TWI506076B - Organic and inorganic composite particles, conductive particles, conductive materials and connecting structures - Google Patents

Description

Organic-inorganic composite particles, conductive particles, conductive materials, and bonded structures

The present invention relates to an organic-inorganic composite particle which is an aggregate of a plurality of inorganic particles. Further, the present invention relates to a conductive particle, a conductive material, and a bonded structure using the above-described organic-inorganic composite particles.

An anisotropic conductive material such as an anisotropic conductive paste or an anisotropic conductive film is known. In the anisotropic conductive material, conductive particles are dispersed in the binder resin. The anisotropic conductive material is used to electrically connect electrodes of various connection target members such as a flexible printed circuit board (FPC), a glass substrate, and a semiconductor wafer to obtain a connection structure. Further, 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 the resin particles used in the above-mentioned conductive particles, Patent Document 1 listed below discloses polymer particles having a breaking point load of 9.8 mN or less. In Patent Document 1, preferred examples of the polymer particles include (a) a metal oxide such as cerium oxide, aluminum oxide or titanium oxide, a metal nitride, a metal sulfide or a metal carbide. a state in which the formed inorganic particles are dispersed in an organic substance; (b) a metal such as an (organic) polysiloxane or a polytitanium alkane An alkyl chain (a molecular chain containing a "metal-oxygen-metal" bond) and a molecular molecule compounded at a molecular level; and (c) an organic inorganic polymer particle containing a vinyl polymer skeleton and a polyoxyalkylene skeleton The situation and so on.

Further, the liquid crystal display element is configured by disposing a liquid crystal between two glass substrates. In the liquid crystal display device, in order to uniformly and fixedly maintain the interval (gap) between the two glass substrates, A spacer is used as the gap control material. As the spacer, resin particles are usually used.

As an example of the conductive particles or the resin particles used in the spacer for a liquid crystal display device, Patent Document 2 discloses that a polyfunctional decane compound having a polymerizable unsaturated group is used as a surfactant. The organic-inorganic composite particles obtained by performing hydrolysis and polycondensation in the presence. In the patent document 2, the polyfunctional decane compound is a first fluorene-containing compound containing at least one radical-polymerizable group selected from the compounds represented by the following formula (X) and derivatives thereof.

In the above formula (X), R1 represents a hydrogen atom or a methyl group, R2 represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent, R3 represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R4 represents an election. At least one monovalent group of a group consisting of a free hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a fluorenyl group having 2 to 5 carbon atoms.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] WO2012/020799A1

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-204119

Regarding the conventional organic-inorganic composite particles described in Patent Documents 1 and 2, there is a case where the breaking load at the time of compression is low.

Therefore, the organic-inorganic composite particles are disposed between the substrates as spacers for liquid crystal display elements, or a conductive layer is formed on the surface to serve as conductive particles, and between the electrodes In the case of electrical connection, when a liquid crystal display element using the spacer for a liquid crystal display element and a connection structure using the conductive particles are applied, the spacer for the liquid crystal display element or the conductive particles may be broken or damaged. Happening.

An object of the present invention is to provide an organic-inorganic composite particle having a high breaking load at the time of compression and having excellent compression deformation characteristics, and conductive particles, a conductive material and a bonded structure using the organic-inorganic composite particles.

According to a broad aspect of the present invention, there is provided an organic-inorganic composite particle comprising a plurality of inorganic particles having a first reactive functional group on a surface thereof and a second reactive group capable of reacting with the first reactive functional group It is obtained by using an alkoxy group-containing organic polyoxyalkylene having a functional group, and is an aggregate of the above inorganic particles.

In a specific aspect of the organic-inorganic composite particles of the present invention, the first reactive functional group is a hydroxyl group.

In a specific aspect of the organic-inorganic composite particles of the present invention, the alkoxy-containing organic polyoxyalkylene has an epoxy group or a (meth) acrylonitrile group as the second reactive functional group.

In a specific aspect of the organic-inorganic composite particles of the present invention, the alkoxy-containing organopolyoxane has an epoxy group as the second reactive functional group.

In a specific aspect of the organic-inorganic composite particles of the present invention, a plurality of the inorganic particles may be integrated via a structure derived from the alkoxy-containing organic polyoxyalkylene to obtain an aggregate of the inorganic particles.

In a specific aspect of the organic-inorganic composite particles of the present invention, the alkoxy-containing organopolysiloxane has a methoxy group as the second reactive functional group.

In a specific aspect of the organic-inorganic composite particles of the present invention, the alkoxy-containing organopolyoxane has an alkyl group directly bonded to a ruthenium atom.

The organic-inorganic composite particles of the present invention are preferably used to form a conductive layer on the surface. Conductive particles having the above conductive layer are obtained or used as spacers for liquid crystal display elements.

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

According to a broad aspect of the present invention, a conductive material comprising conductive particles and a binder resin, and the conductive particles include the organic-inorganic composite particles and a conductive layer disposed on a surface of the organic-inorganic composite particles.

According to a broad aspect of the present invention, a connection structure includes: 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 a connection portion connecting the above a first connection target member and the second connection target member; and the connection portion is formed of conductive particles or a conductive material including the conductive particles and a binder resin; and the conductive particles include the organic-inorganic composite particles And a conductive layer disposed on a surface of the organic-inorganic composite particle; and the first electrode and the second electrode are electrically connected by the conductive particles.

The organic-inorganic composite particles of the present invention are a plurality of inorganic particles having a first reactive functional group on the surface and an alkoxy-containing organic having a second reactive functional group reactive with the first reactive functional group. It is obtained by polyaluminoxane, which is an aggregate of the above inorganic particles, so that the fracture load at the time of compression is high, and the organic-inorganic composite particles have good compression deformation characteristics.

1‧‧‧Organic and inorganic composite particles

11‧‧‧Inorganic particles

12‧‧‧From the structure of the alkoxy-containing organopolyoxane

21, 22‧‧‧ conductive particles

31A, 31B‧‧‧ conductive layer

31Ba‧‧‧1st conductive layer

31Bb‧‧‧2nd conductive layer

32‧‧‧ core material

33‧‧‧Insulating substances

51‧‧‧Connection structure

52‧‧‧1st connection object component

52a‧‧‧1st electrode

53‧‧‧2nd connection object component

53a‧‧‧2nd electrode

54‧‧‧Connecting Department

81‧‧‧Liquid display components

82‧‧‧Transparent glass substrate

83‧‧‧Transparent electrode

84‧‧‧Alignment film

85‧‧‧LCD

86‧‧‧Sealant

Fig. 1 is a cross-sectional view schematically showing an organic-inorganic composite 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 composite particles shown in Fig. 1.

Figure 3 is a schematic representation of the conductivity of the organic-inorganic composite particles shown in Figure 1. A cross-sectional view of a variation of particles.

Fig. 4 is a cross-sectional view schematically showing a connection structure using the conductive particles shown in Fig. 2 .

Fig. 5 is a cross-sectional view schematically showing a liquid crystal display device in which the organic-inorganic composite particles shown in Fig. 1 are used as spacers for liquid crystal display elements.

Hereinafter, the present invention will be described in detail.

(organic-inorganic composite particles)

The organic-inorganic composite particles of the present invention are a plurality of inorganic particles having a first reactive functional group on the surface and an alkoxy-containing organic having a second reactive functional group reactive with the first reactive functional group. Obtained by polyoxyalkylene. The organic-inorganic composite particles of the present invention are an aggregate of the above inorganic particles.

Since the organic-inorganic composite particles of the present invention have the above-described configuration, organic-inorganic composite particles having a high breaking load at the time of compression can be obtained. The organic-inorganic composite particles have a high breaking load at the time of compression, and thus the organic-inorganic composite particles have good compression deformation characteristics. In order to obtain the organic-inorganic composite particles of the present invention, the above-mentioned inorganic particles containing the alkoxy group and the above inorganic particles are used, respectively, and the breaking load is effectively increased. Therefore, when the above-mentioned organic-inorganic composite particles are used as spacers for liquid crystal display elements, they are disposed between substrates, or a conductive layer is formed on the surface to be used as conductive particles, and electrodes are electrically connected to each other. When an impact is applied to the liquid crystal display element of the device spacer and the connection structure using the conductive particles, the spacer or the conductive particles for the liquid crystal display element are less likely to be broken 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 an organic-inorganic composite particle according to a first embodiment of the present invention.

The organic-inorganic composite particle 1 shown in Fig. 1 has a plurality of inorganic particles 11 and a structure portion 12 derived from an alkoxy group-containing organic polyoxyalkylene. The organic-inorganic composite particles 1 are an aggregate of the inorganic particles 11. The structural portion 12 is 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 organopolyoxane having a second reactive functional group reactive with the first reactive functional group is used. The organic-inorganic composite particles 1 are an alkoxy-containing organic polyoxyalkylene having inorganic particles having a first reactive functional group on the surface and a second reactive functional group capable of reacting with the first reactive functional group. And get.

The structure portion 12 is disposed on the surface of the inorganic particles 11. The structure portion 12 exists between the plurality of inorganic particles 11. The plurality of inorganic particles 11 are preferably integrated via a structure (structure portion 12) derived from an alkoxy group-containing organic polyoxyalkylene. The plurality of inorganic particles 11 are preferably integrated via a structure (structure portion 12) derived from an alkoxy group-containing organic polyoxyalkylene to obtain an aggregate of the inorganic particles 11. The structural portion 12 preferably has a plurality of inorganic particles 11 bonded thereto.

Examples of the inorganic particles include particles formed of a metal oxide, a metal nitride, a metal sulfide, a metal carbide, and the like. Examples of the metal oxide include cerium oxide, aluminum oxide, and titanium oxide. Among them, it is preferred that the inorganic particles are cerium oxide particles.

The main component of the above inorganic particles is an inorganic substance. The inorganic particles may contain carbon atoms as long as the carbon atoms are small. 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 contained in the inorganic particles.

Examples of the first reactive functional group include a hydroxyl group, an alkoxy group, an epoxy group, a (meth)acrylinyl group, an amine group, a mercapto group, and an isocyanate group. Among them, a hydroxyl group is preferred in that the functional group is easily and in a large amount to be introduced onto the surface of the inorganic particles.

The inorganic particles preferably contain a polyoxyalkylene skeleton. The above inorganic particles are preferably It is obtained by subjecting a decane compound to hydrolysis and condensation. The above decane compound may have an organic group such as an alkyl group or a vinyl group. The particles obtained by using such an organic group-containing decane compound are also referred to as inorganic particles as long as the main component is an inorganic substance. The inorganic particles may be formed using an organic polysiloxane.

The compound represented by the following formula (1) (hereinafter, referred to as the compound (1)) or the compound represented by the following formula (2) (hereinafter, may be described as a compound (hereinafter may be mentioned) 2)), and a compound represented by the following formula (3) (hereinafter, it may be described as a compound (3)). As the decane compound, at least one selected from the group consisting of the compound (1), the compound (2), and the compound (3) is preferably used. When such a compound is used, the surface of the obtained inorganic particles changes from having a stanol group to having a hydroxyl group.

In the above formula (1), Ra represents a (meth) acrylonitrile group, Rb represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent, and R1 and R2 each represent a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. The base or a fluorenyl group having 2 to 5 carbon atoms, and Z represents an alkyl group having 1 to 5 carbon atoms, a fluorenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

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

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 a mercapto group having 2 to 5 carbon atoms.

The above compound (1) has a Ra-O-Rb- group. This group has a Ra group as a group containing a polymerizable unsaturated group. The polymerizable unsaturated group in the compound (1) is subjected to radical polymerization to form a highly flexible organic polymer skeleton. On the other hand, if the compound (2) is used without using the compound (1), an organic polymer skeleton having sufficiently high flexibility cannot be formed.

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

Rb in the above formula (1) represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent. By virtue of the presence of such an organic group, a highly flexible organic polymer skeleton is formed.

Examples of the divalent organic group having 1 to 20 carbon atoms in the above Rb include a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, and the like. The base bond has a substituent group, or a phenyl group and a group having a substituent bonded to the phenyl group, or a group in which an alkyl group is bonded via an ether bond, or a phenyl group is bonded via an ether bond. The basis of the knot. Among them, a propyl group or a phenyl group is preferred, and a propyl group is more preferred.

In the above formula (1), Z represents an alkyl group having 1 to 5 carbon atoms, a mercapto group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. In terms of an increase in the number of reaction sites, 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. It can also be an alkyl group having 1 to 3 carbon atoms. In the case where Z in the above formula (1) is an alkoxy group, Z is more preferably carbon. Number 1 or 2 alkoxy groups. In the case where Z in the above 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 above formula (3) is preferably a methyl group.

In the above formulae (1), (2) and (3), R1, R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a mercapto group having 2 to 5 carbon atoms. These groups are hydrolyzable groups. In terms of moderately increasing the hydrolysis rate, R1, R2 and R3 in the above formulas (1), (2), and (3) are preferably an alkyl group having 1 to 3 carbon atoms or a fluorenyl group having 2 carbon atoms, respectively. It 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 above compound (1) include 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, and 3-methylpropene oxime. Oxypropylmethyldiethoxydecane, 3-methacryloxypropyltriethoxydecane, and 3-propenyloxypropyltriethoxydecane. The compound (1) may be used alone or in combination of two or more.

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

The compound (3) may, for example, be methyltrimethoxydecane or ethyltrimethoxydecane. The compound (3) may be used alone or in combination of two or more.

The alkoxy group-containing organopolyoxane has a second reactive functional group reactive with the first reactive functional group. The second reactive functional group can be appropriately selected depending on 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)acrylinyl group, an amine group, a mercapto group, and an isocyanate group. For example, when the first reactive functional group is a hydroxyl group, since the hydroxyl group reacts with the alkoxy group, the alkoxy group in the alkoxy group-containing organopolyoxane corresponds to the second reactive functional group. Wherein, in opposition to the first reactive functional group in the above inorganic particles In terms of ease of carrying out, an epoxy group, a (meth) acrylonitrile group, a fluorenyl group or an alkoxy group is preferred, and an epoxy group, a (meth) acryl fluorenyl group or an alkoxy group is more preferred. In the above alkoxy-containing organopolyoxane, the second reactive functional group preferably has an epoxy group, a (meth)acrylinyl group or a fluorenyl group, more preferably an epoxy group or (A) Further, the propylene group is more preferably an epoxy group or a fluorenyl group, more preferably an epoxy group, still more preferably a (meth) acryl fluorenyl group, and further preferably an alkoxy group. It is preferred to have an epoxy group, a (meth)acrylinyl group or a mercapto group and an alkoxy group, and further preferably have an epoxy group or a mercapto group and an alkoxy group, and more preferably have an epoxy group and an alkoxy group. The above alkoxy group is preferably a methoxy group or an ethoxy group.

In view of obtaining further excellent compression set characteristics, the alkoxy group-containing organopolyoxane preferably has an epoxy group, a methoxy group or an ethoxy group as the second reactive functional group.

Examples of the alkoxy group-containing organic polyoxosiloxane include an alkoxy oligomer, and the like, and X-41-1053 and X-41-1059A manufactured by Shin-Etsu Chemical Co., Ltd. (above, having an epoxy resin) , methoxy, ethoxy), X-41-1056 (having an epoxy group, methoxy group), X-41-1805 (having a fluorenyl group, a methoxy group, an ethoxy group), X-41-1818 (having an indenyl group, an ethoxy group), X-41-1810 (having an indenyl group, a methoxy group), X-41-2651 (having an amine group, a methoxy group), and X-40-2655A (having a methyl methacrylate group) , methoxy), KR-513 (with acrylonitrile, methoxy), KC-89S, 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 (above, with methoxy), and X-40-9238 (with ethoxy) Wait. The alkoxy group-containing organopolyoxane may be used alone or in combination of two or more.

The alkoxy group-containing organopolyoxane may be a reaction product of a cyclic siloxane and a decane compound having the above second reactive functional group. With respect to the above reactant, it is preferred that the above cyclic oxirane is opened. The decane compound having the second reactive functional group may also be a decane coupling agent.

Further, the alkoxy group-containing organopolyoxane preferably has an alkyl group directly bonded to a ruthenium 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. The above inorganic particles are further preferably an epoxy group or a (meth)acryl fluorenyl group or a fluorenyl group, an alkoxy group, and an alkyl group directly bonded to a ruthenium atom, and more preferably an epoxy group or a (meth) propylene group. A mercapto group, an alkoxy group, and an alkyl group directly bonded to a halogen atom are preferably an epoxy group, an alkoxy group, and an alkyl group directly bonded to a halogen atom. Further, better compression deformation characteristics can be obtained by the presence of the preferred second reactive functional groups and by the presence of the preferred second reactive functional groups and organic functional groups.

The weight average molecular weight of the alkoxy group-containing organopolyoxane is preferably 500 or more, more preferably 1,000 or more, more preferably 10,000 or less, still more preferably 7,000 or less. The weight average molecular weight is a weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC).

In view of obtaining further excellent compression deformation characteristics, the organic-inorganic composite particles are preferably obtained by reacting the first reactive functional group with the second reactive functional group.

In view of obtaining further excellent compression deformation characteristics, it is preferable that the organic-inorganic composite particles are integrated by a plurality of the inorganic particles via a structure derived from the alkoxy-containing organic polyoxyalkylene.

The organic-inorganic composite particles are a collection of a plurality of the above inorganic particles. In the above organic-inorganic composite particles, the number of the inorganic particles in the aggregate is 2 or more, preferably 5 or more, and more preferably 10 or more. Further, in the following examples, the number of inorganic particles in the aggregate was 10 or more. The upper limit of the number of inorganic particles in the aggregate is not particularly limited.

In the organic-inorganic composite particles, the particle diameter of each of the inorganic particles in the aggregate is preferably 0.1 nm or more, more preferably 1 nm or more, still more preferably 3 nm or more, and is preferably 1000 nm or less, more preferably 500 nm or less. Further preferably 200 nm or less, especially preferably Below 100 nm. When the particle diameter of the inorganic particles in the aggregate is at least the above lower limit, the grain boundary is present in a small amount, so that it is less likely to become brittle. When the content is less than or equal to the above upper limit, a small amount of voids are present in the organic-inorganic composite particles, so that it tends to be less brittle. .

The rupture load of the organic-inorganic composite particles is preferably 5 mN or more, more preferably 10 mN or more, and still more preferably 11 mN or more from the viewpoint of further suppressing damage of the organic-inorganic composite particles. When the breaking load is at least the above lower limit, the organic-inorganic composite particles are less likely to be broken or damaged during compression.

The above rupture load can be measured, for example, in the following manner. The organic-inorganic composite particles were compressed using a micro-compression tester under the conditions of a smooth head end of a cylinder (100 μm in diameter, made of diamond) at 25 ° C, a compression speed of 0.3 mN/sec, and a maximum test load of 20 mN. The load value (N) and the compression displacement (mm) at this time were measured. The above-described compression elastic modulus can be obtained from the obtained measurement values according to the following formula. As the micro-compression tester, for example, "Fischerscope H-100" manufactured by Fischer Co., Ltd. or the like can be used.

The above-mentioned breaking load indicates the load value when the critical point is confirmed in the measurement curve of the load value and the compression displacement.

The compression recovery ratio of the above organic-inorganic composite particles is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more. When the compression recovery ratio is equal to or higher than the lower limit, the organic-inorganic composite particles are less likely to be damaged, and the organic-inorganic composite particles are likely to be sufficiently followed to be deformed in accordance with the fluctuation between the substrates or between the electrodes. Therefore, connection failure between substrates or between electrodes is less likely to occur.

The above compression recovery ratio can be measured, for example, as follows. The organic-inorganic composite particles are spread on the sample stage. The organic-inorganic composite particles dispersed were applied with a load (inversion load value) in the center direction of the organic-inorganic composite particles using a micro-compression tester until the organic-inorganic composite particles were subjected to 30% compression deformation. Thereafter, the unloading was performed until the origin load value (0.40 mN). The load-compression displacement during this period can be measured, and the compression recovery rate can be obtained from the following equation. Furthermore, the load speed was set to 0.33 mN/sec. As above As the micro compression tester, for example, "Fischerscope H-100" manufactured by Fischer Co., Ltd. or the like can be used.

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

L1: compression displacement from the origin load value to the reverse load value when the load is applied

L2: Unloading displacement from the reverse load value when the load is released to the load value at the origin

The particle diameter of the organic-inorganic composite particles is preferably 0.1 μm or more, more preferably 1 μm or more, further preferably 1.5 μm or more, particularly preferably 2 μm or more, and more preferably 1,000 μm or less, more preferably 500 μm or less, further. It is preferably 300 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less, and most preferably 5 μm or less. When the particle diameter of the organic-inorganic composite particles is not less than the above lower limit and not more than the above upper limit, the organic-inorganic composite particles can be preferably used for electronic component applications. The particle diameter of the above organic-inorganic composite particles means the largest diameter.

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

(Method for producing organic-inorganic composite particles)

The method for producing the above organic-inorganic composite particles is not particularly limited. The method for producing the organic-inorganic composite particles preferably includes a step of hydrolyzing and condensing the decane compound to obtain hydrolysis and condensation of the inorganic particles. In this method, organic-inorganic composite particles having a uniform particle diameter and further excellent compression deformation characteristics can be obtained. In the above hydrolysis and condensation step, hydrolysis and condensation reaction occur at the contact interface between the decane compound and the aqueous solvent to form a polyoxyalkylene skeleton, and inorganic particles are obtained.

In the above hydrolysis and condensation steps, a catalyst is usually used. The above decane compound is reacted in the presence of a catalyst. In the above hydrolysis and condensation steps, specifically, for example, water and an acidic catalyst or an alkaline catalyst are used. The above catalysts may be used alone or in combination of two. the above.

Examples of the acidic catalyst include inorganic acid, organic acid, acid anhydride of an inorganic acid and a derivative thereof, and an acid anhydride of an organic acid and a derivative thereof.

In the above hydrolysis and condensation steps, a suitable organic solvent may be used in addition to water. Specific examples of the organic solvent include alcohols, ketones, esters, (cyclo)alkanes, 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 steps is not particularly limited, but is preferably 0 ° C or higher, and preferably 100 ° C or lower, more preferably 70 ° C or lower. The reaction time in the hydrolysis and condensation steps is not particularly limited, but is preferably 30 minutes or longer, and preferably 100 hours or shorter.

The method for producing the organic-inorganic composite particles preferably includes the steps of: a plurality of inorganic particles having a first reactive functional group on the surface; and a second reactive functional group capable of reacting with the first reactive functional group. The alkoxy-containing organopolyoxane is reacted to obtain an aggregate of the above inorganic particles. In this step, it is preferred that a plurality of the above inorganic particles are integrated via a structure derived from the alkoxy group-containing organic polyoxyalkylene. It is preferred that a plurality of inorganic particles are integrated via a structure (structure portion) derived from an alkoxy group-containing organic polyoxyalkylene to obtain an aggregate of inorganic particles.

For example, in a state in which water is separated from a layer containing the above-described decane compound containing an alkoxy group-containing organopolyoxane, or a layer containing water and the above decane compound is contained, In the state in which the layer of the alkoxy group of the polyorganosiloxane is separated, the decane compound is hydrolyzed and condensed to obtain inorganic particles, and the alkoxy group-containing organopolyoxane is attached and precipitated to obtain the obtained inorganic particles. On the surface, a plurality of inorganic particles having a first reactive functional group on the surface are reacted with an alkoxy-containing organic polyoxyalkylene having a second reactive functional group reactive with the first reactive functional group. And an aggregate of the above inorganic particles is obtained.

(Use of organic-inorganic composite particles)

The use of the above organic-inorganic composite particles is not particularly limited. The above organic-inorganic composite particles can be preferably used for various applications requiring a high breaking load. The above organic-inorganic composite particles are preferably used for electronic parts. The organic-inorganic composite particles are preferably organic-inorganic composite particles for electronic parts.

The organic-inorganic composite particles are preferably used to form a conductive layer on the surface to obtain conductive particles having the above-mentioned conductive layer, or to be used as a spacer for a liquid crystal display element. The organic-inorganic composite particles are preferably used to form a conductive layer on the surface to obtain conductive particles having the above-mentioned conductive layer. The organic-inorganic composite particles are preferably used as a spacer for a liquid crystal display element. Since the organic-inorganic composite particles have a high breaking load, the organic-inorganic composite particles are disposed between the substrates as spacers for liquid crystal display elements, or a conductive layer is formed on the surface to serve as conductive particles, and the electrodes are interposed between the electrodes. In the case of electrical connection, the spacer for the liquid crystal display element or the conductive particles is less likely to be broken and is not easily damaged. In particular, when an impact is applied to the liquid crystal display device using the spacer for a liquid crystal display element and the connection structure using the conductive particles, the spacer for the liquid crystal display element and the conductive particles are less likely to be broken and are less likely to be damaged.

Further, the above organic-inorganic composite particles can be preferably used as an impact absorber or a vibration absorber. For example, as the substitute for rubber or a spring or the like, the above-described organic-inorganic composite particles can be used.

In Fig. 2, conductive particles using the organic-inorganic composite particles shown in Fig. 1 are schematically shown in a cross-sectional view.

The conductive particles 21 shown in FIG. 2 have an organic-inorganic composite particle 1 and a conductive layer 31A disposed on the surface of the organic-inorganic composite particle 1.

The conductive layer 31A covers the surface of the organic-inorganic composite particle 1. The conductive particles 21 are coated particles in which the surface of the organic-inorganic composite particles 1 is coated with the conductive layer 31A.

In Fig. 3, the organic-inorganic composite particles shown in Fig. 1 are schematically shown in a sectional view. Examples of changes in the conductive particles of the child.

The conductive particles 22 shown in FIG. 3 have an organic-inorganic composite particle 1, a conductive layer 31B, a plurality of core materials 32, and a plurality of insulating substances 33.

The conductive layer 31B is disposed on the surface of the organic-inorganic composite 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. The first conductive layer 31Ba is disposed on the surface of the organic-inorganic composite 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 protrusions on the surface of the conductivity. 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 surface of the conductive particles and may have protrusions on the outer surfaces of the conductive layer and the second conductive layer. A plurality of core materials 32 are disposed on the surface of the organic-inorganic composite particles 1. A plurality of core 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 is coated with a plurality of core materials 32. The outer surface of the conductive layer 31B is embossed by a plurality of core materials 32 to form protrusions.

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 an insulating material and is an insulating particle. 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 above 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, ruthenium, osmium, iridium, osmium, cadmium, iridium and Such alloys and the like. Further, examples of the metal include tin-doped indium oxide (ITO), solder, and the like. Among them, an alloy containing tin, nickel, palladium, copper or gold is preferable since nickel-palladium is preferable because the connection resistance between the electrodes can be further lowered.

Like the conductive particles 21, the above conductive layer may be formed of 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 laminate of two or more layers. structure. In the case where 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, more preferably a gold layer. In the case where the outermost layer is the preferred conductive layer, the connection resistance between the electrodes is further reduced. Moreover, when the outermost layer is a gold layer, the corrosion resistance is further improved.

The method of forming the conductive layer on the surface of the above-described organic-inorganic composite particles is not particularly limited. Examples of the method of forming the conductive layer include a method using electroless plating, a method using electroplating, a method using physical vapor deposition, and a method of applying a metal powder or a paste containing a metal powder and a binder to an organic-inorganic composite particle. Surface method, etc. Among them, in terms of the ease of formation of the conductive layer, it is preferred to use a method of electroless plating. Examples of the method using physical vapor deposition include vacuum 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, further preferably 1 μm or more, more preferably 520 μm or less, still more preferably 500 μm or less, still more preferably 100 μm or less, and further It is preferably 50 μm or less, and 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 is sufficiently increased when the conductive particles are connected between the electrodes, and the conductive layer is less likely to form when the conductive layer is formed. Sex particles. Moreover, the interval between the electrodes connected via the conductive particles does not excessively increase, and the conductive layer is less likely to be peeled off from the surface of the organic-inorganic composite particles. 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 preferably used for the use of the conductive material.

The particle diameter of the above-mentioned conductive particles indicates a diameter when the conductive particles are in a spherical shape, and indicates a maximum diameter when the conductive particles have a shape other than a spherical shape.

The thickness of the conductive layer (the thickness of the entire conductive layer when the conductive layer is a plurality of layers) is preferably 0.005 μm or more, more preferably 0.01 μm or more, more preferably 10 μm or less, still more preferably 1 μm or less, and further preferably It is 0.3 μm or less. If the thickness of the conductive layer is the above lower limit Above the above and below the above upper limit, sufficient conductivity can be obtained, and the conductive particles are not excessively hardened, and the conductive particles are sufficiently deformed when the electrodes are connected.

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, more preferably 0.5 μm or less, still 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 of the outermost conductive layer becomes uniform, the corrosion resistance is sufficiently improved, and the connection resistance between the electrodes is further lowered. Further, in the case where the outermost layer is a gold layer, the thinner the thickness of the gold layer, the lower the cost.

The thickness of the above conductive layer can be measured by observing a 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. The protrusions are preferably plural. The oxide film is often formed on the surface of the electrode connected by the conductive particles. In the case of using conductive particles having protrusions, by disposing conductive particles between the electrodes and pressing them, the oxide film can be effectively removed by the protrusions. Therefore, the electrode and the conductive layer of the conductive particles can be brought into further firm contact, and the connection resistance between the electrodes can be reduced. Further, when the conductive particles have an insulating material on the surface, or when the conductive particles are dispersed in the binder resin and used as a conductive material, the conductive particles can be effectively removed by the protrusions of the conductive particles. An insulating substance or a binder resin between the particles and the electrode. Therefore, the conduction reliability between the electrodes can be improved.

The method of forming a protrusion on the surface of the conductive particle includes a method of forming a conductive layer by electroless plating after attaching a core substance to a surface of the organic-inorganic composite particle, and forming a conductive layer by electroless plating on the surface of the organic-inorganic composite particle. After the layer, a core material is adhered, and a method of forming a conductive layer by electroless plating is used. Moreover, in order to form a protrusion, the above-mentioned core substance may not be used.

The conductive particles may further include an insulating material disposed on the outer surface of the conductive layer. In this case, if conductive particles are used for the connection between the electrodes, the neighbors can be prevented. A short circuit between the electrodes. 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 not only short-circuiting between the electrodes above and below but also short-circuiting between adjacent electrodes can be prevented. Further, when the conductive particles are pressurized by two electrodes when the electrodes are connected, the insulating material between the conductive layers of the conductive particles and the electrodes can be easily removed. 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 removed. The insulating material 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 contains the conductive particles and the binder resin. The conductive particles are preferably dispersed in a binder resin and used as a conductive material. The above conductive material is preferably an anisotropic conductive material. The above conductive material is preferably a conductive material for circuit connection.

The above binder resin is not particularly limited. As the above binder resin, a known insulating resin can be used. Examples of the binder resin include an ethylene 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 a vinyl acetate resin, an acrylic resin, and a 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. Further, the curable resin may be a room temperature curing resin, a thermosetting resin, a photocurable resin or a moisture curing resin. The curable resin may be used in combination with a curing agent. Examples of the above thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, and a styrene-butadiene-styrene. a hydride of a block copolymer, a hydride of a styrene-isoprene-styrene block copolymer, and the like. As the above elastomer, for example, styrene-butyl A diene copolymer rubber, an acrylonitrile-styrene block copolymer rubber, or the like.

The conductive material may contain, in addition to the conductive particles and the binder resin, a filler, a bulking agent, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, and a heat stabilization. Various additives such as agents, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents and flame retardants.

A conventionally known dispersion method can be used as the method of dispersing the above-mentioned conductive particles in the above-mentioned binder resin, and is not particularly limited. In the method of dispersing the above-mentioned conductive particles in the above-mentioned binder resin, for example, a method in which the conductive particles are added to the binder resin and then kneaded by a planetary mixer or the like is used, and a homogenizer is used. After the conductive particles are uniformly dispersed in water or an organic solvent, they are added to the binder resin, and the mixture is kneaded by a planetary mixer or the like, and the binder resin is water or an organic solvent. After the dilution, the conductive particles are added and mixed by a planetary mixer or the like to disperse the particles.

The above conductive material can be used as a conductive paste, a conductive film, or the like. In the case where the conductive material of the present invention is used as a conductive film, a film containing conductive particles may be laminated on the conductive film containing the conductive particles. The above conductive paste is preferably an anisotropic conductive paste. The above conductive film is preferably an anisotropic conductive film.

The content of the binder resin in 100% by weight of the conductive material is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and particularly preferably 70% by weight or more. 99.99% by weight or less, more preferably 99.9% by 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 disposed between the electrodes, and the connection reliability of the member to be joined connected by the conductive material is further improved.

The content of the conductive particles in 100% by weight of the conductive material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, more preferably 40% by weight or less, still more preferably 20% by weight or less, and still more preferably 10% by weight or less. If the content of the above conductive particles is When the lower limit is equal to or higher than the above upper limit, the conduction reliability between the electrodes is further improved.

(connection structure and liquid crystal display element)

The connection structure can be obtained by connecting the connection member using the conductive particles or a conductive material containing the conductive particles and the binder resin.

Preferably, the connection structure includes a first connection target member, a second connection target member, and a connection portion that connects the first connection target member and the second connection target member, and the connection portion is made of the conductive particles. It is formed or formed of a conductive material containing the above conductive particles and a binder resin. In the case where the conductive particles are used alone, the connecting portion itself is a conductive particle. In other words, the first and second connection target members are connected by conductive particles. The above conductive material for obtaining the above-mentioned connection structure is preferably an anisotropic conductive material.

Preferably, the first connection target member has a first electrode on its surface. Preferably, the second connection target member has a second electrode on its surface. Preferably, 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. 2 .

The connection structure 51 shown in FIG. 4 includes a first connection target member 52, a second connection object member 53, and a connection portion 54 that connects the first connection object member 52 and the second connection object member 53. The connecting portion 54 is formed of a conductive material containing conductive particles 21 and a binder resin. In FIG. 4, the electroconductive particle 21 is shown typically for convenience of illustration. Other conductive particles such as the conductive particles 22 may be used in addition to the conductive particles 21.

The first connection target member 52 has a plurality of first electrodes 52a on the front surface (upper surface). The second connection target member 53 has a plurality of second electrodes 53a on the front surface (lower surface). The first electrode 52a and the second electrode 53a are electrically connected to one or a plurality of conductive particles 1. Therefore, the first and second connection object members 52 and 53 are electrically connected by the conductive particles 21 .

The method for producing the above-described connection structure is not particularly limited. An example of the method of manufacturing the connection structure is a method in which the conductive material is placed between the first connection target member and the second connection target member to obtain a laminate, and the laminate is heated and pressurized. The pressure of the above pressurization is about 9.8 × 10 ⁴ to 4.9 × 10 ⁶ Pa. The heating temperature is about 120 to 220 °C. The pressing pressure of the electrode for connecting the flexible printed circuit 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 a semiconductor wafer, a capacitor, and a diode, and electronic components such as a printed circuit board, a flexible printed circuit board, and a circuit board such as a glass epoxy substrate and a glass substrate. The conductive material is preferably a conductive material for connecting electronic components. The conductive paste is preferably a paste-like conductive material and is applied to the member to be joined in a paste state.

The conductive particles and the conductive material described above can also be preferably used for a touch panel. 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 the resin film. The connection target member is preferably a flexible printed circuit board, and is preferably a connection target member in which an electrode is disposed on the surface of the resin film. The above flexible printed substrate usually has electrodes on its surface.

Examples of the electrode provided in 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. In the case where 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. In the case where 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. Further, in the case where the electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode having an aluminum layer on the surface layer 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, Ga, and the like.

Moreover, the above-mentioned organic-inorganic composite particles can be preferably used as a spacer for a liquid crystal display element. In other words, the organic-inorganic composite particles can be preferably used to obtain a liquid crystal including 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. Display component.

In Fig. 5, a liquid crystal display element in which an organic-inorganic composite particle according to an embodiment of the present invention is used as a spacer for a liquid crystal display element is shown in a cross-sectional view.

The 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 opposite surface. Examples of the material of the insulating film include SiO ₂ and the like. A transparent electrode 83 is formed on the insulating film in the transparent glass substrate 82. As a material of the transparent electrode 83, ITO etc. are mentioned. The transparent electrode 83 can be formed, for example, by patterning by photolithography. An alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82. The material of the alignment film 84 is, for example, polyimine.

The liquid crystal 85 is sealed between the pair of transparent glass substrates 82. A plurality of organic-inorganic composite particles 1 are disposed between the pair of transparent glass substrates 82. The organic-inorganic composite particles 1 can be used as a spacer for a liquid crystal display element. The interval between the pair of transparent glass substrates 82 can be restricted by the plurality of organic-inorganic composite particles 1. A sealant 86 is disposed between the edge portions of the pair of transparent glass substrates 82. The liquid crystal 85 is prevented from flowing out to the outside by the sealant 86. In FIG. 5, the organic-inorganic composite particles 1 are schematically shown for convenience of illustration. Other organic-inorganic composite particles may be used in addition to the organic-inorganic composite particles 1.

In the liquid crystal display device, the arrangement density of the spacer 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. If the above-described arrangement density is 10 pieces/mm ² or more, the cell gap becomes more uniform. When the above arrangement density is 1000/mm ² or less, the contrast of the liquid crystal display element becomes better.

Hereinafter, the present invention will be specifically described by way of examples and comparative examples. The invention is not limited to the following examples.

(Example 1)

To a 500 mL reaction vessel equipped with a stirrer and a thermometer, 300 g of a 0.13 wt% aqueous ammonia solution was added. Then, 4.1 g of methyltrimethoxydecane, 19.2 g of vinyltrimethoxydecane, and a polyoxyalkyloxyoxyl oligomer (X-manufactured by Shin-Etsu Chemical Co., Ltd.) were slowly added to the aqueous ammonia solution in the reaction vessel. 41-1053", a mixture having a methoxy group, an ethoxy group, an epoxy group, and an alkyl group directly bonded to a halogen atom, and having a weight average molecular weight of about 1600) and 0.7 g. After performing hydrolysis and condensation reaction while stirring, 2.4 mL of a 25 wt% aqueous ammonia solution was added, and then the particles were separated from the aqueous ammonia solution, and the obtained particles were subjected to a partial pressure of oxygen at 10 ^-17 atm and 400 ° C. The following baking was carried out for 2 hours to obtain organic-inorganic composite particles. The particle diameter of the obtained organic-inorganic composite particles is shown in Table 1 below.

(Example 2)

The polyoxyalkyloxy oligomer ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to an alkoxy oligomer ("KR-500" manufactured by Shin-Etsu Chemical Co., Ltd.), having a methoxy group. The organic-inorganic composite particles were obtained in the same manner as in Example 1 except that the alkyl group directly bonded to the ruthenium atom had a weight average molecular weight of 3,000 to 10,000.

(Example 3)

Poly-alkoxy alkoxy oligomer ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to poly-xyloxy oligomer (X-41-1805) manufactured by Shin-Etsu Chemical Co., Ltd. Organic-inorganic composite particles were obtained in the same manner as in Example 1 except that the oxy group, the ethoxy group, and the fluorenyl group had a weight average molecular weight of about 1800.

(Example 4)

To a 500 mL reaction vessel equipped with a stirrer and a thermometer, 300 g of a 0.13 wt% aqueous ammonia solution was added. Then, a mixture of 4.1 g of methyltrimethoxydecane and 19.2 g of vinyltrimethoxydecane was slowly added to the aqueous ammonia solution in the reaction vessel. After the hydrolysis and the condensation reaction are carried out while stirring, a polyphosphonium alkoxy oligomer (X-41-1053) manufactured by Shin-Etsu Chemical Co., Ltd. is added, and has a methoxy group, an ethoxy group, and an epoxy group. And 0.7 g directly bonded to the alkyl group of the ruthenium atom, and slowly stirred. After the polyoxyalkyloxy oligomer disappeared, 2.4 mL of a 25 wt% aqueous ammonia solution was added, and then the particles were separated from the aqueous ammonia solution, and the obtained particles were calcined at an oxygen partial pressure of 10 ^-17 atm at 400 ° C. After 2 hours, organic-inorganic composite particles were obtained.

(Example 5)

To a 500 mL reaction vessel equipped with a stirrer and a thermometer, 300 g of a 0.13 wt% aqueous ammonia solution was added. Then, 1.9 g of 3-methylpropenyloxypropyltrimethoxydecane, 4.1 g of methyltrimethoxydecane, 17.3 g of vinyltrimethoxydecane, and polyfluorene were slowly added to the aqueous ammonia solution in the reaction vessel. Oxyalkoxy oligomer (X-41-1053, manufactured by Shin-Etsu Chemical Co., Ltd., a mixture of methoxy, ethoxy, epoxy, and alkyl groups directly bonded to a ruthenium atom) of 0.7 g . After performing hydrolysis and condensation reaction while stirring, 2.4 mL of a 25 wt% aqueous ammonia solution was added, and then the particles were separated from the aqueous ammonia solution, and the obtained particles were subjected to a partial pressure of oxygen at 10 ^-17 atm and 400 ° C. The following baking was carried out for 2 hours to obtain organic-inorganic composite particles.

(Example 6)

Cyclopentaoxane ("KF-995" manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-glycidoxypropyltrimethoxydecane (Xinyue Chemical) as an epoxy decane coupling agent "KBM-403" manufactured by Industrial Co., Ltd. was reacted to obtain an alkoxy group-containing organopolyoxosiloxane A (having an epoxy group and an alkoxy group and having a weight average molecular weight of about 1,500).

The same procedure as in Example 4 except that the polyoxyalkyloxy oligomer ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to the alkoxy-containing organopolyoxane A. In the manner, organic-inorganic composite particles are obtained.

(Example 7)

Cyclopentaoxane ("KF-995" manufactured by Shin-Etsu Chemical Co., Ltd.) as a cyclic oxirane and 3-acryloxypropyltrimethyl methacrylate as a decane coupling agent having an acrylonitrile group Oxydecane ("KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd.) was reacted to obtain an alkoxy-containing organic polyoxosiloxane B (having an acrylonitrile group and an alkoxy group, and a weight average molecular weight: about 1300).

The same procedure as in Example 4 except that the polyoxyalkyloxy oligomer ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to the alkoxy-containing organopolyoxane B. In the manner, organic-inorganic composite particles are obtained.

(Example 8)

Cyclopentaoxane ("KF-995" manufactured by Shin-Etsu Chemical Co., Ltd.) as a cyclic oxirane and 3-methylpropenyloxypropyl group as a decane coupling agent having a methacryl oxime group Trimethoxy decane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd.) is reacted to obtain a methacryloxy group-containing organic polyoxyalkylene C (having a methacryl fluorenyl group and an alkoxy group, weight average molecular weight : About 2000).

The same procedure as in Example 4 except that the polyoxyalkyloxy oligomer ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to the alkoxy-containing organopolyoxane C. In the manner, organic-inorganic composite particles are obtained.

(Example 9)

(1) Palladium attachment step

The organic-inorganic composite particles obtained in Example 4 were prepared. The organic-inorganic composite particles are etched and washed with water. Then, the organic-inorganic composite particles were added to 100 mL of a palladium catalyst solution containing 8 wt% of a palladium catalyst, followed by stirring. Thereafter, filtration and washing are carried out. The organic-inorganic composite particles were added to a 0.5 wt% dimethylamine borane solution having a pH of 6, to obtain an organic-inorganic composite particle to which palladium adhered.

(2) Core substance attachment step

The organic-inorganic composite particles to which palladium adhered were stirred in 300 mL of ion-exchanged water for 3 minutes, and dispersed to obtain a dispersion. Then, 1 g of a metal nickel particle slurry (average particle diameter: 100 nm) was added to the above dispersion liquid over 3 minutes to obtain an organic non-core substance. Machine composite particles.

(3) Electroless nickel plating step

A nickel layer was formed on the surface of the organic-inorganic composite particles to which the core substance adhered by electroless plating to prepare conductive particles. Further, the thickness of the nickel layer was 0.1 μm.

(Embodiment 10)

(1) Production of insulating particles

In a 1000 mL separable flask equipped with four separable caps, stirring leaves, three-way stopcock, cooling tube and temperature probe, it will contain 100 mmol of methyl methacrylate, N, N, N-trimethyl- A monomer composition of 1 mmol of N-2-methylpropenyloxyethylammonium chloride and 1 mmol of 2,2'-azobis(2-amidinopropane) dihydrochloride showed a solid content ratio of 5 After weighing in % by weight, the mixture was stirred at 200 rpm, and polymerization was carried out at 70 ° C for 24 hours under a nitrogen atmosphere. After completion of the reaction, lyophilization was carried out to obtain insulating particles having an ammonium group and an average particle diameter of 220 nm and a CV (Coefficient of Variation) value of 10%.

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

(2) Production of conductive particles with insulating particles

10 g of the conductive particles obtained in Example 9 was 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 μm mesh filter, and further washed with methanol and dried to obtain conductive particles to which insulating particles were attached.

Observation by a scanning electron microscope (SEM) revealed that only one layer of the insulating layer was formed on the surface of the conductive particles. The coating area of the insulating particles (i.e., the projected area of the particle diameter of the insulating particles) with respect to the area of 2.5 μm from the center of the conductive particles was calculated by image analysis, and as a result, the coverage ratio was 30%.

(Comparative Example 1)

The organic-inorganic composite particles were obtained in the same manner as in Example 1 except that the polyoxyalkyloxy oligomer ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

(Comparative Example 2)

Changed polyoxyalkyloxy oligomer ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd.) to non-reactive methylphenyl polyfluorene (KF-manufactured by Shin-Etsu Chemical Co., Ltd.) The organic-inorganic composite particles were obtained in the same manner as in Example 1 except for the above.

(Evaluation)

(1) Particle size of organic-inorganic composite particles

About the particle diameter of the obtained organic-inorganic composite particle, the particle size of about 10,000 organic-inorganic composite particle was measured using the particle size distribution measuring apparatus ("Multisizer3" by the Beckman Coulter company. The average value of the measured particle diameters was determined, and the particle diameter of the organic-inorganic composite particles was determined.

(2) The above rupture load of the organic-inorganic composite particles

The above-mentioned breaking load of the obtained organic-inorganic composite particles was measured by the above method using "Fischerscope H-100" manufactured by Fischer.

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

In the obtained organic-inorganic composite particles, the particle diameter of each inorganic particle in the aggregate is measured by a transmission method using X-ray small-angle scattering (manufactured by RIGAKU Co., Ltd., powder X-ray diffraction device SmartLab (parallel beam method)). Determination. The average size determined using the analytical software NANO-Solver was used. The model in the analytical software NANO-Solver has a scatterer model as a ball, a particle as SiO ₂ , and a matrix as air.

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

(4) Connection resistance

Preparation of Conductive Particles: The organic-inorganic composite 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 composite particles by electroless plating to prepare conductive particles. Further, the thickness of the nickel layer was 0.1 μm. The conductive particles obtained in Examples 9 and 10 were used as they were.

Production of a connection structure: 10 parts by weight of bisphenol A type epoxy resin ("Epikote 1009" manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight: about 800,000), and methyl ethyl ketone 200 50 parts by weight of a microcapsule-type hardening agent ("HX3941HP" manufactured by Asahi Kasei E-MATERIALS Co., Ltd.) and 2 parts by weight of a decane coupling agent ("SH6040" manufactured by Dow Corning Toray Silicone Co., Ltd.) were mixed to obtain a content of 3 parts by weight. Conductive particles were added in a weight % manner and dispersed to obtain a resin composition.

The obtained resin composition was applied to a PET (polyethylene terephthalate) film having a thickness of 50 μm which was subjected to release treatment on one side, and dried by hot air at 70 ° C for 5 minutes to prepare 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. The cut anisotropic conductive film was attached to an ITO (width: 3 cm, length: 3 cm) of a PET substrate (having a height of 0.1 μm, L/S = 20 μm/20 μm) provided with a pull line for electric resistance measurement. The center of the electrode is approximately the center. Then, a two-layer flexible printed circuit board (width: 2 cm, length: 1 cm) provided with the same gold electrode was subjected to alignment and post-bonding so that the electrodes overlap each other. The 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 bonded structure. Further, a two-layer flexible printed circuit board in which a copper electrode was formed on a polyimide film and the surface of the copper electrode was gold-plated was used.

The connection resistance between the opposing electrodes of the obtained connection structure was measured by a four-terminal method. The connection resistance was determined on the basis of the following criteria.

[Evaluation criteria for connection resistance]

○○: The connection resistance is 3.0 Ω or less

○: The connection resistance exceeds 3.0 and is 4.0 Ω or less.

△: The connection resistance exceeds 4.0 and is 5.0 Ω or less.

×: The connection resistance exceeds 5.0Ω

The results are shown in Table 1 below.

(5) Example of use as a spacer for a liquid crystal display element

Preparation of STN (Super Twisted Nematic) type liquid crystal display element: in a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, in a solid content of 100% by weight of the obtained spacer dispersion The spacers (organic-inorganic composite particles) for liquid crystal display devices of Examples 1 to 8 were added and stirred, and the spacer dispersion liquid for liquid crystal display elements was obtained, and the content of the component was 2% by weight.

By depositing a SiO ₂ film by a CVD (Chemical Vapor Deposition) method on one side of a pair of transparent glass plates (50 mm in length, 50 mm in width, and 0.4 mm in thickness), the entire surface of the SiO ₂ film is used. The ITO film was formed by sputtering. The glass substrate with the ITO film obtained was applied by a spin coating method to a polyimide film composition film (manufactured by Nissan Chemical Co., Ltd., SE3510), and calcined at 280 ° C for 90 minutes to form a polysiloxane. Amine alignment film. After the rubbing treatment is applied to the alignment film, the spacer for the liquid crystal display element is wet-laid on the alignment film side of one substrate so as to be 100 to 200 per 1 mm ² . After the sealant was formed on the periphery of the other substrate, the substrate and the substrate on which the spacers were dispersed were placed in a direction in which the rubbing direction was 90°, and the two were bonded together. Thereafter, it was treated at 160 ° C for 90 minutes to harden the sealant to obtain an empty cell (a screen in which no liquid crystal was injected). STN liquid crystal (manufactured by DIC Corporation) to which a chiral agent was added was injected into the obtained empty cell, and then the injection port was blocked with a sealant, and then heat-treated at 120 ° C for 30 minutes to obtain an STN liquid crystal display device.

In the obtained liquid crystal display device, the interval between the substrates obtained by the spacers for liquid crystal display elements of Examples 1 to 8 was favorably limited. Moreover, the liquid crystal display element exhibits good display quality.

1‧‧‧Organic and inorganic composite particles

11‧‧‧Inorganic particles

12‧‧‧From the structure of the alkoxy-containing organopolyoxane

Claims (10)

An organic-inorganic composite particle comprising a plurality of inorganic particles having a first reactive functional group on a surface thereof and an alkoxy-containing organic group having a second reactive functional group reactive with the first reactive functional group The alkoxy group-containing organopolyoxane has a weight average molecular weight of 1,000 or more and 10,000 or less, and the alkoxy group-containing organopolyoxane has a polysiloxane. An epoxy group is used as the second reactive functional group. The organic-inorganic composite particle according to claim 1, wherein the first reactive functional group is a hydroxyl group. The organic-inorganic composite particle according to claim 1 or 2, wherein the plurality of the inorganic particles are integrated by a structure derived from the alkoxy group-containing organic polyoxyalkylene to obtain an aggregate of the inorganic particles. The organic-inorganic composite particle according to claim 1 or 2, wherein the alkoxy-containing organopolyoxane has a methoxy group as the second reactive functional group. The organic-inorganic composite particle of claim 1 or 2, wherein the alkoxy-containing organic polyoxyalkylene has an alkyl group directly bonded to a halogen atom. The organic-inorganic composite particle according to claim 1 or 2, which is used for forming a conductive layer on a surface to obtain conductive particles having the above-mentioned conductive layer, or as a spacer for a liquid crystal display element. The organic-inorganic composite particle according to claim 1 or 2, which is used for forming a conductive layer on a surface to obtain conductive particles having the conductive layer, wherein the conductive particles are used to electrically connect the electrodes. A conductive particle comprising the organic-inorganic composite particle according to any one of claims 1 to 7, and a conductive layer disposed on a surface of the organic-inorganic composite particle. A conductive material comprising: an electroconductive particle and a binder resin, wherein the electroconductive particle comprises: the organic-inorganic composite particle according to any one of claims 1 to 7 and a surface disposed on the surface of the organic-inorganic composite particle Conductive layer. A connection structure comprising: a first connection member having a first electrode on its surface, a second connection member having a second electrode on its surface, and a connection portion connecting the first connection member and the second The connection member is formed of conductive particles or formed of a conductive material containing the conductive particles and a binder resin, and the conductive particles are provided with the organic-inorganic composite according to any one of claims 1 to 7. The particles and the conductive layer disposed on the surface of the organic-inorganic composite particles, wherein the first electrode and the second electrode are electrically connected to each other by the conductive particles.