TWI574283B - Organic and inorganic mixed particles, conductive particles, conductive materials and connecting structures - Google Patents

Description

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

The present invention relates to a core-shell type organic-inorganic hybrid particle comprising an organic core and an inorganic shell disposed on a surface of the organic core. Further, the present invention relates to a conductive particle, a conductive material, and a bonded structure using the above-described organic-inorganic hybrid particles.

Anisotropic conductive materials such as an anisotropic conductive paste and an anisotropic conductive film are widely known. In the anisotropic conductive material described above, 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, a glass epoxy substrate, and a semiconductor wafer to obtain a connection structure. Further, as the conductive particles, conductive particles having a substrate particle and a conductive layer disposed on the surface of the substrate particle may be used.

An example of the substrate particles used for the conductive particles is disclosed in Patent Document 1 below, in which the shell is an inorganic compound (A), the core is an organic polymer (b), and the core is coated with an organic polymer particle. (B) (organic-inorganic hybrid particles). Further, Patent Document 1 also discloses conductive particles in which the organic polymer particles (B) are coated with a conductive metal (C).

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 keep the interval (pitch) of the two glass substrates uniform and fixed, a spacer is used as the pitch control material. Resin particles are generally used as the spacer.

An example of the particles used in the above-mentioned conductive particles or the spacer for a liquid crystal display device is disclosed in Patent Document 2 below, which has a polymerizable unsaturated group. The organic-inorganic composite particles (organic-inorganic hybrid particles) obtained by subjecting the polyfunctional decane compound to hydrolysis and polycondensation in the presence of a surfactant. In the patent document 2, the polyfunctional decane compound is a first fluorene 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 At least one monovalent group of a group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a fluorenyl group having 2 to 5 carbon atoms is selected.

Further, as another example of the substrate particles used for the conductive particles, Patent Literatures 3 and 4 disclose a spherical core particle and an elastic coating layer provided on the surface of the spherical core particle. Substrate particles. Further, in Patent Documents 3 and 4, conductive particles having the substrate particles and a conductive thin film layer disposed on the surface of the elastic coating layer in the substrate particles are also disclosed.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-156068

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

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-11503

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-117759

Regarding the organic-inorganic hybrid particles, since the organic material is usually used, the flexibility is excellent to some extent, and it is sufficiently deformed when a high load is applied for compression. Therefore, when the liquid crystal display element is obtained by disposing the organic-inorganic hybrid particles as a spacer for a liquid crystal display element between the substrates, the spacer for the liquid crystal display element is in sufficient contact with the substrate. In the case where the conductive particles are formed by electrically connecting the conductive particles formed on the surface of the organic-inorganic hybrid particles to each other to obtain a bonded structure, the conductive particles are in sufficient contact with the electrode.

However, when the organic-inorganic hybrid particles described in Patent Documents 1 and 2 are used as spacers for liquid crystal display elements and disposed between the substrates, the adhesion of the spacers for liquid crystal display elements to the substrates may be inferior. In the case where a conductive layer is formed on the surface of the conventional organic-inorganic hybrid particles described in Patent Documents 1 and 2, the adhesion between the organic-inorganic hybrid particles and the conductive layer may be inferior. Therefore, there is a case where the conductive layer is peeled off from the surface of the organic-inorganic hybrid particles.

Further, in the substrate particles described in Patent Documents 3 and 4, the organic material is used as the core, but the content of the ruthenium atoms contained in the shell is much less than 50% by weight. Therefore, even if the substrate particles of the prior art described in Patent Documents 3 and 4 are used as a spacer for a liquid crystal display element and disposed between the substrates, the adhesion of the spacer for the liquid crystal display element to the substrate may be inferior. In the case where a conductive layer is formed on the surface of the prior substrate particles described in Patent Documents 3 and 4, the adhesion between the substrate particles and the conductive layer may be inferior. Therefore, there is a case where the conductive layer is peeled off from the surface of the substrate particles.

Further, when the adhesion between the organic-inorganic hybrid particles and the conductive layer is inferior, the dispersibility of the conductive particles in the binder resin is lowered, and the conductive particles are easily aggregated. Further, when a conductive material in which conductive particles are dispersed in a binder resin is used to electrically connect the electrodes, the connection resistance may become high because the dispersion density of the conductive particles in the conductive material is different. Further, there is a case where insulation defects occur due to the aggregated conductive particles.

On the other hand, in order to improve the adhesion between the substrate particles and the conductive layer, cerium oxide particles are used as the substrate particles. When a conductive layer is formed on the surface of the cerium oxide particles, the adhesion between the cerium oxide particles and the conductive layer becomes high. However, the flexibility of the conductive particles is lowered. Therefore, when the conductive particles in which the conductive layer is formed on the surface of the ceria particle are electrically connected between the electrodes, the contact area between the conductive particles and the electrode is small. When the contact area between the conductive particles and the electrode is small, the connection resistance is high or connection failure is likely to occur.

An object of the present invention is to provide an organic-inorganic hybrid particle which can improve the adhesion between an inorganic shell and a contact object which is in contact with the inorganic shell. Moreover, an object of the present invention is to provide a conductive particle, a conductive material, and a bonded structure using the above-described organic-inorganic hybrid particles.

A limited object of the present invention is to provide an organic-inorganic hybrid particle which can improve the adhesion between an inorganic shell and a conductive layer, and conductive particles, a conductive material and a bonded structure using the organic-inorganic hybrid particle.

A further limited object of the present invention is to provide an organic-inorganic hybrid particle which can effectively reduce the connection resistance and improve the insulation reliability when the electrodes are electrically connected to each other, and conductive particles and conductive materials using the organic-inorganic hybrid particles. Materials and connection structures.

According to a broader aspect of the present invention, there is provided an organic-inorganic hybrid particle comprising an organic core and an inorganic shell disposed on a surface of the organic core, wherein the organic core contains 100% by weight of the organic core The content of the ruthenium atom is 10% by weight or less, and the content of the carbon atom contained in the organic nucleus is 50% by weight or more, and the content of the ruthenium atom contained in the inorganic shell is 50% by weight based on 100% by weight of the inorganic shell. The content of the carbon atoms contained in the inorganic shell is 30% by weight or less, and the ratio of the thickness of the inorganic shell to the radius of the organic core is 0.05 or more and 0.70 or less.

The organic-inorganic hybrid particles of the present invention 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 hybrid particles of the present invention are preferably used to form a conductive layer on the surface to obtain conductive particles having the above-mentioned conductive layer.

In a specific aspect of the organic-inorganic hybrid particle of the present invention, the organic core and the inorganic core are not chemically bonded.

In a specific aspect of the organic-inorganic hybrid particle of the present invention, the inorganic shell has a thickness of 50 nm or more and 2000 nm or less.

In one specific aspect of the organic-inorganic hybrid particles of the present invention, the organic core has a particle diameter of 0.5 μm or more and 100 μm or less.

Among the total number of ruthenium atoms contained in the inorganic shell, four -O-Si groups are directly bonded and a ruthenium atom of four oxygen atoms of four of the above-mentioned -O-Si groups is directly bonded. The ratio of the number is 50% or more.

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

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 organic-inorganic hybrid particles and a conductive layer disposed on a surface of the organic-inorganic hybrid particles .

According to a broad aspect of the present invention, a connection structure including: a first connection member having a first electrode on a surface thereof, a second connection member having a second electrode on a surface thereof, and the first connection are provided a connection portion between the target member and the second connection target member, wherein the connection portion is formed of conductive particles or a conductive material containing the conductive particles and a binder resin, and the conductive particles are provided with the above-described organic-inorganic hybrid The particles and the conductive layer disposed on the surface of the organic-inorganic hybrid particles, wherein the first electrode and the second electrode are electrically connected to each other by the conductive particles.

In the organic-inorganic hybrid particles of the present invention, an inorganic shell is disposed on the surface of the organic core, and in the 100% by weight of the organic core, the content of the ruthenium atom contained in the organic nucleus is 10% by weight or less and the organic nucleus The content of the carbon atom contained is 50% by weight or more, and the content of the ruthenium atom contained in the inorganic shell is 50% by weight or more and the content of the carbon atom contained in the inorganic shell is 100% by weight of the inorganic shell. 30% by weight or less, the ratio of the thickness of the inorganic shell to the radius of the organic core is 0.05 or more and 0.70 or less, so that the adhesion between the inorganic shell and the contact object in contact with the inorganic shell can be improved.

1‧‧‧Electrical particles

2‧‧‧ Conductive layer

11‧‧‧Organic and inorganic mixed particles

12‧‧‧Organic core

13‧‧‧Inorganic shell

21‧‧‧Electrical particles

22‧‧‧ Conductive layer

22A‧‧‧1st conductive layer

22B‧‧‧2nd conductive layer

31‧‧‧Electrical particles

31a‧‧‧ Protrusion

32‧‧‧ Conductive layer

32a‧‧‧ Protrusion

33‧‧‧ core material

34‧‧‧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 showing conductive particles according to a first embodiment of the present invention.

Fig. 2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention.

Fig. 3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention.

Fig. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.

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

Hereinafter, the details of the present invention will be described.

(organic and inorganic mixed particles)

The organic-inorganic hybrid particles of the present invention comprise an organic core and an inorganic shell disposed on the surface of the organic core. In the organic-inorganic hybrid particles of the present invention, the content of the ruthenium atom contained in the organic nucleus is 10% by weight or less and the content of the carbon atom contained in the organic nucleus is 50% by weight or more in 100% by weight of the organic nucleus. Further, in the organic-inorganic hybrid particles of the present invention, the content of the ruthenium atoms contained in the inorganic shell is 50% by weight or more and the content of the carbon atoms contained in the inorganic shell is 100% by weight of the inorganic shell. 30% by weight or less.

The organic core contains 50% by weight or more of carbon atoms, and therefore it is an organic core containing a carbon atom as a main component. The organic nucleus may also contain a ruthenium atom, but in the case of a ruthenium atom, since the carbon atom is a main component, it is called an organic nucleus. The inorganic shell contains 50% by weight or more of a ruthenium atom, and therefore it is an inorganic shell containing a ruthenium atom as a main component. The above inorganic shell may also contain carbon atoms, but in the case of containing carbon atoms, since the ruthenium atom is a main component, it is called an inorganic shell.

Further, in the organic-inorganic hybrid particles of the present invention, the ratio of the thickness of the inorganic shell to the radius of the organic core (the thickness of the inorganic shell/the radius of the organic core) is 0.05 or more and 0.70 or less.

In the organic-inorganic hybrid particles of the present invention, an inorganic shell is disposed on the surface of the organic core, and therefore, especially in the core-shell type particles, the core is an organic core, and the content of the germanium atom contained in the organic core is 10 When the content of the carbon atoms contained in the organic core is 50% by weight or more, the flexibility of the organic-inorganic hybrid particles can be improved. Therefore, when the organic-inorganic hybrid particles are used as a spacer for a liquid crystal display element and disposed between the substrates, or when electrically conductive particles having a conductive layer formed on the surface of the organic-inorganic hybrid particles are used to electrically connect the electrodes, The spacer or the conductive particles for the liquid crystal display element are efficiently disposed between the substrates or between the electrodes. Further, the contact area of the liquid crystal display element spacer or the conductive particles and the substrate or the electrode can be increased. Therefore, for example, the display quality of the liquid crystal display element is improved, and the connection resistance between the electrodes is lowered.

Further, in the organic-inorganic hybrid particles of the present invention, an inorganic shell is disposed on the surface of the organic core, and the content of the ruthenium atom and the carbon atom in the organic nucleus and the inorganic shell satisfies the above relationship, and the inorganic shell The ratio of the thickness to the radius of the organic core is 0.05 or more and 0.70 or less, whereby the adhesion between the inorganic shell and the contact object in contact with the inorganic shell can be improved. For example, when the organic-inorganic hybrid particles are used as a spacer for a liquid crystal display element and disposed between the substrates, the adhesion of the spacer for the liquid crystal display element to the substrate is changed. high. Further, when a conductive layer is formed on the surface of the organic-inorganic hybrid particles, the adhesion between the organic-inorganic hybrid particles and the conductive layer becomes high. Therefore, the conductive layer becomes difficult to peel off from the surface of the organic-inorganic hybrid particles, and the connection resistance between the electrodes connected by the conductive particles becomes low.

Further, since the adhesion between the organic-inorganic hybrid particles and the conductive layer is increased, the dispersibility of the conductive particles in the binder resin is improved, and the conductive particles are less likely to aggregate. Further, when the electrodes are electrically connected by using a conductive material in which conductive particles are dispersed in the binder resin, the difference in dispersion density of the conductive particles in the conductive material is small, so that it is difficult to increase the connection resistance. Further, since it is difficult to generate aggregated conductive particles, the insulation reliability in the bonded structure can be improved.

The ratio of the thickness of the inorganic shell to the radius of the organic core (the thickness of the inorganic shell/the radius of the organic core) is 0.05 or more and 0.70 or less. The above ratio (thickness of the inorganic shell / radius of the organic core) is preferably 0.10 or more, and preferably 0.60 or less. When the ratio is not less than the above lower limit and not more than the above upper limit, the adhesion between the inorganic shell and the contact object in contact with the inorganic shell is effectively increased. Moreover, the connection resistance between the electrodes electrically connected by the conductive particles can be reduced, and the insulation reliability can be improved.

In 100% by weight of the organic core, the content of the ruthenium atom contained in the organic nucleus is 10% by weight or less, preferably 5% by weight or less. The above organic core may also be free of germanium atoms. The above organic core is preferably free of germanium atoms. The content of the carbon atom contained in the organic core in 100% by weight of the organic core is 50% by weight or more, preferably 60% by weight or more, and more preferably 65% by weight or more. The smaller the content of the ruthenium atom in the organic nucleus, the more the content of the carbon atom in the organic nucleus is, and the adhesion between the inorganic shell and the contact object in contact with the inorganic shell is further increased, and further, The softness of the organic-inorganic hybrid particles of the organic core is further increased.

In 100% by weight of the inorganic shell, the content of the ruthenium atom contained in the inorganic shell is 50% by weight or more, preferably 54% by weight or more, more preferably 56% by weight or more, and further Preferably, it is 60% by weight or more. The above inorganic shell may also contain no carbon atoms. The above inorganic shell preferably contains no carbon atoms. In 100% by weight of the inorganic shell, the content of carbon atoms contained in the inorganic shell is 30% by weight or less, preferably 20% by weight or less, and more preferably 10% by weight or less. The more the content of the ruthenium atoms in the inorganic shell, the smaller the content of the carbon atoms in the inorganic shell, and the higher the adhesion between the inorganic shell and the contact object in contact with the inorganic shell, and further the source The hardness from the initial stage of compression of the inorganic shell is further improved.

When the content of the ruthenium atom contained in the inorganic shell is 54% by weight or more in 100% by weight of the inorganic shell, the adhesion between the inorganic shell and the conductive layer is further increased, and if it is 60% by weight or more, no The adhesion between the casing and the conductive layer becomes quite high. In addition, when the content of the ruthenium atom contained in the inorganic shell is 54% by weight or more in 100% by weight of the inorganic shell, the adhesion of the spacer for a liquid crystal display element to the substrate is further increased, and is 60% by weight. As described above, the adhesion of the spacer for the liquid crystal display element to the substrate is relatively high.

The content of the ruthenium atom and the carbon atom in the organic nucleus and the inorganic shell in the above organic-inorganic hybrid particles can be measured by line analysis by TEM/EDS method.

Among the total number of ruthenium atoms contained in the inorganic shell, four -O-Si groups are directly bonded and a ruthenium atom of four oxygen atoms of four of the above-mentioned -O-Si groups is directly bonded. The ratio of the number is preferably 50% or more. In this case, the compression elastic modulus at a compression of 10% is relatively high, and the compression elastic modulus at a compression of 30% is relatively low, and the organic-inorganic hybrid particles have further excellent compression deformation characteristics.

The use of the above organic-inorganic hybrid particles is not particularly limited. The above organic-inorganic hybrid particles can be preferably used in various applications. The organic-inorganic hybrid 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 hybrid particles of the present invention are preferably used to form a conductive layer on the surface to obtain conductive particles having the above-mentioned conductive layer. The organic-inorganic hybrid particles are preferably used as a spacer for a liquid crystal display element. In the above-mentioned organic-inorganic hybrid particles, the adhesion between the inorganic shell and the contact object in contact with the inorganic shell is high, so that it is used. When the organic-inorganic hybrid particles are disposed between the substrates as a spacer for a liquid crystal display element, or when a conductive layer is formed on the surface and used as conductive particles to electrically connect the electrodes, the spacer for the liquid crystal display element or the conductive material is used. The particles are efficiently disposed between the substrates or between the electrodes. Further, when an impact is applied to the liquid crystal display element using the spacer for a liquid crystal display element and the connection structure using the conductive particles, the interval between the substrate and the electrode fluctuates, and the spacer for the liquid crystal display element or the conductive particles sufficiently follows easily transformed. Therefore, unevenness in spacing between the substrates or between the electrodes is hard to occur, and connection failure between the electrodes becomes difficult to occur.

Further, the above-mentioned organic-inorganic hybrid particles can also be preferably used as an inorganic filler, an additive for a toner, an impact absorber or a vibration absorber. For example, the above-mentioned organic-inorganic hybrid particles can be used as a substitute for rubber or a spring or the like.

The compression elastic modulus (10% K value) when the organic-inorganic hybrid particles are subjected to 10% compression deformation is preferably 2000 N/mm ² or more, more preferably 3,000 N/mm ² or more, and still more preferably 4,000 N/mm ² or more. , particularly preferably 5000N / mm ² or more, most preferably 6000N / mm ² or more, and preferably 15000N / mm ² or less, more preferably 10000N / mm ² or less, and further preferably 8500N / mm ² or less. The organic-inorganic hybrid particles having a 10% K value and not less than the above lower limit and not more than the above upper limit have good compression set characteristics.

The organic-inorganic hybrid particles 30% compression modulus of compressive elasticity (30% K value) is preferably 300N / mm ² or more when deformed, more preferably 600N / mm ² or more, and further preferably 800N / mm ² or more , particularly preferably 1000N / mm ² or more, and preferably 5000N / mm ² or less, more preferably 4500N / mm ² or less, and further preferably 4000N / mm ² or less. The organic-inorganic hybrid particles having a 30% K value and not less than the above lower limit and not more than the above upper limit have good compression set characteristics.

The compression elastic modulus (10% K value) when the organic-inorganic hybrid particles are compressed by 10% with respect to the compression elastic modulus when the organic-inorganic hybrid particles are compressed by 30% in terms of obtaining good compression deformation characteristics ( 30% K value) ratio (10% K value / 30% K value) is preferably 1 The above is more preferably 1.3 or more, still more preferably 1.8 or more, still more preferably 2.0 or more, and still more preferably 10.0 or less, more preferably 5.0 or less, still more preferably 4.4 or less.

The above-mentioned compression elastic modulus (10% K value and 30% K value) in the above organic-inorganic hybrid particles can be measured in the following manner.

The organic-inorganic hybrid particles were compressed on a smooth indenter end face 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 using a micro compression tester. The load value (N) and the compression displacement (mm) at this time were measured. The measured value can be obtained from the measured value, and the above-described compression elastic modulus can be obtained by the following formula. For example, "Fischerscope H-100" manufactured by Fischer Co., Ltd. or the like can be used as the above-described micro compression tester.

K value (N/mm ² )=(3/2 ^1/2 )‧F‧S ^-3/2 ‧R ^-1/2

F: load value when the organic-inorganic hybrid particles are subjected to 10% or 30% compression deformation (N)

S: Compressive displacement (mm) when the organic-inorganic hybrid particles are subjected to 10% or 30% compression deformation

R: radius of organic-inorganic hybrid particles (mm)

The above-mentioned compression elastic modulus generally and quantitatively indicates the hardness of the organic-inorganic hybrid particles. By using the above-described compression elastic modulus, the hardness of the organic-inorganic hybrid particles can be quantitatively and singly expressed.

The organic core is preferably an organic particle. Various organic substances can be preferably used as the material for forming the above organic core. For example, polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyisobutylene, polybutadiene, etc.; polymethyl methacrylate, polymethyl acrylate can be used; Acrylic resin; polyalkylene terephthalate, polyfluorene, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, and one or two A polymer obtained by polymerizing various polymerizable monomers having an ethylenically unsaturated group or the like is used as a material for forming the organic core. By using one or two or more kinds of polyunsaturated groups The merging monomer is polymerized, and it is easy to design and synthesize an organic-inorganic hybrid particle suitable for a conductive material having any physical properties at the time of compression.

When the monomer having an ethylenically unsaturated group is polymerized to obtain the organic nucleus, the monomer having an ethylenically unsaturated group may be a non-crosslinkable monomer and a crosslinkable monomer.

Examples of the non-crosslinkable monomer include a styrene monomer such as styrene or α-methylstyrene, and a carboxyl group such as (meth)acrylic acid, maleic acid or maleic anhydride. Monomer; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) ) lauryl acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate Alkyl (meth) acrylate such as ester; 2-hydroxyethyl (meth) acrylate, glyceryl (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, etc. (meth) acrylate containing oxygen atom; nitrile containing monomer such as (meth) acrylonitrile; vinyl ether such as methyl vinyl ether, ethyl vinyl ether or propyl vinyl ether; vinyl acetate , vinyl acetate such as vinyl butyrate, vinyl laurate, vinyl stearate; unsaturated hydrocarbons such as ethylene, propylene, isoprene, butadiene; trifluoromethyl (meth)acrylate, A halogen-containing monomer such as pentafluoroethyl methacrylate, vinyl chloride, vinyl fluoride or chlorostyrene.

Examples of the crosslinkable monomer include tetramethylol methane tetra(meth)acrylate, tetramethylol methane tri(meth)acrylate, and tetramethylolmethane di(meth)acrylate. Ester, trimethylolpropane tri(meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri(meth) acrylate, glycerol di(methyl) Acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)1,4-butanediol di(meth)acrylate, 1,4 - Polyfunctional (meth) acrylates such as butanediol di(meth) acrylate; triallyl (iso) cyanurate, triallyl trimellitate, divinyl benzene, phthalic acid Allyl ester, diallyl acrylamide, A decane-containing monomer such as diallyl ether, γ-(meth)acryloxypropyltrimethoxydecane, trimethoxydecylstyrene or vinyltrimethoxydecane.

The above organic nucleus can be obtained by polymerizing the above polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of the method include a method in which suspension polymerization is carried out in the presence of a radical polymerization initiator, and a method in which a non-crosslinked seed particle is swollen with a radical polymerization initiator to polymerize the monomer.

The decomposition temperature of the organic core is preferably more than 200 ° C, more preferably more than 250 ° C, and even more preferably more than 300 ° C from the viewpoint of forming an inorganic shell and suppressing deformation of the organic core when the organic-inorganic hybrid particles are used. . The decomposition temperature of the above organic core may also exceed 400 ° C, may exceed 500 ° C, may exceed 600 ° C, and may exceed 800 ° C.

The particle diameter of the organic core is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 500 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, still more preferably 20 μm or less, and most preferably 10 μm or less. . When the particle diameter of the organic core is not less than the above lower limit and not more than the above upper limit, the 10% K value and the 30% K value show further preferable values, and the organic-inorganic hybrid particles can be preferably used for the conductive particles and the liquid crystal display. The use of spacers for components. For example, when the particle diameter of the organic core is not less than the above lower limit and not more than the above upper limit, when the electrodes are connected by using the conductive particles, the contact area between the conductive particles and the electrode is sufficiently increased, and the conductive layer is formed. At the time of the layer, it becomes difficult to form agglomerated conductive particles. Moreover, the interval 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.

The particle diameter of the organic nucleus means a diameter when the organic nucleus is a true spherical shape, and means a maximum diameter when the organic nucleus has a shape other than a true spherical shape. Further, in the present invention, the particle diameter means an average value obtained by observing an organic nucleus using a scanning electron microscope and measuring the particle diameter of arbitrarily selected 50 organic nuclei by a vernier caliper.

The above organic-inorganic hybrid particles are core-shell particles. The inorganic shell is disposed on the surface of the organic core. The inorganic shell preferably covers the surface of the organic core.

The inorganic shell is preferably formed by baking a metal alkoxide on a surface of the organic core by a sol-gel method and then baking the shell. In the sol-gel method, a shell is easily disposed on the surface of the above organic core. In the case of performing the above calcination, in the organic-inorganic hybrid particles, the organic core is not removed by volatilization or the like after calcination. The organic-inorganic hybrid particles have the organic core after firing. Further, if the organic nucleus is removed by volatilization or the like after firing, the 10% K value becomes relatively low.

Specific examples of the sol-gel method include that an inorganic monomer such as tetraethoxysilane is present in a dispersion containing a solvent such as an organic nucleus, water or an alcohol, a surfactant, or a catalyst such as an aqueous ammonia solution. a method of performing an interfacial sol reaction; and performing a sol-gel reaction by an inorganic monomer such as tetraethoxy decane coexisting with a solvent such as water or an alcohol or an aqueous ammonia solution, and then causing the sol-gel reactant to be agglutinated in the organic nucleus Method and so on. In the above sol-gel method, the metal alkoxide is preferably subjected to hydrolysis and polycondensation.

In the above sol-gel method, a surfactant is preferably used. Preferably, the metal alkoxide is formed into a shell by a sol-gel method in the presence of a surfactant. The above surfactant is not particularly limited. The above surfactant can be appropriately selected for use to form a good shell. Examples of the surfactant include a cationic surfactant, an anionic surfactant, and a nonionic surfactant. Among them, a cationic surfactant is preferred in that a good inorganic shell can be formed.

Examples of the cationic surfactant include a quaternary ammonium salt and a quaternary phosphonium salt. Specific examples of the above cationic surfactant include cetyl ammonium bromide and the like.

In order to form the above inorganic shell on the surface of the above organic core, it is preferred to calcine the above shell. The degree of crosslinking in the inorganic shell can be adjusted by using the firing conditions. Further, by performing the calcination, the 10% K value and the 30% K value of the above-mentioned organic-inorganic hybrid particles showed a further preferable value as compared with the case where the calcination was not performed. Especially by increasing the degree of crosslinking, The 10% K value is sufficiently high.

Preferably, the inorganic shell is formed by baking a metal alkoxide on a surface of the organic core by a sol-gel method, and then baking the shell at 100 ° C or higher (baking temperature). form. The calcination temperature is more preferably 150 ° C or higher, and still more preferably 200 ° C or higher. When the calcination temperature is at least the above lower limit, the degree of crosslinking in the inorganic shell is further moderated, and the 10% K value and the 30% K value show further preferable values, so that the organic-inorganic hybrid particles can be further preferably used. Use for conductive particles and spacers for liquid crystal display elements.

Preferably, the inorganic shell is formed by forming a metal alkoxide into a shell by a sol-gel method on the surface of the organic core, and the shell is below a decomposition temperature of the organic core (baking temperature). It is formed by baking. The calcination temperature is preferably a temperature lower than the decomposition temperature of the organic core by 5 ° C or higher, and more preferably a temperature lower than the decomposition temperature of the organic core by 10 ° C or higher. Further, the baking temperature is preferably 800 ° C or lower, more preferably 600 ° C or lower, and still more preferably 500 ° C or lower. When the calcination temperature is at most the above upper limit, thermal deterioration and deformation of the organic core can be suppressed, and organic-inorganic hybrid particles having a 10% K value and a 30% K value which exhibits a good value can be obtained.

Examples of the metal alkoxide include a decane oxide, a titanium alkoxide, a zirconium alkoxide, and an aluminoxane. The metal alkoxide is preferably a decane oxide, a titanium alkoxide, a zirconium alkoxide or an aluminum alkoxide, more preferably a decane oxide or a titanium alkoxide, from the viewpoint of forming a good inorganic shell. Or a zirconium alkoxide, more preferably a decane oxide. From the viewpoint of forming a good inorganic shell, the metal atom in the above metal alkoxide is preferably a ruthenium atom, a titanium atom, a zirconium atom or an aluminum atom, more preferably a ruthenium atom, a titanium atom or a zirconium atom, and further Jia is a scorpion atom. The metal alkoxide may be used alone or in combination of two or more.

The metal alkoxide is preferably a metal alkoxide represented by the following formula (1) from the viewpoint of forming a good inorganic shell.

M(R1) _n (OR2) _4-n (1)

In the above formula (1), M is a halogen atom, a titanium atom or a zirconium atom, and R1 represents a phenyl group, an alkyl group having 1 to 30 carbon atoms, an organic group having a carbon number of 1 to 30 having a polymerizable double bond, or an epoxy group. The organic group having a carbon number of 1 to 30, R2 represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 2. When n is 2, a plurality of R1s may be the same or different. A plurality of R2s may be the same or different.

The metal alkoxide is preferably a decane oxide represented by the following formula (1A) from the viewpoint of forming a good inorganic shell.

Si(R1) _n (OR2) _4-n (1A)

In the above formula (1A), R1 represents a phenyl group, an alkyl group having 1 to 30 carbon atoms, an organic group having a carbon number of 1 to 30 having a polymerizable double bond, or an organic group having 1 to 30 carbon atoms having an epoxy group. R2 represents an alkyl group having 1 to 6 carbon atoms. When n is 2, a plurality of R1s may be the same or different. A plurality of R2s may be the same or different. In order to effectively increase the content of the ruthenium atom contained in the inorganic shell, n in the above formula (1A) preferably represents 0 or 1, more preferably 0. When the content of the ruthenium atoms contained in the inorganic shell is high, the effects of the present invention are further excellent.

In the case where R1 is an alkyl group having 1 to 30 carbon atoms, specific examples of R1 include methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, n-hexyl group, cyclohexyl group, and n-octyl group. Base, and positive base. The carbon number of the alkyl group is preferably 10 or less, more preferably 6 or less. Further, the alkyl group contains a cycloalkyl group.

The polymerizable double bond may, for example, be a carbon-carbon double bond. In the case where the above R1 is an organic group having a carbon number of 1 to 30 having a polymerizable double bond, examples of R1 include a vinyl group, an allyl group, an isopropenyl group, and a 3-(meth)acryl oxime. Oxyalkyl and the like. Examples of the (meth)acryloxyalkylene group include (meth)acryloxymethyl group, (meth)acryloxyethyl group, and (meth)acryloxypropyl group. The carbon number of the organic group having 1 to 30 carbon atoms having a polymerizable double bond is preferably 2 or more, and is preferably 30 or less, more preferably 10 or less. The above "(meth)acryloxy group" means a methacryloxy group or an acryloxy group.

In the case where the above R1 is an organic group having an epoxy group having 1 to 30 carbon atoms, specific examples of R1 include 1,2-epoxyethyl group and 1,2-epoxypropyl group. 2,3-epoxypropyl, 3,4-epoxybutyl, 3-glycidoxypropyl, and 2-(3,4-epoxycyclohexyl)ethyl, and the like. The carbon number of the organic group having 1 to 30 carbon atoms having an epoxy group is preferably 8 or less, more preferably 6 or less. Further, the organic group having 1 to 30 carbon atoms having an epoxy group contains a group derived from an oxygen atom derived from an epoxy group in addition to a carbon atom and a hydrogen atom.

Specific examples of the above R2 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. In order to effectively increase the content of the ruthenium atoms contained in the shell, the above R2 preferably represents a methyl group or an ethyl group.

Specific examples of the above decane oxide include tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, and ethyl triethyl ethane. Oxy decane, isopropyl trimethoxy decane, isobutyl trimethoxy decane, cyclohexyl trimethoxy decane, n-hexyl trimethoxy decane, n-octyl triethoxy decane, n-decyl trimethoxy decane And phenyltrimethoxydecane, dimethyldimethoxydecane, and diisopropyldimethoxydecane. It is also possible to use decane oxides other than these.

In order to effectively increase the content of the ruthenium atom contained in the inorganic shell, it is preferred to use tetramethoxy decane or tetraethoxy decane as the material of the above inorganic shell. The total content of tetramethoxy decane and tetraethoxy decane in 100% by weight of the material of the inorganic shell is preferably 50% by weight or more (may also be the total amount). In 100% by weight of the inorganic shell, the total content of the skeleton derived from tetramethoxynonane and the skeleton derived from tetraethoxysilane is preferably 50% by weight or more (may also be the total amount).

Specific examples of the titanium alkoxide include titanium tetramethoxide, titanium tetraethoxy oxide, titanium tetraisopropyl oxide, and titanium tetrabutyl oxide. Titanium alkoxides other than these may also be used.

Specific examples of the zirconium alkoxide include zirconium tetramethoxide, zirconium tetraethoxy oxide, zirconium tetraisopropoxide, and zirconium tetrabutoxide. Can also use other than these Zirconium alkoxide.

The metal alkoxide is preferably a metal alkoxide having a structure in which four oxygen atoms are directly bonded to a metal atom. The metal alkoxide preferably contains a metal alkoxide represented by the following formula (1a).

M(OR2) ₄ (1a)

In the above formula (1a), M is a halogen atom, a titanium atom or a zirconium atom, R2 represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 2. A plurality of R2s may be the same or different.

The metal alkoxide preferably contains a decane oxide having a structure in which a halogen atom is directly bonded to four atoms. In the decane oxide, usually four oxygen atoms are bonded to a ruthenium atom by a single bond. The metal alkoxide preferably contains a decane oxide represented by the following formula (1Aa).

Si(OR2) ₄ (1Aa)

In the above formula (1Aa), R2 represents an alkyl group having 1 to 6 carbon atoms. A plurality of R2s may be the same or different.

In view of the fact that the 10% K value is effectively increased and the 30% K value is effectively lowered, in the above 100 mol% of the metal alkoxide for forming an inorganic shell, the above has a direct bond to the metal atom. a metal alkoxide having a structure of four oxygen atoms, a metal alkoxide represented by the above formula (1a), a decane oxide having a structure in which a halogen atom is directly bonded to four oxygen atoms, or the above formula ( The content of the decane oxide represented by 1Aa) is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, and still more preferably 55 mol% or more. Preferably, it is 60% by mole or more, and is 100% by mole or less. The total amount of the metal alkoxide to form the inorganic shell may be the metal alkoxide having a structure in which four oxygen atoms are directly bonded to the metal atom, and the metal alkoxide represented by the above formula (1a) And a decane oxide having a structure in which a ruthenium atom is directly bonded to four oxygen atoms or a decane oxide represented by the above formula (1Aa).

From the viewpoint of effectively making the 10% K value high and effectively making the 30% K value lower, In the total number of metal atoms of the metal alkoxide contained in the inorganic shell, the ratio of the number of metal atoms directly bonded to four oxygen atoms is directly bonded to four -O-Si The ratio of the number of the ruthenium atoms directly bonded to the four oxygen atoms of the four -O-Si groups is preferably 20% or more, more preferably 40% or more, and still more preferably 50% or more. More preferably, it is 55 mol% or more, and more preferably 60% or more.

Further, in terms of effectively increasing the 10% K value and effectively lowering the 30% K value, in the total number of metal atoms contained in the inorganic shell, 100% of the oxygen is directly bonded. The ratio of the number of metal atoms of the atom is preferably 20% or more, more preferably 40% or more, further preferably 50% or more, further preferably 55 % by mole or more, and particularly preferably 60% or more. The metal alkoxide is a decane oxide and the total number of ruthenium atoms contained in the inorganic shell is 100% from the viewpoint of effectively increasing the 10% K value and effectively lowering the 30% K value. In the above, the ratio of the number of the argon atoms directly bonded to the four -O-Si groups and directly bonded to the four oxygen atoms of the four -O-Si groups is preferably 20% or more, more preferably 40% or more, further preferably 50% or more, and particularly preferably 60% or more.

Further, a germanium atom directly bonded to four -O-Si groups and directly bonded to four of the above-mentioned -O-Si groups is, for example, a structure represented by the following formula (11) Helium atom. Specifically, it is a germanium atom represented by an arrow A in the structure represented by the following formula (11X).

Further, the oxygen atom in the above formula (11) usually forms a decane bond with an adjacent ruthenium atom.

The ratio (number of the number of Q4) of the number of 矽 atoms which have four -O-Si groups directly bonded and four of the above-mentioned -O-Si groups are directly bonded. For the method of performing the measurement, for example, Q4 (4 -O-Si groups directly bonded and directly bonded to 4 of the above-mentioned -O-Si groups) may be used. The peak area of the ruthenium atom is the same as Q1~Q3 (1~3 -O-Si groups are directly bonded and 1~3 oxygen atoms in the above -O-Si group are directly bonded) The method of comparing the peak areas of atoms. By this method, it is found that 100% of the total number of germanium atoms contained in the inorganic shell is directly bonded to four -O-Si groups and directly bonded to four of the above -O-Si groups. The ratio of the number of 矽 atoms of the four oxygen atoms (the ratio of the number of Q4). Further, in the NMR measurement results obtained by determining the ratio of the number of Q4 in the following examples, there were four -O-Si groups derived from direct bonding and four above-mentioned -O-Si were directly bonded. The peaks of the ruthenium atoms of the four oxygen atoms in the group were evaluated.

The thickness of the inorganic shell is preferably 1 nm or more, more preferably 10 nm or more, further preferably 50 nm or more, particularly preferably 100 nm or more, and more preferably 100000 nm or less, more preferably 10000 nm or less, still more preferably 2,000 nm or less. . When the thickness of the inorganic shell is not less than the above lower limit and not more than the above upper limit, the 10% K value and the 30% K value show further preferable values, and the organic-inorganic hybrid particles can be preferably used for the conductive particles and the liquid crystal display. The use of spacers for components. The thickness of the above inorganic shell is the level of each of the organic-inorganic hybrid particles Average thickness. The thickness of the above inorganic shell can be controlled by controlling the sol-gel method.

In the present invention, the thickness of the inorganic shell can be observed by scanning electron microscopy, and the average value obtained by measuring the particle diameter of arbitrarily selected 50 organic-inorganic hybrid particles by using a vernier caliper is obtained. The difference between the average values of the particle diameters of the organic nuclei was obtained. The particle size of the organic-inorganic hybrid particles means a diameter when the organic-inorganic hybrid particles are in a true spherical shape, and means a maximum diameter when the organic-inorganic hybrid particles have a shape other than a true spherical shape.

The aspect ratio of the organic-inorganic hybrid particles is preferably 2 or less, more preferably 1.5 or less, still more preferably 1.2 or less. The above aspect ratio means long diameter/short diameter.

Preferably, no chemical bonding is performed between the organic core and the inorganic shell. When the organic core and the inorganic shell are not chemically bonded, the inorganic shell becomes difficult to be excessively broken, and the contact area between the electrode and the conductive particles to the connecting member can be increased, and the electrode can be made. The connection resistance between the two is further lowered.

Preferably, chemical bonding is not performed between the organic core and the inorganic shell, but chemical bonding may also be performed. The method of chemically bonding the organic nucleus to the inorganic shell may be a method of introducing a functional group reactive with a functional group of a material constituting the inorganic shell on the surface of the organic nucleus, and then on the surface of the organic nucleus. A method of forming an inorganic shell by the above-described material constituting the inorganic shell. Specifically, a method of subjecting the surface of the organic core to a surface of the organic core by a coupling agent to form a metal alkoxide into a shell by a sol-gel method.

(conductive particles)

The conductive particles include the organic-inorganic hybrid particles and a conductive layer disposed on a surface of the organic-inorganic hybrid particles.

The conductive particles according to the first embodiment of the present invention are shown in cross section in Fig. 1 .

The conductive particles 1 shown in FIG. 1 have organic-inorganic hybrid particles 11 and a conductive layer 2 disposed on the surface of the organic-inorganic hybrid particles 11. Conductive layer 2 coated with organic-inorganic hybrid particles 11 surface. The conductive particles 1 are coated particles in which the surface of the organic-inorganic hybrid particles 11 is covered with the conductive layer 2 .

The organic-inorganic hybrid particles 11 include an organic core 12 and an inorganic shell 13 disposed on the surface of the organic core 12 . The inorganic shell 13 coats the surface of the organic core 12. The conductive layer 2 is disposed on the surface of the inorganic shell 13. The conductive layer 2 coats the surface of the inorganic shell 13.

The conductive particles of the second embodiment of the present invention are shown in cross section in Fig. 2 .

The conductive particles 21 shown in FIG. 2 have organic-inorganic hybrid particles 11 and a conductive layer 22 disposed on the surface of the organic-inorganic hybrid particles 11. The conductive layer 22 has a first conductive layer 22A as an inner layer and a second conductive layer 22B as an outer layer. The first conductive layer 22A is disposed on the surface of the organic-inorganic hybrid particles 11. The first conductive layer 22A is disposed on the surface of the inorganic shell 13. The second conductive layer 22B is disposed on the surface of the first conductive layer 22A.

Fig. 3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention.

The conductive particles 31 shown in FIG. 3 have organic-inorganic hybrid particles 11, a conductive layer 32, a plurality of core materials 33, and a plurality of insulating materials 34.

The conductive layer 32 is disposed on the surface of the organic-inorganic hybrid particles 11. A conductive layer 32 is disposed on the surface of the inorganic shell 13.

The conductive particles 31 have a plurality of protrusions 31a on the surface of the conductivity. The conductive layer 32 has a plurality of protrusions 32a on the outer surface. As described above, the conductive particles may have protrusions on the surface of the conductive layer, or may have protrusions on the outer surface of the conductive layer. A plurality of core materials 33 are disposed on the surface of the organic-inorganic hybrid particles 11. A plurality of core materials 33 are disposed on the surface of the inorganic shell 13. A plurality of core materials 33 are embedded in the conductive layer 32. The core material 33 is disposed inside the protrusions 31a and 32a. The conductive layer 32 is coated with a plurality of core materials 33. The outer surfaces of the conductive layer 32 are embossed by the plurality of core materials 33, and the projections 31a, 32a are formed.

The conductive particles 31 have an insulating material 34 disposed on the outer surface of the conductive layer 32. At least a portion of the outer surface of the conductive layer 32 is covered with an insulating material 34. insulation The substance 34 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, antimony, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, ruthenium, osmium, iridium, osmium, cadmium, and antimony. Such alloys and the like. Further, examples of the metal include tin-doped indium oxide (ITO), solder, and the like. Among them, since the connection resistance between the electrodes can be further lowered, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable.

The conductive layer may be formed of one layer as in the case of the conductive particles 1 and 31. The conductive layer may be formed of a plurality of layers as in the case of the conductive particles 21. That is, the conductive layer may have a laminated structure of two or more layers. 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 such a preferred conductive layer, the connection resistance between the electrodes is further lowered. Further, when the outermost layer is a gold layer, the corrosion resistance is further increased.

The method of forming the conductive layer on the surface of the above-described organic-inorganic hybrid 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 hybrid particle. Surface method, etc. Among them, the method of electroless plating is preferred because the formation of the conductive layer is simple. 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 0.5 μm or more, more preferably 1 μm or more, further preferably 520 μm or less, more preferably 500 μm or less, still more preferably 100 μm or less, still more 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, when the electrodes are connected by using the conductive particles, the contact area between the conductive particles and the electrode is sufficiently increased, and the conductive layer is changed. It is difficult to form agglomerated conductive particles. Moreover, the electrodes are connected via conductive particles The interval does not become excessive, and the conductive layer becomes difficult to peel off from the surface of the organic-inorganic hybrid 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 conductive particles means a diameter when the conductive particles are in a true spherical shape, and means a maximum diameter when the conductive particles have a shape other than a true spherical shape.

The thickness of the conductive layer is preferably 0.005 μm or more, more preferably 0.01 μm or more, and is preferably 10 μm or less, more preferably 1 μm or less, further preferably 0.5 μm or less, and particularly preferably 0.3 μm or less. The thickness of the conductive layer is the thickness of the entire conductive layer when the conductive layer is a plurality of layers. When the thickness of the conductive layer is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles are not excessively hard, 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, and is preferably 0.5 μm or less, more preferably 0.1 μm or less. When the thickness of the outermost conductive layer is not less than the above lower limit and not more than the above upper limit, the coating of the outermost conductive layer is uniform, the corrosion resistance is sufficiently increased, 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 conductive layer can be measured, for example, by observing a cross section of the conductive particles using a transmission electron microscope (TEM).

The conductive particles may have protrusions on the surface of the conductivity. The conductive particles may have protrusions on the outer surface of the conductive layer. The protrusions are preferably plural. In many cases, an oxide film is formed on the surface of the electrode to which the conductive particles are connected. When the conductive particles having protrusions are used, the conductive particles are placed between the electrodes and pressure-bonded, whereby the oxide film is effectively removed by the protrusions. Therefore, the electrode and the conductive layer of the conductive particles can be further reliably contacted, and the connection resistance between the electrodes can be lowered. Further, when the conductive particles have an insulating material on the surface, they may be electrically conductive. When the particles are dispersed in the binder resin and used as a conductive material, the insulating material or the binder resin between the conductive particles and the electrode can be effectively removed by the protrusion of the conductive particles. Therefore, the conduction reliability between the electrodes can be improved.

The method of forming a protrusion on the surface of the conductive particles includes a method of forming a conductive layer by electroless plating after attaching a core substance to a surface of the organic-inorganic hybrid particle, and a surface of the organic-inorganic hybrid particle. A method of forming a conductive layer by electroless plating, forming a conductive layer, and forming a conductive layer by electroless plating. 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, when the conductive particles are used for the connection between the electrodes, the short circuit between the adjacent electrodes can be prevented. Specifically, when a plurality of conductive particles are in contact with each other, an insulating material is present between the plurality of electrodes. Therefore, it is possible to prevent short-circuiting between the electrodes adjacent in the lateral direction, and is not a short circuit between the upper and lower electrodes. Further, when the electrodes are connected, the conductive particles are pressurized by the two electrodes, whereby 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 further 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 above-mentioned conductive particles and a 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 can be preferably used for electrical connection of electrodes. The above conductive material is preferably a circuit connecting material.

The above binder resin is not particularly limited. As the above-mentioned binder resin, a known insulating resin can be used. Examples of the binder resin include a vinyl resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer, and an elastomer. Above 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. Examples of the elastomer include a styrene-butadiene copolymer rubber and an acrylonitrile-styrene block copolymer rubber.

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 stabilizer. Various additives such as agents, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents and flame retardants.

The method of dispersing the above-mentioned conductive particles in the above-mentioned binder resin can be a conventionally known dispersion method, and is not particularly limited. As a 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 dispersed, and homogenization is used. a method in which the conductive particles are uniformly dispersed in water or an organic solvent, and then added to the binder resin, kneaded by a planetary mixer or the like, and dispersed, and diluted with water or an organic solvent. After the binder resin, the above-mentioned conductive particles are added, and a method of kneading by a planetary mixer or the like is dispersed.

The above conductive material can be used as a conductive paste, a conductive film, or the like. When the conductive material of the present invention is a conductive film, the conductive film containing the conductive particles may be laminated without a guide. A film of electrical 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 is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, and more preferably 100% by weight of the conductive material. It is 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 increased.

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, and is preferably 40% by weight or less, more preferably 20% by weight or less, and further preferably It is 10% by weight or less. When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further increased.

(connection structure and liquid crystal display element)

The connection structure can be obtained by using the above-described conductive particles or by using a conductive material containing the above-described conductive particles and a binder resin to connect the connection member.

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 formed of the conductive particles. Alternatively, it may be formed of a conductive material containing the above-described 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 the surface. Preferably, the second connection target member has a second electrode on the surface. Preferably, the first electrode and the second electrode are electrically connected by the conductive particles.

Fig. 4 is a front cross-sectional view schematically showing a connection structure using the conductive particles 1 shown in Fig. 1 .

The connection structure body 51 shown in FIG. 4 includes the first connection object member 52, the second connection object member 53, and the 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 the conductive particles 1 and a binder resin. In Fig. 4, the conductive particles 1 are simply shown for convenience of illustration. In addition to the conductive particles 1, other conductive particles such as conductive particles 21 and 31 may be used.

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 1 .

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 pressure of the pressurization 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, a glass substrate such as a glass 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 connecting object member is preferably a flexible printing base The plate is preferably a member to be connected to 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 formed of an aluminum layer on a surface layer of a 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.

Further, the organic-inorganic hybrid particles can be preferably used as a spacer for a liquid crystal display element. In other words, the organic-inorganic hybrid particles are preferably used to obtain a liquid crystal display device comprising: a pair of substrates constituting the liquid crystal cell, a liquid crystal sealed between the pair of substrates, and disposed between the pair of substrates A spacer for a liquid crystal display element.

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

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 of 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 hybrid particles 11 are disposed between the pair of transparent glass substrates 82. The organic-inorganic hybrid particles 11 are used as spacers for liquid crystal display elements. Controlling a pair by a plurality of organic-inorganic hybrid particles 11 The spacing of the transparent glass substrates 82. 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 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. When the above-described arrangement density is 10 pieces/mm ² or more, the cell pitch is further uniformized. When the above-described arrangement density is 1000/mm ² or less, the contrast of the liquid crystal display element is further improved.

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

(1) Production of organic-inorganic hybrid particles

(Example 1)

"Micropearl EYP-00375" (acrylic polymer, average particle diameter 3.75 μm) manufactured by Sekisui Chemical Industry Co., Ltd. was prepared as an organic core. 100 parts by weight of the organic core and 40 parts by weight of cetyltrimethylaluminum bromide as a surfactant are dispersed in a mixed solvent of 1800 parts by weight of ethanol and 200 parts by weight of water, and placed in a separable flask. . 80 parts by weight of a 25 wt% aqueous ammonia solution was added, and the mixture was stirred while applying ultrasonic waves. A solution obtained by dissolving 600 parts by weight of tetraethoxy decane in 1200 parts by weight of ethanol was added, and the mixture was stirred at 25 ° C for 24 hours while applying ultrasonic waves. The reaction solution was taken out, and subjected to suction filtration using a membrane filter made of PTFE (polytetrafluoroethylene), and washed twice with ethanol, and then dried by a vacuum dryer at 50 ° C for 24 hours to obtain an organic-inorganic hybrid. particle.

(2) Production of conductive particles

After the obtained organic-inorganic hybrid particles were washed and dried, a nickel layer was formed on the surface of the obtained organic-inorganic hybrid particles by electroless plating to prepare conductive particles. Further, the thickness of the nickel layer was 0.1 μm.

(Example 2)

The organic core was changed to "Micropearl EX-00375" (styrene polymer, average particle diameter 3.75 μm) manufactured by Sekisui Chemical Co., Ltd., and the addition of tetraethoxy decane was added. The organic-inorganic hybrid particles and the conductive particles were obtained in the same manner as in Example 1 except that the amount was changed to 300 parts by weight.

(Example 3)

The organic core was changed to "Micropearl ELP-00375" (styrene-acrylate copolymer, average particle diameter 3.75 μm) manufactured by Sekisui Chemical Co., Ltd., and ethanol was changed to isopropanol to add tetraethoxydecane. The organic-inorganic hybrid particles and the conductive particles were obtained in the same manner as in Example 1 except that the amount was changed to 900 parts by weight.

(Example 4)

The organic core was changed to "Micropearl ELP-00375" (styrene-acrylate copolymer, average particle diameter 3.75 μm) manufactured by Sekisui Chemical Co., Ltd., and ethanol was changed to isopropanol to add tetraethoxydecane. The organic-inorganic hybrid particles and the conductive particles were obtained in the same manner as in Example 1 except that the amount was changed to 1200 parts by weight.

(Example 5)

In addition, the organic nucleus was changed to "Micropearl EX-00375" (styrene-based polymer, average particle diameter: 3.75 μm) manufactured by Sekisui Chemical Co., Ltd., and the amount of tetraethoxy decane was changed to 100 parts by weight. Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1.

(Example 6)

(1) Palladium attachment step

The organic-inorganic hybrid particles obtained in Example 1 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 a palladium catalyst solution containing 8 wt% of a palladium catalyst and stirred. Thereafter, it was filtered and washed. The organic-inorganic hybrid particles were added to a 0.5 wt% dimethylamine borane solution having a pH of 6, to obtain an organic-inorganic hybrid particle to which palladium was attached.

(2) Core substance attachment step

The organic-inorganic hybrid particles to which palladium is attached are stirred for 3 minutes in 300 mL of ion-exchanged water. The bell was dispersed to obtain a dispersion. Then, 1 g of a metal nickel particle paste (average particle diameter: 100 nm) was added to the above dispersion liquid for 3 minutes to obtain an organic-inorganic hybrid particle to which a core substance was attached.

(3) Electroless nickel plating step

A nickel layer was formed on the surface of the organic-inorganic hybrid particles in the same manner as in Example 1 to prepare conductive particles. Further, the thickness of the nickel layer was 0.1 μm.

(Example 7)

(1) Production of insulating particles

To a 1000 mL separable flask equipped with four separable caps, stirring blades, three-way cocks, cooling tubes and temperature probes, 100 mmol of methyl methacrylate, N, N, N-trimethyl a monomer composition of 1 mmol of -N-2-methylpropenyloxyethylamine chloride and 1 mmol of 2,2'-azobis(2-amidinopropane) dihydrochloride was obtained as a solid component ratio After weighing into 5 parts by weight of the ion-exchanged water, 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 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% by weight aqueous dispersion of the insulating particles.

10 g of the conductive particles obtained in Example 6 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. After filtering with a 3 μm mesh filter, it was 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 coating layer using insulating particles was formed on the surface of the conductive particles. The coverage area of the insulating particles with respect to the area of 2.5 μm from the center of the conductive particles (that is, the projected area of the particle diameter of the insulating particles) was calculated by image analysis, and as a result, the coverage ratio was 30%.

(Example 8)

Organic-inorganic hybrid particles and conductivity were obtained in the same manner as in Example 1 except that 650 parts by weight of tetraethoxy decane was changed to 550 parts by weight of tetraethoxy decane and 50 parts by weight of methyltrimethoxy decane. particle.

(Example 9)

Organic-inorganic hybrid particles and conductivity were obtained in the same manner as in Example 1 except that 600 parts by weight of tetraethoxy decane was changed to 500 parts by weight of tetraethoxy decane and 100 parts by weight of methyltrimethoxy decane. particle.

(Embodiment 10)

The organic-inorganic hybrid particles and the conductive particles were obtained in the same manner as in Example 1 except that the amount of the addition of the 25% by weight aqueous ammonia solution was changed from 80 parts by weight to 20 parts by weight.

(Example 11)

"Micropearl EYP-0025" (acrylic polymer, average particle size: 2.5 μm) manufactured by Sekisui Chemical Co., Ltd., and replaced by "Micropearl EYP-00375" (acrylic polymer, manufactured by Sekisui Chemical Co., Ltd.). The organic-inorganic hybrid particles and the conductive particles were obtained in the same manner as in Example 1 except that the average particle diameter was 3.75 μm.

(Comparative Example 1)

"Micropearl SI-GH038" (cerium oxide, average particle diameter 3.80 μm) manufactured by Sekisui Chemical Co., Ltd., which is a cerium oxide particle, is a particle (inorganic particle) of Comparative Example 1. Using the particles, conductive particles were obtained in the same manner as in Example 1.

(Comparative Example 2)

"Micropearl ELP-00375" (particle diameter: 3.75 μm) manufactured by Sekisui Chemical Co., Ltd. was used as the particles (organic polymer particles) of Comparative Example 2. Using the particles, conductive particles were obtained in the same manner as in Example 1.

(Comparative Example 3)

1600 parts by weight of ion-exchanged water was placed in a separable flask. 10 parts by weight of a 25 wt% aqueous ammonia solution was added and stirred slowly. On the upper layer, 100 parts by weight of methyltrimethoxydecane was slowly added in such a manner that the interface was good. After the oil-water interface disappeared, 30 parts by weight of a 25 wt% aqueous ammonia solution was added, and the mixture was further stirred for 24 hours. The reaction solution was taken out, and subjected to suction filtration using a membrane filter made of PTFE, and washed twice with ethanol, and then dried by a vacuum dryer at 50 ° C for 24 hours to obtain non-core-shell type organic-inorganic hybrid particles. Conductive particles were obtained in the same manner as in Example 1 using the obtained organic-inorganic hybrid particles.

(Comparative Example 4)

10 parts by weight of toluene was added to 6.5 parts by weight of polyethylene terephthalate, and further 1.42 parts by weight of diphenylmethane diisocyanate was added, and the reaction was carried out at 120 ° C for 5 hours under reflux of toluene. Thereafter, the mixture was cooled to room temperature, and 0.15 parts by weight of ethylenediamine and 0.1 part by weight of an amine-based decane coupling agent ("KBM-9103" manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and the reaction was carried out at 60 ° C for 5 hours. Then, toluene was distilled off under reduced pressure to obtain a polyurethane resin having a hydroxyl group at both terminals and having a urethane bond and a urea bond.

400 parts by weight of the obtained polyurethane resin, 12 parts by weight of iron oxide yellow, and 380 parts by weight of ethyl acetate were mixed to obtain a mixture. The obtained mixture was added dropwise to 2000 parts by weight of a polyvinyl alcohol 0.5% by weight aqueous solution and dispersed to obtain a resin. The resin obtained by filtration through a filter paper was taken out from the water and dried by a vacuum dryer at 50 ° C for 24 hours to obtain a polyurethane microparticle fine particle incorporating a decane coupling agent.

100 parts by weight of the obtained polyurethane microparticles were placed in a 1 L flask, and 75 parts by weight of methanol, 25 parts by weight of water, 2 parts by weight of tetraethoxydecane, and 10 parts by weight of a 25% by weight aqueous ammonia solution were added. The tetraethoxy decane solution was reacted for 2 hours with stirring. After the filtration and washing, the same treatment liquid as the above-mentioned tetraethoxysilane liquid was used again, and the obtained particles were subjected to the same treatment. The reaction solution was taken out, and the membrane filter made of PTFE was used for suction filtration, and the washing was repeated twice with ethanol, and then 50 ° C was used. The air dryer was dried for 24 hours to obtain organic-inorganic hybrid particles. Conductive particles were obtained in the same manner as in Example 1 using the organic-inorganic hybrid particles.

(Comparative Example 5)

The organic-inorganic hybrid particles were obtained in the same manner as in Comparative Example 4 except that the amount of the tetraethoxy decane was changed to 20 parts by weight. Conductive particles were obtained in the same manner as in Example 1 using the organic-inorganic hybrid particles.

(Evaluation)

(1) Content of germanium atoms and carbon atoms in organic and inorganic shells in organic-inorganic hybrid particles (other particles)

The content of the ruthenium atom, the carbon atom, the oxygen atom and the nitrogen atom in the organic nucleus and the inorganic shell in the organic-inorganic hybrid particles was measured by line analysis by the TEM/EDS method. The weight % of each atom in an amount of 100% by weight based on the total of a halogen atom, a carbon atom, an oxygen atom, and a nitrogen atom is defined as a content. Further, in the organic-inorganic hybrid particles in the examples, atoms other than a halogen atom, a carbon atom, an oxygen atom, and a nitrogen atom are not contained in the organic core and the inorganic shell. Further, the content of the ruthenium atom, the carbon atom, the oxygen atom and the nitrogen atom in the other particles was measured.

(2) Particle size of organic-inorganic hybrid particles (other particles), particle size of organic core, and thickness of inorganic shell

Using a scanning electron microscope ("S-3500N" manufactured by Hitachi High-Technologies Co., Ltd.), a particle image of 3000 times was taken for the obtained organic-inorganic hybrid particles (other particles), and particles in the obtained image were obtained by vernier calipers. The particle diameters of 50 were measured, and the number average was determined to determine the particle diameter of the organic-inorganic hybrid particles (other particles).

The particle diameter of the organic nucleus used in the production of the organic-inorganic hybrid particles was also measured by the same method as described above. The thickness of the inorganic shell was determined from the difference between the particle diameter of the organic-inorganic hybrid particles and the particle diameter of the organic core.

(3) The above-mentioned compressive elastic modulus of organic-inorganic hybrid particles (other particles) (10% K value and 30% K value)

The above-mentioned compression elastic modulus (10% K value and 30% K) of the obtained organic-inorganic hybrid particles (other particles) by a micro compression tester (Fischerscope H-100 manufactured by Fischer Co., Ltd.) by the above method Value) The measurement was performed.

(4) The ratio of the number of Q4 atoms (4%) directly bonded to four O-Si groups and directly bonded to four of the above-mentioned -O-Si groups ))

The inorganic shell in the obtained organic-inorganic hybrid particles was analyzed by solid ²⁹ Si NMR spectrum using an NMR spectrum analyzer (JEOL, ECX400) (measurement frequency: 79.4254 MHz, pulse width: 3.7, sample holder) : 8mm, sample rotation number: 7kHz, cumulative number of times: 3600, measurement temperature, 25 ° C, waiting time: 60 seconds) Q4 obtained (direct bonding has 4 -O-Si groups and direct bonding has 4 above) The peak area of the four oxygen atoms in the -O-Si group is Q1~Q3 (1~3 -O-Si groups are directly bonded and 1~3 above-O-Si are directly bonded) Comparing the peak areas of the ruthenium atoms of 1 to 3 oxygen atoms in the base, thereby obtaining 100% of the total number of ruthenium atoms contained in the inorganic shell, and directly bonding 4 -O-Si And the ratio of the number of the argon atoms of the four oxygen atoms of the four -O-Si groups (the ratio of the number of Q4) is directly bonded.

(5) Dispersibility 1

The obtained organic-inorganic hybrid particles (other particles) were used as a spacer for a liquid crystal display element. Further, the evaluation of the dispersibility 1 was not performed on the organic-inorganic hybrid particles obtained in Examples 6 and 7. In the dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, the spacer for a liquid crystal display element is added and stirred in such a manner that the concentration of the solid content component is 2% by weight in the obtained spacer dispersion liquid. Further, a spacer dispersion liquid for a liquid crystal display element was obtained.

The obtained liquid crystal display element spacer dispersion was allowed to stand at 25 ° C for 1 minute. It was observed whether or not the spacer for the liquid crystal display element was precipitated in the dispersion liquid after standing. The dispersibility 1 was determined by the following criteria.

[Determination of Dispersion 1]

○: In the dispersion after the placement, no precipitate of the spacer for the liquid crystal display element was found at the bottom of the container.

×: In the dispersion liquid after standing, the precipitate of the spacer for the liquid crystal display element can be confirmed at the bottom of the container

(6) Dispersibility 2

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), 200 parts by weight of methyl ethyl ketone, and microcapsule type hardening 50 parts by weight of the agent ("HX3941HP" manufactured by Asahi Kasei Chemicals Co., Ltd.) and 2 parts by weight of a decane coupling agent ("SH6040" manufactured by Dow Corning Toray Silicon Co., Ltd.) were mixed, and the obtained conductive particles were 3% by weight. The addition is carried out in a manner and dispersed to obtain a conductive material (resin composition).

The obtained conductive material was allowed to stand at 25 ° C for 1 hour. Whether or not the conductive particles were precipitated in the dispersion after standing was observed. The dispersibility 1 was determined by the following criteria.

[Determination of Dispersion 2]

○: Conductive particles were not precipitated and not agglomerated in the dispersion after standing

×: Conductive particles precipitate or agglomerate in the dispersion after standing

(7) Connection resistance

Production of the connection structure: A resin composition (conductive material) obtained before the evaluation of the above (6) Dispersibility 2 (before standing). The conductive material was allowed to stand at 25 ° C for 1 hour.

The placed conductive material 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 anisotropic conductive film obtained was 12 μm.

The obtained anisotropic conductive film was cut into a size of 5 mm × 5 mm. Will be cut The anisotropic conductive film was attached to the ITO electrode side of a PET substrate (width: 3 cm, length: 3 cm) on which an ITO electrode (height of 0.1 μm, L/S = 20 μm / 20 μm) having a surrounding line for resistance measurement was attached. Basically central. Then, two flexible printed boards (width: 2 cm, length: 1 cm) provided with the same gold electrode were aligned so that the electrodes overlap each other, and then bonded. The laminate of the PET substrate and the two-layer flexible printed substrate 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 is formed on a polyimide film and Au is plated on the surface of the copper electrode is used.

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

[Evaluation criteria for connection resistance]

○○: The connection resistance is 3.0 Ω or less

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

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

×: The connection resistance exceeds 5.0Ω

(8) Insulation reliability

The bonded structure obtained in the evaluation of the above (7) connection resistance was allowed to stand in an environment of 85 ° C and 85% for 100 hours. Thereafter, at 25 points, it was measured whether the adjacent electrodes were in an insulated state or a conductive state. The insulation reliability was determined using the following criteria.

[Determination of insulation reliability]

○○: 25 places between the electrodes in the insulated state

○: There are 20 or more electrodes in the insulated state and less than 25 places.

△: 15 or more electrodes and less than 20 places in the insulated state

×: less than 15 between the electrodes in the insulated state

(9) Adhesion between inorganic shell and conductive layer 1

1.0 g of conductive particles and zirconia balls of 1 mm in diameter (AS ONE) 45 g of the manufactured "YTZ-10" and 17 g of toluene were placed in a 200 mL beaker (inner diameter: 6.7 cm), and stirred at 400 rpm for 6 minutes at 25 ° C using a Sany motor mixer ("BL1200" manufactured by HEIDON Corporation). . Then, the agitated organic-inorganic hybrid particles are each dispersed so that the inorganic shell of the organic-inorganic hybrid particles after stirring does not break. Thereafter, the conductive particles were observed by a scanning electron microscope.

From the above observation, 100 pieces of the conductive particles after stirring were counted, and the number of conductive particles from which the conductive layer was peeled off was found. The adhesion between the inorganic shell and the conductive layer was determined by the following criteria.

[Criteria for judging the adhesion of the inorganic shell to the conductive layer 1]

○: The number of conductive particles in which the conductive layer was peeled off was found to be less than five

△: The number of conductive particles in which the conductive layer was peeled off was found to be 5 or more and less than 10

×: The number of conductive particles in which the conductive layer was peeled off was found to be 10 or more

(10) Adhesion between inorganic shell and conductive layer 2

In the evaluation of the adhesion 1 of the inorganic shell and the conductive layer, the stirring condition of the Sany motor mixer was changed to be stirred at 600 rpm for 12 minutes at 25 ° C, and the inorganic shell and the conductive layer were treated in the same manner. The adhesion 2 was evaluated. The adhesion between the inorganic shell and the conductive layer 2 was determined on the same basis as the criterion for determining the adhesion between the inorganic shell and the conductive layer.

The results are shown in Tables 1 and 2 below. Further, the aspect ratio of the organic-inorganic hybrid particles obtained in Examples 1 to 5 and 8 to 11 was 1.2 or less. In addition, the evaluation results of the connection resistances in Examples 1, 3, 4, 6 to 9, and 11 were all "○", but the connection resistances in Examples 1, 3, 4, 6, 7, 9, and 11 were The value is lower than the value of the connection resistance in the embodiment 8.

Further, the values of the connection resistances in the embodiments 6 and 7 are lower than the values of the connection resistances in the first, third, fourth, ninth, and eleventh embodiments, and the value of the connection resistance in the embodiment 6 is lower than that in the seventh embodiment. The value of the resistor. It can be considered to be affected by the protrusions.

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

Preparation of STN-type liquid crystal display device: In the dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, the solid content component concentration was 2% by weight in 100% by weight of the obtained spacer dispersion liquid. A spacer (organic-inorganic hybrid particle) for a liquid crystal display element of 1 to 5 and 8 to 11 is stirred and a spacer dispersion liquid for a liquid crystal display element is obtained.

An SiO ₂ film was deposited on one surface of a pair of transparent glass plates (length 50 mm, width 50 mm, thickness 0.4 mm) by a CVD method, and then an ITO film was formed on the entire surface of the SiO ₂ film by sputtering. The polyimine alignment film composition (manufactured by Nissan Chemical Co., Ltd., SE3510) was applied onto the obtained glass substrate with an ITO film by a spin coating method, and baked at 280 ° C for 90 minutes to form a polyfluorene. Amine alignment film. After the rubbing treatment is applied to the alignment film, the spacer for the liquid crystal display element is wet-laid so as to be 100 to 200 per 1 mm ^{2 on} the alignment film side of the substrate. After the sealant is formed on the periphery of the other substrate, the substrate and the substrate on which the spacer is dispersed are disposed to face each other with the rubbing direction at 90°, and the two are bonded together. Thereafter, the treatment was carried out at 160 ° C for 90 minutes to harden the sealant to obtain an empty cell (display without liquid crystal injection). In the obtained empty cell, STN-type liquid crystal (manufactured by DIC Corporation) containing a chiral agent was injected, and then the injection port was blocked with a sealant, and then heat-treated at 120 ° C for 30 minutes to obtain an STN-type liquid crystal display device.

In the obtained liquid crystal display device, the spacers for the liquid crystal display devices of Examples 1 to 5 and 8 to 11 were used to favorably control the interval between the substrates. Moreover, the liquid crystal display element exhibits good display quality.

1‧‧‧Electrical particles

2‧‧‧ Conductive layer

11‧‧‧Organic and inorganic mixed particles

12‧‧‧Organic core

13‧‧‧Inorganic shell

Claims (10)

An organic-inorganic hybrid particle comprising an organic core and an inorganic shell disposed on a surface of the organic core, wherein the content of the ruthenium atom contained in the organic nucleus is 10% by weight or less and 100% by weight or more of the organic core The content of the carbon atom contained in the organic nucleus is 50% by weight or more, and the content of the ruthenium atom contained in the inorganic shell is 50% by weight or more and the carbon atom contained in the inorganic shell is 100% by weight of the inorganic shell. The content is 30% by weight or less, and the ratio of the thickness of the inorganic shell to the radius of the organic core is 0.05 or more and 0.70 or less. The organic-inorganic hybrid particle of claim 1, 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 hybrid particle of claim 2, which is used for forming a conductive layer on a surface to obtain conductive particles having the above-mentioned conductive layer. The organic-inorganic hybrid particle according to any one of claims 1 to 3, wherein no chemical bonding is carried out between the organic core and the inorganic shell. The organic-inorganic hybrid particle according to any one of claims 1 to 3, wherein the inorganic shell has a thickness of 50 nm or more and 2000 nm or less. The organic-inorganic hybrid particle according to any one of claims 1 to 3, wherein the organic core has a particle diameter of 0.5 μm or more and 100 μm or less. The organic-inorganic hybrid particle according to any one of claims 1 to 3, wherein 100% of the total number of germanium atoms contained in the inorganic shell is directly bonded with 4 -O-Si groups and directly bonded Proportion of the number of germanium atoms of four oxygen atoms in the above four -O-Si groups More than 50%. An electroconductive particle comprising the organic-inorganic hybrid particle according to any one of claims 1 to 7 and a conductive layer disposed on a surface of the organic-inorganic hybrid particle. A conductive material comprising a conductive particle and a binder resin, wherein the conductive particle comprises the organic-inorganic hybrid particle according to any one of claims 1 to 7, and a conductive layer disposed on a surface of the organic-inorganic hybrid particle . A connection structure 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 a connection between the first connection target member and the second connection target member a connection portion formed of conductive particles or formed of a conductive material containing the conductive particles and a binder resin, and the conductive particles having the organic-inorganic hybrid according to any one of claims 1 to 7. The particles and the conductive layer disposed on the surface of the organic-inorganic hybrid particles, wherein the first electrode and the second electrode are electrically connected to each other by the conductive particles.