obtain a resin composition.

The obtained resin composition was applied to a 50 μm-thick PET (polyethylene terephthalate) film whose one surface was release-treated, and dried with hot air at 70 ° C. for 5 minutes to produce an anisotropic conductive film. The thickness of the obtained anisotropic conductive film was 12 μm.

The obtained anisotropic conductive film was cut into a size of 5 mm × 5 mm. PET substrate (width 3 cm, length 3 cm) provided with ITO (height 0.1 μm, L / S = 20 μm / 20 μm) having a lead wire for resistance measurement on one side of the cut anisotropic conductive film Affixed to the center of the ITO electrode. Subsequently, the two-layer flexible printed circuit board (width 2cm, length 1cm) provided with the same gold electrode was bonded after aligning so that electrodes might overlap. A laminate of the PET substrate and the two-layer flexible printed circuit board was thermocompression bonded under pressure bonding conditions of 10 N, 180 ° C., and 20 seconds to obtain a connection structure. In addition, the two-layer flexible printed board by which the copper electrode was formed in the polyimide film and the copper electrode surface was Au-plated was used.

The connection resistance between the opposing electrodes of the obtained connection structure was measured by the 4-terminal method. Connection resistance was determined according to the following criteria.

[Evaluation criteria for connection resistance]
◯: Connection resistance is 3.0Ω or less ○: Connection resistance exceeds 3.0, 4.0Ω or less △: Connection resistance exceeds 4.0, 5.0Ω or less ×: Connection resistance exceeds 5.0Ω

The results are shown in Table 1 below.

(5) Example of use as spacer for liquid crystal display element Production of STN type liquid crystal display element:
In a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, the spacers (organic-inorganic hybrid particles) for liquid crystal display elements of Examples 1 to 8 in 100% by weight of the obtained spacer dispersion liquid had a solid content concentration of 2 It added so that it might become weight%, and stirred, and the spacer dispersion liquid for liquid crystal display elements was obtained.

An SiO ₂ film was deposited on one surface of a pair of transparent glass plates (length 50 mm, width 50 mm, thickness 0.4 mm) by a CVD method, and then an ITO film was formed on the entire surface of the SiO ₂ film by sputtering. A polyimide alignment film composition (SE3510, manufactured by Nissan Chemical Industries, Ltd.) was applied to the obtained glass substrate with an ITO film by spin coating, and baked at 280 ° C. for 90 minutes to form a polyimide alignment film. After the rubbing treatment for the alignment film, the liquid crystal display element spacers were wet-sprayed on the alignment film side of one substrate so that the number of spacers for a liquid crystal display element was 100 to 200 per 1 mm ² . After forming a sealant around the other substrate, this substrate and the substrate on which the spacers were spread were placed opposite to each other so that the rubbing direction was 90 °, and both were bonded together. Then, it processed at 160 degreeC for 90 minute (s), the sealing agent was hardened, and the empty cell (screen which does not contain a liquid crystal) was obtained. An STN type liquid crystal containing a chiral agent (made by DIC) was injected into the obtained empty cell, and then the injection port was closed with a sealant, followed by heat treatment at 120 ° C. for 30 minutes to produce an STN type liquid crystal display element. Obtained.

In the obtained liquid crystal display elements, the distance between the substrates was well regulated by the liquid crystal display element spacers of Examples 1 to 8. Moreover, the liquid crystal display element showed favorable display quality.

DESCRIPTION OF SYMBOLS 1 ... Organic-inorganic hybrid particle 11 ... Inorganic particle 12 ... Structure part derived from alkoxy-group-containing

organopolysiloxane

21, 22 ... Conductive particle 31A, 31B ... Conductive layer 31Ba ... First conductive layer 31Bb ... Second conductive layer 32 ... Core material 33 ... Insulating material 51 ... Connection structure 52 ... First connection object member 52a ... First electrode 53 ... Second connection object member 53a ... Second electrode 54 ... Connection part 81 ... Liquid crystal display Element 82 ... Transparent glass substrate 83 ... Transparent electrode 84 ... Alignment film 85 ... Liquid crystal 86 ... Sealing agent

Claims

It is obtained by using a plurality of inorganic particles having a first reactive functional group on the surface and an alkoxy group-containing organopolysiloxane having a second reactive functional group capable of reacting with the first reactive functional group. ,
Organic-inorganic hybrid particles, which are aggregates of the inorganic particles.
The organic-inorganic hybrid particle according to claim 1, wherein the first reactive functional group is a hydroxyl group.
The organic-inorganic hybrid particle according to claim 1 or 2, wherein the alkoxy group-containing organopolysiloxane has an epoxy group or a (meth) acryloyl group as the second reactive functional group.
The organic-inorganic hybrid particle according to claim 3, wherein the alkoxy group-containing organopolysiloxane has an epoxy group as the second reactive functional group.
The aggregate of the inorganic particles is obtained by integrating the plurality of the inorganic particles through a structure derived from the alkoxy group-containing organopolysiloxane. Organic-inorganic hybrid particles.
The organic-inorganic hybrid particle according to any one of claims 1 to 5, wherein the alkoxy group-containing organopolysiloxane has a methoxy group as the second reactive functional group.
The organic-inorganic hybrid particle according to any one of claims 1 to 6, wherein the alkoxy group-containing organopolysiloxane has an alkyl group directly bonded to a silicon atom.
The organic / inorganic material according to any one of claims 1 to 7, wherein a conductive layer is formed on a surface and used to obtain conductive particles having the conductive layer, or used as a spacer for a liquid crystal display element. Hybrid particles.
Organic-inorganic hybrid particles according to any one of claims 1 to 8,
A conductive particle comprising a conductive layer disposed on a surface of the organic-inorganic hybrid particle.
Containing conductive particles and a binder resin,
A conductive material, wherein the conductive particles include the organic-inorganic hybrid particles according to any one of claims 1 to 8, and a conductive layer disposed on a surface of the organic-inorganic hybrid particles.
A first connection object member having a first electrode on its surface;
A second connection target member having a second electrode on its surface;
A connection portion connecting the first connection target member and the second connection target member;
The connecting portion is formed of conductive particles or formed of a conductive material containing the conductive particles and a binder resin;
The conductive particle comprises the organic-inorganic hybrid particle according to any one of claims 1 to 8, and a conductive layer disposed on a surface of the organic-inorganic hybrid particle,
A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles.