KR101538904B1 - Organic-inorganic hybrid particles, conductive particles, conductive material and connection structure - Google Patents

Abstract

Inorganic hybrid particles having a high fracture load at the time of compression and having good compressive strain characteristics. The organic-inorganic hybrid particles according to the present invention are obtained by using a plurality of inorganic particles having a first reactive functional group on its surface and an alkoxy group-containing organopolysiloxane having a second reactive functional group capable of reacting with the first reactive functional group, And is an aggregate of the inorganic particles.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic-inorganic hybrid particle, a conductive particle, a conductive material, and a connection structure. BACKGROUND ART < RTI ID = 0.0 >

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

Anisotropic conductive paste such as anisotropic conductive paste and anisotropic conductive film are widely known. In the anisotropic conductive material, the conductive particles are dispersed in the binder resin. The anisotropic conductive material is used for electrically connecting 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. As the conductive particles, conductive particles having resin particles and a conductive layer disposed on the surface of the resin particles may be used.

As an example of resin particles used for the conductive particles, the following Patent Document 1 discloses polymer particles having a fracture point load of 9.8 mN or less. (A) an inorganic particle formed by a metal oxide such as silica, alumina, or titania, a metal nitride, a metal sulfide, a metal carbide or the like is dispersed in the organic material, (b) (Molecular chain containing a " metal-oxygen-metal " bond) and an organic molecule at a molecular level, and (c) a mode in which a vinyl polymer skeleton and a polysiloxane An organic inorganic aggregate particle including a skeleton, and the like.

The liquid crystal display element is constituted by arranging liquid crystals between two glass substrates. In the liquid crystal display element, a spacer is used as a gap control material in order to keep the gap (gap) between the 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 spacer, Patent Document 2 discloses an organic-inorganic hybrid particle obtained by hydrolysis and polycondensation of a polyfunctional silane compound having a polymerizable unsaturated group in the presence of a surfactant . In Patent Document 2, the polyfunctional silane compound is a first silicone compound containing at least one radically polymerizable group selected from a compound represented by the following formula (X) and derivatives thereof.

Represents a hydrogen atom or a methyl group, R 2 represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent, R 3 represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R 4 represents a hydrogen Represents an atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.

WO2012 / 020799A 1 Japanese Patent Application Laid-Open No. 2000-204119

In the conventional organic-inorganic hybrid particles as described in Patent Documents 1 and 2, the breaking load at the time of compression may be low.

Therefore, when the above-mentioned organic-inorganic hybrid particles are used as a spacer for a liquid crystal display element and arranged between substrates, or when a conductive layer is formed on the surface and used as conductive particles to electrically connect the electrodes, Cracks or damage may occur in the liquid crystal display element spacer or the conductive particles when an impact is applied to the liquid crystal display element using the spacer and the connection structure using the conductive particles.

An object of the present invention is to provide organic-inorganic hybrid particles having a high fracture load at the time of compression and good compressive strain characteristics, and conductive particles, conductive materials and connection structures using the organic-inorganic hybrid particles.

According to a broad aspect of the present invention, there is provided a process for producing an organic electroluminescent device, which comprises using a plurality of inorganic particles having a first reactive functional group on its 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 particles, are provided.

In a specific aspect of the organic-inorganic hybrid particles 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 particles 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 particles 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.

In a specific aspect of the organic-inorganic hybrid particles 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 particles according to the present invention, the alkoxy group-containing organopolysiloxane has an alkyl group directly bonded to the 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 thereof and having the conductive layer, or as a spacer for a liquid crystal display element.

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

According to a broad aspect of the present invention, there is provided a conductive material comprising conductive particles and a binder resin, wherein the conductive particles comprise the above-mentioned organic-inorganic hybrid particles and a conductive layer disposed on the surface of the organic-inorganic hybrid particles do.

According to a broad aspect of the present invention, there is provided a liquid crystal display device including a first connection target member having a first electrode on a surface thereof, a second connection target member having a second electrode on a surface thereof, And the connection part is formed by conductive particles or is formed by a conductive material including the conductive particles and a binder resin, and the conductive particles are formed by the above-mentioned organic-inorganic hybrid particles and the above- And a conductive layer disposed on the surface of the organic-inorganic hybrid particles, wherein the first electrode and the second electrode are electrically connected by the conductive particles.

The organic-inorganic hybrid particles according to the present invention are obtained by using a plurality of inorganic particles having a first reactive functional group on its surface and an alkoxy group-containing organopolysiloxane having a second reactive functional group capable of reacting with the first reactive functional group, Because of the aggregation of the inorganic particles, the fracture load at the time of compression is high, and the organic-inorganic hybrid particles have good compressive strain characteristics.

1 is a cross-sectional view schematically showing an organic-inorganic hybrid particle according to a 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. 1. Fig.
3 is a cross-sectional view schematically showing a modified example of the conductive particles using the organic-inorganic hybrid particles shown in Fig.
4 is a cross-sectional view schematically showing a connection structure using the conductive particles shown in 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 particles according to the present invention are 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. 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 are provided with the above-described constitution, the organic-inorganic hybrid particles having a high fracture load at the time of compression can be obtained. Since the fracture load at the time of compression of the organic-inorganic hybrid particles is high, the organic-inorganic hybrid particles have good compressive strain characteristics. In order to obtain the organic-inorganic hybrid particles according to the present invention, the fracture load is effectively increased by using the alkoxy group-containing organopolysiloxane separately from the inorganic particles. Therefore, when the above-mentioned organic-inorganic hybrid particles are used as a spacer for a liquid crystal display element and arranged between substrates, or when a conductive layer is formed on the surface and used as conductive particles to electrically connect the electrodes, When a shock is applied to the liquid crystal display element using the spacer and the connection structure using the conductive particles, cracks or damage to the spacer or the conductive particle for the liquid crystal display element are less likely to occur.

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

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

The organic-inorganic hybrid particles (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 particles (1) are aggregates of the inorganic particles (11). The structure portion 12 is a material 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 thereof 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 particles (1) are obtained by using an inorganic particle having a first reactive functional group on its surface and an alkoxy group-containing organopolysiloxane having a second reactive functional group capable of reacting with the first reactive functional group.

The structure portion 12 is disposed on the surface of the inorganic particles 11. And the structure portion 12 is present between the plurality of inorganic particles 11. It is preferable that a plurality of the inorganic particles 11 are integrated through a structure (structure portion 12) derived from an alkoxy group-containing organopolysiloxane. It is preferable that a plurality of the inorganic particles 11 are integrated through the structure derived from the alkoxy group-containing organopolysiloxane (the structure portion 12) to obtain an aggregate of the inorganic particles 11. [ It is preferable that the structure section 12 binds the plurality of inorganic particles 11.

Examples of the inorganic particles include particles formed by a metal oxide, a metal nitride, a metal sulfide, a metal carbide, a composite thereof, and the like. Examples of the metal oxide include silica, alumina and titania. Among them, the inorganic particles are preferably silica particles.

The main component of the inorganic particles is an inorganic substance. The inorganic particles may contain carbon atoms in a small amount. The content of carbon atoms in 100 wt% of the inorganic particles is preferably 20 wt% or less, more preferably 10 wt% or less. Particles containing small amounts 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 them, a hydroxyl group is preferable in that a functional group can be introduced easily and in a large amount on the surface of the inorganic particles.

The inorganic particles preferably include a polysiloxane skeleton. The inorganic particles are preferably obtained by hydrolysis and condensation of a silane compound. The silane compound may have an organic group such as an alkyl group and a vinyl group. The particles obtained by using such an organic group-containing silane compound are also referred to as inorganic particles if the main component is an inorganic substance. The inorganic particles may be formed using an organopolysiloxane.

Examples of the silane compound include a compound represented by the following formula (1) (hereinafter sometimes referred to as a compound (1)) and a compound represented by the following formula (2) , And a compound represented by the following formula (3) (hereinafter sometimes referred to as a compound (3)). As the silane compound, at least one selected from the group consisting of compounds (1), (2) and (3) is preferably used. When such a compound is used, the resulting inorganic particle has a hydroxyl group in that it has a silanol group on its surface.

(1), Ra represents a (meth) acryloyl group, Rb represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent, R1 and R2 each represent a hydrogen atom, An alkyl group 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.

In the above formula (2), R 1, R 2, and R 3 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 of 1 to 5 carbon atoms or an acyl group of 2 to 5 carbon atoms.

The compound (1) has an Ra-O-Rb- group. This group contains a polymerizable unsaturated group and has an Ra 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 Compound (2) is used without using Compound (1), an organic polymer skeleton having a sufficiently high flexibility is not formed.

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

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

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, groups in which a substituent is bonded to the alkylene group, 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, or a group in which a phenylene group is bonded through an ether bond. Among them, 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. 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 may be an alkoxy group having 1 to 5 carbon atoms, 3 < / RTI > When Z in the formula (1) is an alkoxy group, it is more preferable that Z is 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 still more preferably a methyl group.

In the above formula (3), Ra represents a methyl group or an ethyl group. Ra in the above 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. R 1, R 2 and R 3 in the above formulas (1), (2) and (3) are preferably an alkyl group having 1 to 3 carbon atoms or an acyl group having 2 carbon atoms, More preferably an alkyl group having 1 to 3 carbon atoms, further preferably an alkyl group having 1 or 2 carbon atoms, particularly preferably a methyl group.

Examples of the compound (1) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Ethoxy silane, and 3-acryloxypropyl triethoxy silane. The compound (1) may be used alone or in combination of two or more.

Examples of the compound (2) include vinyltrimethoxysilane and vinyltriethoxysilane. The compound (2) may be used alone or in combination of two or more.

Examples of the compound (3) include methyltrimethoxysilane and ethyltrimethoxysilane. The compound (3) may be used alone or in combination of two or more.

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 depending on the kind 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 the alkoxy group, and thus 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, and an epoxy group, a (meth) acryloyl group or an alkoxy group is preferable in that the reaction with the first reactive functional group in the above- The value of g is more preferable. The alkoxy group-containing organopolysiloxane preferably has an epoxy group, (meth) acryloyl group or mercapto group as the second reactive functional group, more preferably an epoxy group or (meth) acryloyl group, and an epoxy group or (Meth) acryloyl group, and further preferably an alkoxy group, and it is more preferable to use an epoxy group, a (meth) acryloyl group or a mercapto group, and more preferably an epoxy group. More preferably an eutectic and an alkoxy group, more preferably an epoxy group or a mercapto group and an alkoxy group, particularly preferably an epoxy group and an alkoxy group. The alkoxy group is preferably a methoxy group or an ethoxy group.

It is preferable that the alkoxy group-containing organopolysiloxane has an epoxy group, a methoxy group or an ethoxy group as the second reactive functional group from the viewpoint of obtaining better compressive strain characteristics.

Examples of the alkoxy-containing organopolysiloxane include alkoxy oligomers and the like, and X-41-1053 and X-41-1059A (having an epoxy group, a methoxy group and an ethoxy group) , X-41-1056 (having an epoxy group and a methoxy group), X-41-1805 (having a mercapto group, a methoxy group and an ethoxy group), X-41-1818 (having a mercapto group and an ethoxy group) 41 to 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-500, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308 (having a methoxy group), and X-40-9238 (having an ethoxy group). The alkoxy-containing organopolysiloxane may be used alone or in combination of two or more.

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

It is more preferable that the inorganic particles have an epoxy group and an alkoxy group as the second reactive functional group. The inorganic particles preferably 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, more preferably an epoxy group or a (meth) acryloyl group and an alkoxy group and an alkyl group directly bonded to a silicon atom And most preferably has an epoxy group, an alkoxy group and an alkyl group directly bonded to a silicon atom. Depending on the presence of these preferred second reactive functional groups and the presence of these preferred second reactive functional groups and organic functional groups, better compressive strain characteristics are obtained.

The weight average molecular weight of the alkoxy group-containing organopolysiloxane is preferably 500 or more, more preferably 1000 or more, preferably 10000 or less, more preferably 7000 or less. The weight average molecular weight refers to the weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC).

It is preferable that the organic-inorganic hybrid particles are obtained by reacting the first reactive functional group and the second reactive functional group in that further excellent compression deformation characteristics can be obtained.

It is preferable that a plurality of the inorganic particles are integrated through the structure derived from the alkoxy group-containing organopolysiloxane in the organic-inorganic hybrid particles from the viewpoint of obtaining better compressive strain characteristics.

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

In the organic-inorganic hybrid particle, the particle diameter of each inorganic particle in the aggregate is preferably 0.1 nm or more, more preferably 1 nm or more, further preferably 3 nm or more, preferably 1000 nm or less, More preferably 500 nm or less, further preferably 200 nm or less, particularly preferably 100 nm or less. If the particle diameter of the inorganic particles in the aggregate is not less than the lower limit, brittleness tends not to be present due to a small grain size. If the particle size is less than the upper limit, brittleness tends to be hardly present due to small voids in the organic-inorganic hybrid particles.

From the viewpoint of further suppressing the damage of the organic-inorganic hybrid particles, the fracture load of the organic-inorganic hybrid particles is preferably 5 mN or more, more preferably 10 mN or more, furthermore preferably 11 mN or more. If the fracture load is lower than the lower limit, it is difficult for the organic-inorganic hybrid particles to be broken or damaged at the time of compression.

The breaking load can be measured, for example, as follows. The organic-inorganic hybrid particles are compacted at 25 캜 at a compression rate of 0.3 mN / sec and a maximum test load of 20 mN on the smooth indenter end face of a cylindrical column (diameter 100 탆, made of diamond) using a micro compression tester. At this time, the load value N and the compression displacement (mm) are measured. From the obtained measured values, the above-described compressive modulus can be obtained by the following formula. As the micro compression tester, for example, "Fisher Scope H-100" manufactured by Fisher Co., Ltd. or the like is used.

The breaking load represents a load value at the time when the inflection point is confirmed in the measurement value 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 even more preferably 80% or more. If the compression recovery rate is not lower than the lower limit, the organic-inorganic hybrid particles are less likely to be damaged and the organic-inorganic hybrid particles sufficiently follow and deform easily in response to variations in the intervals between the substrates or between the electrodes. This makes it difficult to cause connection defects between the substrates or between the electrodes.

The compression recovery rate can be measured, for example, as follows. Organic-inorganic hybrid particles are sprayed onto the sample track. The load (inverse load value) is applied to the organic-inorganic hybrid particles spread by 30% in the direction of the center of the organic-inorganic hybrid particles using a micro-compression tester, until the organic-inorganic hybrid particles are compression-deformed by 30%. Thereafter, the load is reduced to the original point load value (0.40 mN). And the compression-recovery rate can be obtained from the following equation by measuring the load-compression displacement between them. The load speed is 0.33 mN / sec. As the micro compression tester, for example, "Fisher Scope H-100" manufactured by Fisher Co., Ltd. or the like is used.

Compression recovery rate (%) = [(L1-L2) / L1] 100

L1: Compressive displacement from the original point load value to the reverse load value when the load is applied

L2: Deflection displacement from the inverse load value to the original point load value when releasing the load

The particle diameter of the organic-inorganic hybrid particles is preferably 0.1 mu m or more, more preferably 1 mu m or more, still more preferably 1.5 mu m or more, particularly preferably 2 mu m or more, preferably 1,000 mu m or less Is not more than 500 mu m, more preferably not more than 300 mu m, further preferably not more than 50 mu m, particularly preferably not more than 30 mu m, and most preferably not more than 5 mu m. 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 applications. 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 instrument using a principle such as laser light scattering, change in electric resistance value, image analysis after image pickup, etc. 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. In this method, organic-inorganic hybrid particles having a uniform particle diameter and further superior compressive strain characteristics are obtained. In the hydrolysis and condensation step, a hydrolysis and condensation reaction takes place at the contact interface between the silane compound and the water solvent to form a polysiloxane skeleton, and inorganic particles are obtained.

In the hydrolysis and condensation step, a catalyst is generally used. In the presence of a catalyst, the silane compound is reacted. In the hydrolysis and condensation step, for example, water and an acidic catalyst or a basic catalyst are used. The catalyst may be used alone or in combination of two or more.

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

In the hydrolysis and condensation step, an organic solvent other than water may be used. Specific examples of the organic solvent include alcohols, ketones, esters, (cyclo) paraffins, ethers and aromatic hydrocarbons. The organic solvent may be used alone or in combination of two or more.

The reaction temperature in the hydrolysis and condensation step is not particularly limited, but is preferably 0 ° C or higher, preferably 100 ° C or lower, more preferably 70 ° C or lower. 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 particles comprises reacting a plurality of inorganic particles having a first reactive functional group on its surface with an alkoxy group-containing organopolysiloxane having a second reactive functional group capable of reacting with the first reactive functional group, And a step of obtaining an aggregate of particles. In this step, it is preferable that a plurality of the inorganic particles are integrated through a structure derived from the alkoxy group-containing organopolysiloxane. It is preferable to integrate a plurality of inorganic particles through a structure (structure portion) derived from an alkoxy group-containing organopolysiloxane to obtain an aggregate of inorganic particles.

For example, in the case where the layer of the silane compound containing water and the alkoxy group-containing organopolysiloxane is separated in the vessel, or the water and the layer containing the silane compound and the alkoxy group-containing organopolysiloxane And the alkoxy group-containing organopolysiloxane is adhered and precipitated on the surface of the obtained inorganic particle to form a plurality of the first functional groups having the first reactive functional group on the surface thereof An aggregate of the inorganic particles may be obtained by reacting an inorganic particle and an alkoxy group-containing organopolysiloxane having a second reactive functional group capable of reacting with the first reactive functional group.

(Uses of Organic Inorganic Hybrid Particles)

The use of the organic-inorganic hybrid particles is not particularly limited. The above-mentioned organic-inorganic hybrid particles are suitably used for various applications where a high breaking load is required. The organic-inorganic hybrid particles are preferably used for electronic parts. The organic-inorganic hybrid particles are preferably organic-inorganic hybrid particles for electronic components.

The organic-inorganic hybrid particles are preferably used to form conductive layers on the surface and to obtain conductive particles having the conductive layers, or to use them as spacers for liquid crystal display elements. It is preferable that the organic-inorganic hybrid particles are used for forming a conductive layer on the surface and obtaining the conductive particles having the conductive layer. The organic-inorganic hybrid particles are preferably used as a spacer for a liquid crystal display element. Since the breakdown load of the organic-inorganic hybrid particles is high, the organic-inorganic hybrid particles are used as a spacer for a liquid crystal display element and arranged between the substrates, or a conductive layer is formed on the surface and used as conductive particles to electrically connect the electrodes In one case, the liquid crystal display element spacer or the conductive particle is hardly broken and hardly damaged. Particularly, when a shock 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 hardly broken and hardly damaged.

In addition, the organic-inorganic hybrid particles are suitably used as an impact absorbing agent or a vibration absorbing agent. For example, the above organic-inorganic hybrid particles can be used as a substitute for rubber or a spring.

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

The conductive particles 21 shown in Fig. 2 have organic-inorganic hybrid particles 1 and a conductive layer 31A disposed on the surface of the organic-inorganic hybrid particles 1. [

The conductive layer 31A 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 particles 1 is covered with the conductive layer 31A.

Fig. 3 is a cross-sectional view schematically showing a modified example of the conductive particles using the organic-inorganic hybrid particles shown in Fig.

The conductive particles 22 shown in Fig. 3 have organic-inorganic hybrid particles 1, a conductive layer 31B, a plurality of core materials 32 and a plurality of insulating materials 33. [

The conductive layer 31B is disposed on the surface of the organic-inorganic hybrid particle 1. The conductive layer 31B has a first conductive layer 31Ba as an inner layer and a second conductive layer 31Bb as an outer layer. A first conductive layer 31Ba is disposed on the surface of the organic-inorganic hybrid particles 1. [ The second conductive layer 31Bb is disposed on the surface of the first conductive layer 31Ba.

The conductive particles 22 have a plurality of projections on the conductive surface. The conductive layer 31B and the second conductive layer 31Bb have a plurality of projections 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 deep seam materials (32) are arranged on the surface of the organic-inorganic hybrid particles (1). A plurality of deep seam materials 32 are embedded in the conductive layer 31B. The core material 32 is disposed inside the protrusions of the conductive particles 22 and the conductive layer 31B. The conductive layer 31B covers a plurality of deep seam materials 32. [ The outer surface of the conductive layer 31B is raised by the plurality of deep seam 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 31B is covered with the insulating material 33. [ The insulating material 33 is formed of a material having an insulating property and is insulating particles. As described above, the conductive particles may have an insulating material disposed on the outer surface of the 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, And the like. Examples of the metal include indium tin oxide (ITO) and solder. Among them, an alloy including tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable because connection resistance between electrodes can be further lowered.

Like the conductive particles 21, the conductive layer may be formed by one 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 laminated structure of two or more layers. When the conductive layer is formed of a plurality of layers, it is preferable that the outermost layer is a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, more preferably a gold layer. When the outermost layer is the preferable conductive layer, the connection resistance between the electrodes is further lowered. Further, when the outermost layer is a gold layer, corrosion resistance is further increased.

The method for forming the 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 of electroless plating, a method of electroplating, a method of physical vapor deposition, and a paste containing metal powder or metal powder and a binder are coated on the surface of the organic-inorganic hybrid particle And a coating method. Among them, the electroless plating method is preferable because the formation of the conductive layer is simple. Examples of the physical deposition method include vacuum deposition, ion plating and ion sputtering.

The particle diameter of the conductive particles is preferably 0.1 mu m or more, more preferably 0.5 mu m or more, further preferably 1 mu m or more, preferably 520 mu m or less, more preferably 500 mu m or less, Is not more than 100 mu m, more preferably not more than 50 mu m, particularly preferably not more than 20 mu m. When the particle diameters of the conductive particles are not less than the lower limit and not more than the upper limit, when the electrodes are connected using the conductive particles, the contact area between the conductive particles and the electrode becomes sufficiently large, . Further, the gap between the electrodes connected via the conductive particles does not become excessively large, and the conductive layer becomes difficult to peel off from the surface of the organic-inorganic hybrid particles. When the particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, the conductive particles can be suitably used for the conductive material.

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

The thickness of the conductive layer is preferably 0.005 탆 or more, more preferably 0.01 탆 or more, preferably 10 탆 or less, more preferably 1 탆 or less , More preferably not more than 0.3 mu m. When the thickness of the conductive layer is not less than the lower limit and not more than the upper limit, sufficient conductivity is obtained and the conductive particles are not too hard and the conductive particles are sufficiently deformed at the time of connection between the electrodes.

When the conductive layer is formed of a plurality of layers, the thickness of the conductive layer in the outermost layer is preferably 0.001 탆 or more, more preferably 0.01 탆 or more, preferably 0.5 탆 or less, more preferably 0.1 Mu m or less. When the thickness of the conductive layer in the outermost layer is not less than the lower limit and not more than the upper limit, the covering by the conductive layer in the outermost layer becomes uniform, the corrosion resistance becomes sufficiently high and the connection resistance between the electrodes becomes further lower. In addition, when the outermost layer is a gold layer, the thinner the thickness of the 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 the projection has a plurality of projections. In many cases, an oxide film is formed on the surface of an electrode connected by conductive particles. When conductive particles having protrusions are used, conductive particles are disposed between the electrodes and pressed, whereby the oxide film is effectively removed by protrusions. As a result, the electrode and the conductive layer of the conductive particle can be more reliably contacted, and the connection resistance between the electrodes can be lowered. When the conductive particles are provided with an insulating material on the surface or when the conductive particles are dispersed in the binder resin so that they can be used as the conductive material, the protrusions of the conductive particles prevent the insulating particles between the conductive particles and the electrodes, The resin can be effectively excluded. As a result, the reliability of conduction between the electrodes can be improved.

Methods for forming protrusions on the surface of the conductive particles include a method in which a core material is attached to the surface of the organic-inorganic hybrid particle and then a conductive layer is formed by electroless plating and a method in which electroless plating , A method of forming a conductive layer by depositing a core material after the formation of the conductive layer by electroless plating, and the like. Further, in order to form the projections, the core material may not be used.

The conductive particles may include an insulating material disposed on an outer surface of the conductive layer. In this case, if the conductive particles are used for connection between the electrodes, it is possible to prevent short-circuiting between adjacent electrodes. More specifically, when a plurality of conductive particles are brought into contact with each other, an insulating material exists between a plurality of electrodes, so that a short circuit between adjacent electrodes in the lateral direction as well as between the upper and lower electrodes can be prevented. Further, at the time of connection between the electrodes, the conductive particles of the conductive particles can be easily excluded from the insulating material between the electrodes by pressing the conductive particles with the two electrodes. When the conductive particles have protrusions on the surface of the conductive layer, the insulating material between the conductive layer of the conductive particles and the electrode can be more easily excluded. The insulating material is preferably an insulating resin layer or insulating particles, more preferably insulating particles. The insulating particles are preferably insulating resin particles.

(Conductive material)

The conductive material includes the above-described conductive particles and a binder resin. The conductive particles are preferably dispersed in a binder resin and can be 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 a vinyl resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer and an elastomer. The binder resin may be used alone or in combination of two or more.

Examples of the vinyl resin include vinyl acetate resin, acrylic resin and styrene resin. Examples of the thermoplastic resin include a polyolefin resin, an ethylene-vinyl acetate copolymer and a 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 photo-curable 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 hydrogenated product of a styrene- Additives and the like. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

The conductive material may contain, in addition to the conductive particles and the binder resin, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, Flame retardant, and the like.

As a method for dispersing the conductive particles in the binder resin, conventionally known dispersion methods can be used, and there is no particular limitation. Examples of the 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 by a planetary mixer or the like to disperse the conductive particles in water or an organic solvent A method in which the binder resin is uniformly dispersed using a homogenizer or the like and then added to the binder resin and kneaded and dispersed by a planetary mixer or the like and a method in which the binder resin is diluted with water or an organic solvent, And the mixture is kneaded and dispersed by a planetary mixer or the like.

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 containing conductive particles may be laminated on the conductive film containing the conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.

The content of the binder resin in 100 wt% of the conductive material is preferably 10 wt% or more, more preferably 30 wt% or more, still more preferably 50 wt% or more, particularly preferably 70 wt% Is 99.99% by weight or less, and more preferably 99.9% by weight or less. When the content of the binder resin is not less than the lower limit and not more than the upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the member to be connected connected by the conductive material is further enhanced.

The content of the conductive particles in 100 wt% of the conductive material is preferably at least 0.01 wt%, more preferably at least 0.1 wt%, preferably at most 40 wt%, more preferably at most 20 wt% By weight is not more than 10% by weight. When the content of the conductive particles is not less than the lower limit and not more than the upper limit, the reliability of conduction between the electrodes is further increased.

(Connection structure and liquid crystal display element)

The connection structure can be obtained by connecting the members to be connected using the above-described conductive particles or by using a conductive material including the above-described conductive particles and a binder resin.

The connection structure includes a first connection object member, a second connection object member, and a connection portion connecting the first connection object member and the second connection object member, and the connection portion is formed by the above-described conductive particles Or a connection structure formed by a conductive material containing the above-mentioned conductive particles and a binder resin. When the conductive particles are used alone, the connection portion itself is 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.

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

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 has the first connection target member 52, the second connection target member 53, the first connection target member 52 and the second connection target member 53 And a connecting portion 54 connected thereto. The connecting portion 54 is formed of a conductive material including the conductive particles 21 and a binder resin. In Fig. 4, for convenience of illustration, the conductive particles 21 are schematically shown. 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 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 to each other by one or more conductive particles 1. [ Therefore, 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 the manufacturing method of the connection structure, there can be mentioned a method of arranging the conductive material between the first connection target member and the second connection target member, obtaining a laminate, and then heating and pressing the laminate. The pressure of the pressurization is about 9.8 x 10 ⁴ to 4.9 x 10 ⁶ Pa. The temperature of the heating is about 120 to 220 占 폚. The pressurizing pressure for connecting the electrodes of the flexible printed substrate, the electrodes disposed on the resin film, and the electrodes of the touch panel is about 9.8 x 10 ⁴ to 1.0 x 10 ⁶ Pa.

Specific examples of the member to be connected include electronic parts such as semiconductor chips, capacitors and diodes, and electronic parts such as printed boards, flexible printed boards, glass epoxy boards, and circuit boards such as glass boards. The conductive material is preferably a conductive material for connecting electronic components. It is preferable that the conductive paste is a paste-like conductive material and is coated on the member to be connected in a state of paste.

The conductive particles and the conductive material are suitably used for a touch panel. Therefore, it is preferable that the connection target member is a flexible printed substrate or a connection target member in which electrodes are disposed on the surface of the resin film. Preferably, the connection target member is a flexible printed circuit board, and is a connection target member in which electrodes are disposed on the surface of the resin film. The flexible printed circuit board generally has an electrode on its surface.

Examples of the electrode provided on the member to be connected include a metal electrode 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 target member is a flexible printed circuit 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. When the electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode in which an aluminum layer is laminated on the surface of the metal oxide layer. Examples of the material of 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 suitably used as a spacer for a liquid crystal display element. That is, the organic-inorganic hybrid particles include a pair of substrates constituting a liquid crystal cell, liquid crystal sealed between the pair of substrates, and a liquid crystal display element having a liquid crystal display element spacer disposed between the pair of substrates Is used suitably to obtain the < RTI ID = 0.0 >

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

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

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 particles 1 are used as spacers for liquid crystal display elements. The spacing of the pair of transparent glass substrates 82 is regulated by the plurality of organic-inorganic hybrid particles 1. A sealant 86 is disposed between the edge portions of the pair of transparent glass substrates 82. The sealant 86 prevents the liquid crystal 85 from flowing out to the outside. In Fig. 5, for convenience of illustration, the organic-inorganic hybrid particles 1 are schematically shown. Instead of the organic-inorganic hybrid particles (1), other organic-inorganic hybrid particles may be used.

The arrangement density of the liquid crystal display element spacers per mm 2 in the liquid crystal display element is preferably 10 / mm 2 or more, and preferably 1000 / mm 2 or less. When the batch density is 10 pieces / mm < 2 > or more, the cell gaps become even more uniform. When the arrangement density is 1000 pieces / mm 2 or less, the contrast of the liquid crystal display element is further improved.

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

(Example 1)

300 g of 0.13 wt% aqueous ammonia solution was placed in a 500 mL reaction vessel equipped with a stirrer and a thermometer. Subsequently, 4.1 g of methyltrimethoxysilane, 19.2 g of vinyltrimethoxysilane, 0.2 g of a silicone alkoxy oligomer ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd., And an epoxy group and an alkyl group directly bonded to the silicon atom: weight average molecular weight: about 1600) 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 the particles were isolated in an aqueous ammonia solution. The resulting particles were calcined at 400 DEG C under an oxygen partial pressure of 10 ^-17 atm for 2 hours , And organic-inorganic hybrid particles were obtained. The particle diameters of the obtained organic-inorganic hybrid particles are shown in Table 1 below.

(Example 2)

(KR-500, manufactured by Shin-Etsu Chemical Co., Ltd., having a methoxy group and an alkyl group directly bonded to a silicon atom and having a weight average molecular weight: 3000 to 10000), organic-inorganic hybrid particles were obtained.

(Example 3)

(X-41-1805 " manufactured by Shin-Etsu Chemical Co., Ltd.), and a silicone oligomer (X-41-1053 manufactured by Shin-Etsu Chemical Co., : About 1800), organic-inorganic hybrid particles were obtained.

(Example 4)

300 g of 0.13 wt% aqueous ammonia solution was placed in a 500 mL reaction vessel equipped with a stirrer and a thermometer. Subsequently, 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 proceeded with stirring, 0.7 g of a silicon alkoxy oligomer ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd., having an ethoxy group and an epoxy group and an alkyl group directly bonded to a silicon atom) And the mixture was slowly stirred. After the silicon alkoxy oligomer was disappeared, 2.4 mL of a 25 wt% ammonia aqueous solution was added, and particles were isolated from the aqueous ammonia solution. The obtained particles were sintered at 400 ° C for 2 hours at an oxygen partial pressure of 10 ^-17 atm to prepare an organic-inorganic hybrid particle .

(Example 5)

300 g of 0.13 wt% aqueous ammonia solution was placed in a 500 mL reaction vessel equipped with a stirrer and a thermometer. Subsequently, in the aqueous ammonia solution in the reaction vessel, 1.9 g of 3-methacryloxypropyltrimethoxysilane, 4.1 g of methyltrimethoxysilane, 17.3 g of vinyltrimethoxysilane, 0.2 g of a silicone alkoxy oligomer Quot; X-41-1053 ", having a methoxy group and an ethoxy group, and an epoxy group and an alkyl group directly bonded to a silicon atom) was added slowly. After the hydrolysis and condensation reaction proceeded with stirring, 2.4 mL of a 25 wt% aqueous ammonia solution was added, and the particles were isolated in an aqueous ammonia solution. The resulting particles were calcined at 400 DEG C under an oxygen partial pressure of 10 ^-17 atm for 2 hours , And organic-inorganic hybrid particles were obtained.

(Example 6)

(KF-995, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), which is an epoxy silane coupling agent, To obtain an alkoxy group-containing organopolysiloxane A (having an epoxy group and an alkoxy group and having 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)

(KF-995, manufactured by Shin-Etsu Chemical Co., Ltd.) 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 (weight-average molecular weight having an acryloyl group and an alkoxy group: 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)

("KF-995" manufactured by Shin-Etsu Chemical Co., Ltd.) as a cyclic siloxane and 3-methacryloxypropyltrimethoxysilane as a silane coupling agent having a methacryloyl group ("KBM -503 ") was reacted to obtain a methacryloxy group-containing organopolysiloxane C (weight average molecular weight having a methacryloyl group and an alkoxy group: 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 replaced by an alkoxy group-containing organopolysiloxane C.

(Example 9)

(1) palladium deposition process

The organic-inorganic hybrid particles obtained in Example 4 were prepared. The organic-inorganic hybrid particles were etched and washed with water. Then, the organic-inorganic hybrid particles were added to 100 mL of the palladium catalyst solution containing 8 wt% of the palladium catalyst and stirred. Thereafter, it was filtered and washed. Organic-inorganic hybrid particles were added to a 0.5 wt% dimethylamine borane solution at pH 6 to obtain palladium-coated organic-inorganic hybrid particles.

(2) Core material adhesion process

The organic-inorganic hybrid particles having palladium attached thereto were stirred and dispersed in 300 ml of ion-exchanged water for 3 minutes to obtain a dispersion. Subsequently, 1 g of a metallic nickel particle slurry (average particle diameter 100 nm) was added to the above dispersion for 3 minutes to obtain an organic-inorganic hybrid particle having a core material attached thereto.

(3) Electroless nickel plating process

A nickel layer was formed on the surface of the organic-inorganic hybrid particles having the core material attached thereto by the electroless plating method to prepare conductive particles. The thickness of the nickel layer was 0.1 mu m.

(Example 10)

(1) Fabrication of insulating particles

In a 1000 mL separable flask equipped with a four-neck separable cover, a stirring blade, a three-way cock, a cooling tube, and a temperature probe, 100 mmol of methyl methacrylate and 100 mmol of N, N, N-trimethyl- A monomer composition containing 1 mmole of monooxyethylammonium chloride and 1 mmole of 2,2'-azobis (2-amidinopropane) dihydrochloride was weighed in ion-exchanged water to a solid content of 5% by weight , And the mixture was stirred at 200 rpm, and polymerization was carried out at 70 deg. C in a nitrogen atmosphere for 24 hours. After completion of the reaction, the resultant was lyophilized to obtain insulating particles having an ammonium group on the surface and having an average particle diameter of 220 nm and a CV value of 10%.

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

(2) Production of conductive particles having 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. The mixture was filtered through a 3 탆 mesh filter, washed with methanol, and dried to obtain conductive particles with insulating particles.

As a result of observation by a scanning electron microscope (SEM), only one covering layer of insulating particles was formed on the surface of the conductive particles. The coated area of the insulating particles (that is, the projected area of the insulating particles) was calculated from the center of the conductive particles by an image analysis to find that the covering ratio was 30%.

(Comparative Example 1)

Organic-inorganic hybrid particles were obtained in the same manner as in Example 1 except that no silicon alkoxy oligomer ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

(Comparative Example 2)

Except that the silicone alkoxy oligomer ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to a methylphenyl silicone oil having no reactivity ("KF-56A" available from Shin- Similarly, organic-inorganic hybrid particles were obtained.

(evaluation)

(1) Particle diameter of organic-inorganic hybrid particles

With regard to the particle diameters of the obtained organic-inorganic hybrid particles, the particle diameters of about 10,000 organic-inorganic hybrid particles were measured using a particle size distribution measuring apparatus ("Multisizer 3" manufactured by Beckman Coulter, Inc.). The average value of the measured particle diameters was determined to be the particle diameter of the organic-inorganic hybrid particles.

(2) The breaking load of the organic-inorganic hybrid particles

The fracture load of the obtained organic-inorganic hybrid particles was measured by the above-described method using a "Fisher Scope H-100" manufactured by Fisher Company.

(3) Particle diameter of each inorganic particle (per one inorganic particle) in the aggregate

In the obtained organic-inorganic hybrid particles, the particle diameters of the respective inorganic particles in the aggregate were measured by X-ray small angle scattering (SmartLab (parallel beam method) manufactured by Rigaku Co., Ltd., powder X-ray diffraction method) . We adopted the average size obtained using the analysis software NANO-Solver. In the analysis software nano-solver model, the scatterer model was used as a sphere, the particles were made of SiO ₂ , and the matrix was made of 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

Preparation of conductive particles:

The organic-inorganic hybrid particles obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were washed and dried. Thereafter, a nickel layer was formed on the surface of the obtained organic-inorganic hybrid particles by an electroless plating method to prepare conductive particles. The thickness of the nickel layer was 0.1 mu m. In Examples 9 and 10, the obtained conductive particles were used as they were.

Fabrication of the connection structure:

, 10 parts by weight of a bisphenol A type epoxy resin ("Epicoat 1009" available from Mitsubishi Chemical Corporation), 40 parts by weight of an acrylic rubber (weight average molecular weight: about 800,000), 200 parts by weight of methyl ethyl ketone, , And 2 parts by weight of a silane coupling agent ("SH6040" manufactured by Dow Corning Toray Silicone Co., Ltd.) were added, and the content of the conductive particles was adjusted to 3 wt% A composition was obtained.

The resulting resin composition was applied to a PET (polyethylene terephthalate) film having a thickness of 50 占 퐉 which had been subjected to one side surface release treatment and dried for 5 minutes by hot air at 70 占 폚 to produce an anisotropic conductive film. The thickness of the obtained anisotropic conductive film was 12 占 퐉.

The obtained anisotropic conductive film was cut into a size of 5 mm x 5 mm. The cut anisotropic conductive film was placed on one side of a PET substrate (3 cm wide, 3 cm long) provided with ITO (height 0.1 m, L / S = 20 m / 20 m) In the center of the attachment. Subsequently, a two-layer flexible printed circuit board (width 2 cm, length 1 cm) provided with the same gold electrode was positioned and aligned so that the electrodes overlapped with each other. The laminate of the PET substrate and the two-layer flexible printed substrate was subjected to thermocompression bonding under conditions of 10 N, 180 캜 and 20 seconds to obtain a connection structure. Further, a two-layer flexible printed substrate in which a copper electrode was formed on a polyimide film and a copper electrode surface was plated with Au was used.

The connection resistance between the opposing electrodes of the resulting connection structure was measured by the four-terminal method. The connection resistance was judged by the following criteria.

[Evaluation Criteria of Connection Resistance]

○○: Connection resistance is 3.0Ω or less

?: The connection resistance exceeds 3.0, 4.0?

DELTA: Connection resistance exceeding 4.0, 5.0 or less

×: Connection resistance exceeds 5.0Ω

The results are shown in Table 1 below.

(5) Examples of use as spacers for liquid crystal display elements

Production of STN type liquid crystal display device:

To the dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, a spacer (organic-inorganic hybrid particles) for liquid crystal display elements of Examples 1 to 8 was added in an amount of 2% by weight in the solid content concentration And stirred to obtain a dispersion liquid for a liquid crystal display element.

An SiO ₂ film was deposited on one surface of a pair of transparent glass plates (50 mm in length, 50 mm in width, and 0.4 mm in thickness) by the 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 coated on the glass substrate provided with the obtained ITO film by spin coating and baked at 280 占 폚 for 90 minutes to form a polyimide alignment film. After the rubbing treatment was applied to the alignment film, the liquid crystal display element spacer was wet-sprayed on the alignment film side of one of the substrates so as to have 100 to 200 pieces per 1 mm 2 of the film. A sealing agent was formed around the other substrate, and then the substrate and the substrate on which the spacer was spread were arranged so as to face each other at a rubbing direction of 90 占 and both were bonded. Thereafter, the sealing agent was cured at 160 DEG C for 90 minutes to obtain an empty cell (a screen containing no liquid crystal). An STN type liquid crystal (manufactured by DIC Co.) containing a chiral agent was injected into the obtained empty cell. Then, the injection port was sealed with a sealant and then heat-treated at 120 DEG C for 30 minutes to obtain an STN type liquid crystal display device.

In the liquid crystal display element obtained, spacings between the substrates were well regulated by the liquid crystal display element spacers of Examples 1 to 8. Further, the liquid crystal display element exhibited good display quality.

One… Organic-inorganic hybrid particles
11 ... Inorganic particle
12 ... A structural part derived from an alkoxy group-containing organopolysiloxane
21, 22 ... Conductive particle
31A, 31B ... Conductive layer
31Ba ... The first conductive layer
31Bb ... The second conductive layer
32 ... Seam material
33 ... Insulating material
51 ... Connection structure
52 ... The first connection object member
52a ... The first electrode
53 ... The second connection object member
53a ... The second electrode
54 ... Connection
81 ... Liquid crystal display element
82 ... Transparent glass substrate
83 ... Transparent electrode
84 ... Alignment film
85 ... Liquid crystal
86 ... Sealant

Claims (11)

A plurality of inorganic particles having a first reactive functional group on the surface thereof and an alkoxy group-containing organopolysiloxane having a second reactive functional group capable of reacting with the first reactive functional group,
The aggregation of the inorganic particles,
The weight-average molecular weight of the alkoxy group-containing organopolysiloxane is 1000 or more and 10000 or less,
Wherein the alkoxy group-containing organopolysiloxane has an epoxy group as the second reactive functional group. 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 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. 3. The organic-inorganic hybrid particle according to claim 1 or 2, wherein the alkoxy group-containing organopolysiloxane has a methoxy group as the second reactive functional group. 3. The organic-inorganic hybrid particle according to claim 1 or 2, wherein the alkoxy group-containing organopolysiloxane has an alkyl group directly bonded to a silicon atom. The organic-inorganic hybrid particle according to any one of claims 1 to 3, which is used for obtaining a conductive particle having a conductive layer formed on its surface and having the conductive layer, or used as a spacer for a liquid crystal display element. The conductive particle according to claim 1 or 2, wherein a conductive layer is formed on the surface and used to obtain conductive particles having the conductive layer,
Wherein the conductive particles are used for electrically connecting electrodes. The organic-inorganic hybrid particle according to claim 1 or 2,
And a conductive layer disposed on a surface of the organic-inorganic hybrid particle. A conductive particle and a binder resin,
Wherein the conductive particles comprise the organic-inorganic hybrid particles according to claim 1 or 2 and a conductive layer disposed on the surface of the organic-inorganic hybrid particles. A first connection target member having a first electrode on its surface,
A second connection target member having a second electrode on its surface,
And a connecting portion connecting the first connection target member and the second connection target member,
Wherein the connection portion is formed of conductive particles or formed of a conductive material containing the conductive particles and a binder resin,
Wherein the conductive particles comprise the organic-inorganic hybrid particles according to claim 1 or 2 and a conductive layer disposed on the surface of the organic-inorganic hybrid particles,
Wherein the first electrode and the second electrode are electrically connected by the conductive particles. delete

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