TWI612081B - Organic-inorganic hybrid particles, conductive particles, conductive materials, and bonded 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. Moreover, 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. The anisotropic conductive material has conductive particles 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 (FPC), a glass substrate, and a semiconductor wafer to obtain a connection structure. Further, as the conductive particles, conductive particles having resin particles and a conductive layer disposed on the surface of the resin particles may be used.

As an example of the resin particles used for the above-mentioned conductive particles, Patent Document 1 discloses a method for producing a core-shell type organic-inorganic composite particle, which comprises the step (I), which is polymerizable. The organic-based hydrolyzable hydrazine compound is required to be hydrolyzed and condensed to obtain a polymerizable organopolyoxane particle (S1); and the step (II) is carried out to obtain the polymerizable organopolyoxane particle ( S1) polymerization to obtain organic-inorganic composite particles (P1); step (III), adding a polymerizable monomer (M1) to the organic-inorganic composite particles (P1) to obtain organic-inorganic composite particles (P2); And the step (IV) of polymerizing the organic-inorganic composite particles (P2) to obtain core-shell type organic-inorganic composite particles (P3). Further, Patent Document 1 discloses an organic-inorganic composite particle obtained by the method for producing a core-shell type organic-inorganic composite particle.

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

An example of the resin particles used for the conductive particles or the spacer for a liquid crystal display device is disclosed in Patent Document 2 below, in which a polyfunctional decane compound having a polymerizable unsaturated group is used as a surfactant. The organic-inorganic hybrid particles obtained by hydrolysis and polycondensation in the presence of the organic-inorganic hybrid particles. In the above-described polyfunctional decane compound, at least one of the compound represented by the following formula (X) and a derivative thereof, is a first fluorene compound containing a radical polymerizable group.

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

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-229303

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

Regarding the prior organic-inorganic hybrid particles described in Patent Documents 1 and 2, The compression elastic modulus (10% K value) when the organic-inorganic hybrid particles are compressed at 10% is relatively low, or the compression elastic modulus (30% K value) when the organic-inorganic hybrid particles are compressed by 30% is relatively high.

Therefore, when the organic-inorganic hybrid particles are disposed between the substrates as a spacer for a liquid crystal display element, or a conductive layer is formed on the surface and used as a conductive particle to electrically connect the electrodes, the liquid crystal display element is used. The spacer or the conductive particles may not be in sufficient contact with the substrate or the electrode. Further, when an impact is applied to the liquid crystal display element using the spacer for a liquid crystal display device and the connection structure using the conductive particles, the spacer for the liquid crystal display element or the conductive particles do not correspond to the inter-substrate or between the electrodes. The change in the interval is fully deformed. Therefore, there is a problem that the interval between the substrates or between the electrodes is uneven, or the connection between the electrodes is poor.

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic-inorganic hybrid particle having a relatively high compression elastic modulus when compressed at 10%, a relatively low compression elastic modulus at 30% compression, and good compression deformation characteristics. 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.

According to a broad 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, the inorganic shell being formed of alkane oxide, the inorganic shell In the total number of 100% of the ruthenium atoms contained, the ratio of the number of ruthenium atoms directly bonded to the four O-Si groups and the four oxygen atoms of the above four -O-Si groups is directly bonded 50% or more, and the ratio of the compression elastic modulus at the time of compression of 10% to the compression elastic modulus at the time of compression of 30% is 1.3 or more and 10.0 or less.

In a specific aspect of the organic-inorganic hybrid particles of the present invention, the compression elastic modulus at a compression of 10% is 2000 N/mm ² or more, and the compression elastic modulus at a compression of 30% is 5000 N/mm ² or less.

The organic-inorganic hybrid particles of the present invention are preferably used to form a conductive layer on the surface. The conductive particles having the above conductive layer are obtained or used as a spacer for a liquid crystal display element. The organic-inorganic hybrid particles of the present invention preferably form a conductive layer on the surface and are used to obtain conductive particles having the above-mentioned conductive layer.

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

In a 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.

According to a broad 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 particle.

According to a broad aspect of the present invention, there is provided a conductive material comprising conductive particles and a binder resin, wherein the conductive particles comprise the 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 includes: 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 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 include the 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 by the conductive particles.

The organic-inorganic hybrid particle of the present invention has an inorganic shell disposed on the surface of the organic core, and the inorganic shell is formed of alkoxylated decane, and the direct bond is in the total number of 100% of the ruthenium atoms contained in the inorganic shell. The ratio of the number of argon atoms directly bonded to four of the four O-Si groups and four of the above-mentioned -O-Si groups is 50% or more, and the compression elastic modulus at the time of compression of 10% The ratio of the compressive elastic modulus with respect to 30% compression is 1.3 or more and 10.0 Hereinafter, 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 good compression deformation characteristics.

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

Hereinafter, the present invention will be described in detail.

(organic and inorganic mixed particles)

The organic-inorganic hybrid particles of the present invention include 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 inorganic shell is formed of alkoxylated decane, and four -O-Si groups are directly bonded to the total number of ruthenium atoms contained in the inorganic shell. And the ratio of the number of the argon atoms directly bonded to the four oxygen atoms of the four above-mentioned O-Si groups is 50% or more, and the compression elastic modulus when the organic-inorganic hybrid particles are compressed by 10% is compared with the compression The ratio of the compressive elastic modulus at 30% is 1.3 or more and 10.0 or less.

In the organic-inorganic hybrid particles of the present invention, since the above configuration is included, a compression elastic modulus (10% K value) at a compression of 10% is relatively high, and a compression elastic modulus at 30% compression is obtained (30%). K value) relatively low organic-inorganic hybrid particles. In particular, it is possible to suppress the above 30% K value from becoming high and to effectively increase the above 10% K value. The organic-inorganic hybrid particles have a relatively high 10% K value, and the organic-inorganic hybrid particles have a relatively low 30% K value, and the organic-inorganic hybrid particles have good compression deformation characteristics.

The above-mentioned ruthenium atom directly bonded to four -O-Si groups and 4 of the above-mentioned -O-Si groups is directly bonded to the ruthenium atom represented by the arrow A in the following formula (1) . The three groups of four Si bonded to the four -O-Si groups (the groups bonded via the dotted line portion) are not particularly limited.

The above organic-inorganic hybrid particles are preferably obtained by forming a shell of alkoxylated decane by a sol-gel method on the surface of an organic core, thereby sintering the shell, thereby forming an inorganic shell. Thus, the organic-inorganic hybrid particles including the organic core and the inorganic shell disposed on the surface of the organic core can be easily obtained. Further, by preparing the above-described organic-inorganic hybrid particles in this manner, it is extremely easy to satisfy the above configuration. However, the method for producing the organic-inorganic hybrid particles of the present invention is not limited to the method for producing a sintered shell. Even if the sintering step is not carried out, the above configuration can be satisfied by selecting the kind of alkoxylated decane or controlling the hydrolysis and polycondensation conditions of the alkoxylated decane.

The use of the above organic-inorganic hybrid particles is not particularly limited. The above organic-inorganic hybrid particles can be preferably used for various applications requiring a relatively high 10% K value and a relatively low 30% K value. The organic-inorganic hybrid particles are preferably formed by forming a conductive layer on the surface to obtain conductive particles having the above-mentioned conductive layer, or for use as a liquid crystal display element. Spacer. The organic-inorganic hybrid particles of the present invention preferably form a conductive layer on the surface and are used 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. Since the above-mentioned 10% K value of the organic-inorganic hybrid particles is relatively high and the 30% K value is relatively low, the organic-inorganic hybrid particles are disposed between the substrates, or on the surface, as a spacer for a liquid crystal display element. When a conductive layer is formed and used as the conductive particles, and the electrodes are electrically connected to each other, the spacer for the liquid crystal display element or the conductive particles are likely to sufficiently contact the substrate or the electrode. 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 spacer for the liquid crystal display element or the conductive particles easily correspond to the interval between the substrates or between the electrodes. The changes are fully followed and deformed. Therefore, unevenness in the interval between the substrates or between the electrodes is less likely to occur, and connection failure between the electrodes is less likely to occur.

Further, the above organic-inorganic hybrid particles can also be preferably used as 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 organic-inorganic hybrid particles at 10% compressive deformation of the compression elastic modulus (10% K value) is preferably 2000N / mm ² or more, more preferably 3000N / mm ² or more, and further preferably 3300N / mm ² or more, particularly preferably 4000N / mm ² or more, most preferably 4400N / 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 compression elastic modulus (30% K value) when the organic-inorganic hybrid particles are 30% compressed and deformed is preferably 500 N/mm ² or more, more preferably 1000 N/mm ² or more, and still more preferably 1500 N/mm ² or more. particularly preferably 3000N / 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 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) is preferably 1 or more, more preferably 1.3 Further, it is preferably 1.8 or more, more preferably 2.0 or more, and is 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) of the above-mentioned organic-inorganic hybrid particles can be measured in the following manner.

The organic-inorganic hybrid particles were compressed using a micro-compression tester using 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. The load value (N) and the compression displacement (mm) at this time were measured. The above-described compressive elastic modulus can be obtained from the obtained measured values according to the following formula. As the micro compression tester, for example, "Fischerscope H-100" manufactured by Fischer Co., Ltd. or the like can be used.

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 compression-deformed by 10% or 30% (N)

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

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

The above-described 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. As the material for forming the above organic core, various organic substances can be preferably used. As a material for forming the above organic core, for example, a polyolefin resin such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyisobutylene or polybutadiene can be used; Acrylic resin such as methyl acrylate or polymethyl acrylate; polyalkylene terephthalate, polyfluorene, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea A formaldehyde resin and a polymer obtained by polymerizing one or two or more kinds of polymerizable monomers having an ethylenically unsaturated group. It is easy to design and synthesize a material suitable for a conductive material by polymerizing one or two or more kinds of polymerizable monomers having an ethylenically unsaturated group. The organic-inorganic hybrid particles of physical properties at any time of compression.

When the monomer having an ethylenically unsaturated group is polymerized to obtain the above organic nucleus, examples of the monomer having an ethylenically unsaturated group include a non-crosslinkable monomer and a crosslinkable monomer.

Examples of the non-crosslinkable monomer include styrene monomers such as styrene and α-methylstyrene; and carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (methyl) (Methyl methacrylate) such as lauryl acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, or (meth) acrylate Alkyl esters; 2-hydroxyethyl (meth)acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, etc. Acrylates; nitrile-containing monomers such as (meth)acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; vinyl acetate, vinyl butyrate, ethylene laurate Acid esters such as esters and vinyl stearate; unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; trifluoromethyl (meth)acrylate and pentafluoro(meth)acrylate Acetate, vinyl chloride, vinyl fluoride, chlorine-containing monomers such as styrene, halogen or the like.

Examples of the crosslinkable monomer include tetramethylol methane tetra(meth)acrylate, tetramethylol methane tri(meth)acrylate, and tetramethylolmethane di(meth)acrylate. Trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri(meth) acrylate, glycerol di(a) Acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)tetramethylene glycol di(meth)acrylate, 1, Polyfunctional (meth) acrylates such as 4-butanediol di(meth)acrylate; triallyl (iso) cyanurate, triallyl trimellitate, divinylbenzene, phthalic acid Diallyl ester, diallyl acrylamide, diallyl ether, γ-(meth) propylene methoxy propyl trimethoxy decane, trimethoxy a decane-containing monomer such as a nonyl styrene or a vinyl trimethoxy decane.

The organic core can be obtained by polymerizing the above polymerizable monomer having an ethylenically unsaturated group by a known method. As such a method, for example, a method of performing suspension polymerization in the presence of a radical polymerization initiator and a method of swelling and polymerizing a monomer together with a radical polymerization initiator using non-crosslinked particles are exemplified.

The decomposition temperature of the organic core is preferably more than 200 ° C, more preferably more than 250 ° C, more preferably more than 300, from the viewpoint of suppressing deformation of the organic core when the inorganic shell is formed and when the organic-inorganic hybrid particles are used. °C. The decomposition temperature of the above organic core may exceed 400 ° C, may exceed 500 ° C, may exceed 600 ° C, may also 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 element. Use of spacers. 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 between the electrodes by using the conductive particles, the contact area between the conductive particles and the electrode is sufficiently large, and formation is difficult to be formed. Conductive particles agglomerated when the conductive layer is formed. Moreover, the interval between the electrodes connected via the conductive particles does not become excessively large, and the conductive layer is less likely to be peeled 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.

Preferably, the inorganic shell is made of a sol gel by using the surface of the organic core After the alkoxylated decane is formed into a shell, the shell is sintered to form. When the sol-gel method is used, it is easy to arrange a shell on the surface of the organic core. In the case of performing the above sintering, after the organic-inorganic hybrid particles are sintered, the organic core is not removed by volatilization or the like. The organic-inorganic hybrid particles have the organic core after sintering. Further, if the organic nucleus is removed by volatilization or the like after sintering, the 10% K value is relatively low.

Specific examples of the sol-gel method include coexistence of an inorganic monomer such as tetraethoxysilane 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. And a method for performing an interfacial sol reaction; and a method of performing a sol-gel reaction using an inorganic monomer such as tetraethoxy decane coexisting with a solvent such as water or an alcohol and an aqueous ammonia solution, and causing the sol-gel reactant to be heterogeneously aggregated in the organic nucleus Wait. In the above sol-gel method, the alkoxylated alkane is preferably subjected to hydrolysis and polycondensation.

In the above sol-gel method, a surfactant is preferably used. Preferably, the alkoxylated decane 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, the shell is preferably sintered. The degree of crosslinking of the inorganic shell can be adjusted by sintering conditions. Further, by sintering, 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 sintering was not performed. In particular, by increasing the degree of crosslinking, the value of 10% can be sufficiently increased.

The inorganic shell is preferably formed by forming a shell of alkoxylated decane on the surface of the organic core by a sol-gel method and then sintering the shell at 100 ° C or higher (sintering temperature). The sintering temperature is more preferably 150 ° C or higher, and still more preferably 200 ° C or higher. When the sintering temperature is at least the above lower limit, the degree of crosslinking of the inorganic shell becomes more moderate, and the 10% K value and the 30% K value show further preferable values, and the organic-inorganic hybrid particles can be further preferably used for electrical conduction. Use of spacers for particles and liquid crystal display elements.

Preferably, the inorganic shell is obtained by subjecting the alkoxylated decane to a shell by a sol-gel method on the surface of the organic core, and sintering the shell at a temperature below the decomposition temperature of the organic core (sintering temperature). And formed. The sintering temperature is preferably a temperature lower than a decomposition temperature of the organic core by 5 ° C or higher, and more preferably a temperature lower than a decomposition temperature of the organic core by 10 ° C or higher. Further, the sintering temperature is preferably 800 ° C or lower, more preferably 600 ° C or lower, and still more preferably 500 ° C or lower. When the sintering temperature is not more than the above upper limit, thermal deterioration and deformation of the organic core can be suppressed, and organic-inorganic hybrid particles having a value of 10% K and a value of 30% K can be obtained.

The above inorganic shell is formed of alkoxylated decane. The alkoxylated decane may be used singly or in combination of two or more.

The alkoxylated decane is preferably an alkoxydecane 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, 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.

In the case where R1 is an alkyl group having 1 to 30 carbon atoms, specific examples of R1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a n-hexyl group, a cyclohexyl group, and an n-octyl group. And Zheng Qiji. The carbon number of the alkyl group is preferably 10 or less, more preferably 6 or less. Again, the alkane The base 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)acryloxyalkyl 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, 1,2-epoxypropyl group, and 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.

Specific examples of the alkoxylated decane include tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, and ethyl triethoxy hydride. Base decane, isopropyl trimethoxy decane, isobutyl trimethoxy decane, cyclohexyl trimethoxy decane, n-hexyl trimethoxy decane, n-octyl triethoxy decane, n-decyl trimethoxy decane, Phenyltrimethoxydecane, dimethyldimethoxydecane, diisopropyldimethoxydecane, and the like. Alkoxylated decanes other than those may also be used.

The above alkoxylated decane is preferably an alkoxylated decane having a structure in which four oxygen atoms are directly bonded to a ruthenium atom. In the alkoxylated decane, generally four oxygen atoms are bonded to the ruthenium atom by a single bond. The alkoxylated decane preferably contains an alkoxylation represented by the following formula (1Aa) Decane.

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 terms of effectively increasing the value of 10% K and effectively reducing the value of 30%, in the 100% by mole of alkoxydecane used to form the above inorganic shell, the above has 4 oxygen atoms directly bonded to The content of the alkoxylated decane having a structure of a ruthenium atom or the alkoxylated decane represented by the above formula (1Aa) is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more. More preferably, it is 60 mol% or more, and is 100 mol% or less. The total amount of the alkoxylated decane to form the above inorganic shell may be the above alkoxylated decane having a structure in which four oxygen atoms are directly bonded to a ruthenium atom or the alkoxy decane represented by the above formula (1Aa).

In terms of effectively increasing the value of 10% K and effectively reducing the value of 30%, direct bonding is performed in 100% of the total number of germanium atoms derived from the above alkoxylated decane contained in the above inorganic shell. The ratio of the number of the ruthenium atoms having 4 -O-Si groups and 4 of the 4 -O-Si groups directly bonded is preferably 20% or more, more preferably 40% or more, and further Preferably, it is 50% or more, further preferably 55% or more, and particularly preferably 60% or more.

In terms of effectively increasing the value of 10% K and effectively reducing the value of 30%, in the total number of 100% of the germanium atoms contained in the above inorganic shell, there are 4 -O- directly bonded. The ratio of the number of the ruthenium atoms to which the four oxygen atoms of the four above-mentioned -O-Si groups are directly bonded is preferably 55% or more, and more preferably 60% or more.

Further, the ruthenium atom directly bonded to the four -O-Si groups and the four ruthenium atoms of the above four -O-Si groups are directly bonded, for example, in the structure represented by the following formula (11) The atom is specifically a ruthenium atom indicated by an arrow A in the structure represented by the above formula (1).

[Chemical 3]

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

The ratio (the ratio (%) of the number of Q4) of the number of the argon atoms to which the four argon atoms of the four above -O-Si groups are directly bonded is determined as a direct bond. For example, an NMR (Nuclear Magnetic Resonance) spectroscopic analyzer can be used to compare Q4 (four O-Si groups directly bonded and four oxygen atoms in four of the above -O-Si groups) The peak area of the direct bond 矽 atom is directly bonded to Q1~Q3 (1~3 -O-Si groups are directly bonded and 1~3 oxygen atoms in 1~3 above-O-Si groups are directly bonded) The method of the peak area of the atom. According to this method, it is possible to determine that the total number of ruthenium atoms contained in the inorganic shell is 100%, and four -O-Si groups are directly bonded and four of the four above-mentioned -O-Si groups are bonded. The ratio of the number of 矽 atoms directly bonded by a ruthenium atom (the ratio of the number of Q4). Further, in the NMR measurement results of the ratio of the number of Q4 obtained in the following examples, 4 of the above-mentioned -O-Si groups derived from the direct bonding were 4 -O-Si groups. The peak of the ruthenium atom directly bonded by the ruthenium atom was 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 element. Use of spacers. The thickness of the above inorganic shell is the average thickness per one organic-inorganic hybrid particle. The thickness of the above inorganic shell can be controlled by the control of the sol-gel method.

In order to thicken the above inorganic shell, it is preferred to control the amount of water added in the sol-gel reaction. The amount of water added is preferably 20 parts by weight or less based on 1 part by weight of the organic core. The amount of the water added is more preferably 15 parts by weight or less, further preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less. When the amount of water added is not more than the above upper limit, the inorganic shell can be appropriately thickened in the sol-gel reaction.

In order to thicken the above inorganic shell, it is preferred to use a polar solvent in the sol-gel reaction. The above polar solvent is preferably an alcohol solvent or acetonitrile, and more preferably isopropanol or acetonitrile. The inorganic shell can be appropriately thickened by using the above polar solvent.

In the present invention, the thickness of the inorganic shell can be determined by observing the organic-inorganic hybrid particles using a scanning electron microscope, and the average particle size and the organic core are determined by using a vernier caliper to measure the particle diameters of arbitrarily selected 50 organic-inorganic hybrid particles. The difference between the average values of the particle diameters was obtained. The particle diameter of the organic-inorganic hybrid particle means a diameter when the organic-inorganic hybrid particle is a true spherical shape, and means a maximum diameter when the organic-inorganic hybrid particle has 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.

(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.

In Fig. 1, the conductive particles of the first embodiment of the present invention are shown in cross section.

The conductive particles 1 shown in FIG. 1 include organic-inorganic hybrid particles 11 and a conductive layer 2 disposed on the surface of the organic-inorganic hybrid particles 11. The conductive layer 2 covers the surface of the organic-inorganic hybrid particles 11. 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 inorganic shell 13 On the surface. The conductive layer 2 covers the surface of the inorganic shell 13.

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

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 buried 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 surface of the conductive layer 32 is embossed by a plurality of core materials 33 to form protrusions 31a and 32a.

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 by the insulating material 34. The insulating material 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, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, ruthenium, osmium, iridium, osmium, cadmium, osmium, and the like. Alloys, etc. Again, as the above gold The genus includes tin-doped indium oxide (ITO, Indium Tin Oxide), solder, and the like. Among them, since the connection resistance between the electrodes can be further reduced, 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 shown by the conductive particles 1 and 31. The conductive layer may be formed of a plurality of layers as indicated by 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 for forming the conductive layer include a method using electroless plating, a method using electrolytic plating, a method using physical vapor deposition, and applying a metal powder or a slurry containing a metal powder and a binder to an organic layer. A method of inorganizing the surface of the particles, and the like. Among them, since it is simple to form a conductive layer, it is preferable to use a method of electroless plating. Examples of the method using physical vapor deposition include vacuum deposition, ion plating, and ion sputtering.

The particle diameter of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, and is preferably 520 μm or less, more preferably 500 μm or less, further preferably 100 μm or less, further 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 large, and it is difficult to form the conductive layer. Conductive particles agglomerated at the time. Moreover, the interval between the electrodes connected via the conductive particles does not become excessively large, and the conductive layer is less likely to be peeled off from the surface of the organic-inorganic hybrid particles. In addition, 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 is intended to be straight when the conductive particles are in a true spherical shape. The diameter means a maximum diameter when the conductive particles are in 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, still more preferably 0.3 μm or less. In the case where the conductive layer is a plurality of layers, the thickness of the conductive layer is the thickness of the entire conductive layer. 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 can be 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, by disposing the conductive particles between the electrodes and performing pressure bonding, the oxide film can be 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 reduced. Further, when the conductive particles have an insulating material on the surface or when the conductive particles are dispersed in the binder resin and used as a conductive material, the protrusions of the conductive particles can be effectively excluded. An insulating substance or a binder resin between the conductive particles and the electrode. Therefore, the conduction reliability between the electrodes can be improved.

As a method of forming a protrusion on the surface of the above-mentioned conductive particles, a core is exemplified. a method in which a substance adheres to a surface of an organic-inorganic hybrid particle, and a conductive layer is formed by electroless plating; and a conductive layer is formed on the surface of the organic-inorganic hybrid particle by electroless plating, and then the core material is adhered, and electroless plating is further utilized. A method of forming a conductive layer or the like. Further, the above-described core material may not be used to form protrusions.

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, since an insulating material is present between the plurality of electrodes, it is possible to prevent short-circuiting between the electrodes adjacent in the lateral direction and not between the electrodes in the upper and lower directions. Further, when the electrodes are connected, the insulating particles between the conductive layers of the conductive particles and the electrodes can be easily removed by pressurizing the conductive particles by the two electrodes. When the conductive particles have protrusions on the surface of the conductive layer, the insulating material between the conductive layer of the conductive particles and the electrode can be further easily removed. The insulating material is preferably an insulating resin layer or insulating particles. The insulating particles are preferably insulating resin particles.

(conductive material)

The conductive material includes the conductive particles and the binder resin. The conductive particles are preferably dispersed in a binder resin and used as a conductive material. The conductive material is preferably an anisotropic conductive material.

The above binder resin is not particularly limited. A known insulating resin can be used as the above binder resin. Examples of the binder resin include a vinyl resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer, and an elastomer. The binder resin may be used alone or in combination of two or more.

Examples of the vinyl resin include 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 resin. Polyester resin, etc. Further, the curable resin may be a room temperature curing resin, a thermosetting resin, a photocurable resin, or a moisture curing resin. The above curable resin can be used in combination with a hardener. 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 block. a hydride of a segment 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. In the method of dispersing the above-mentioned conductive particles in the above-mentioned binder resin, for example, a method in which the conductive particles are added to the binder resin and then kneaded by a planetary mixer or the like is 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, and kneaded by a planetary mixer or the like, and dispersed; and water or an organic solvent is used. After the above-mentioned binder resin is diluted, the conductive particles are added and kneaded by a planetary mixer or the like to be dispersed.

The above conductive material may be used in the form of a conductive paste, a conductive film, or the like. When the conductive material of the present invention is used in the form of a film-like adhesive such as a conductive film, it may be a film-form adhesive which does not contain conductive particles in a film-form adhesive layer containing the conductive particles. The above conductive paste is preferably an anisotropic conductive paste. The above conductive film is preferably an anisotropic conductive film.

The content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, and still more preferably 50% by weight or more, based on 100% by weight of the conductive material. It is preferably 70% by weight or more, and preferably 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 is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and preferably 40% by weight or less, more preferably 20% by weight or less, based on 100% by weight of the conductive material. It is preferably 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-mentioned conductive particles or by connecting the connection target member using the above-described conductive material containing the conductive particles and the binder resin.

Preferably, the connection structure includes a first connection target member, a second connection target member, and a connection portion that connects the first connection target member and the second connection target member, and the connection portion is formed of the conductive particles, or It is formed of the above-mentioned conductive material containing a conductive particle 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 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 51 shown in FIG. 4 includes a first connection object member 52, a second connection object member 53, and a connection portion that connects the first connection object member 52 and the second connection object member 53. 54. 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 shown in a schematic view for convenience of illustration. Instead of 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 by one or a plurality of conductive particles 1. Therefore, the first and second connection target 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 for pressing the electrode of 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 epoxy substrate, and a circuit board such as a glass substrate. The conductive material is preferably a conductive material for connecting electronic parts. It is preferable that the conductive paste is a paste-like conductive material and is applied to the connection member in a paste state.

The conductive particles and the conductive material described above can also be preferably used for a touch panel. Therefore, the connection target member is preferably a flexible printed circuit board or a connection target member in which an electrode is disposed on the surface of the resin film. The connection target member is preferably a flexible printed circuit board, and is preferably a connection target member in which an electrode is disposed on the surface of the resin film. The above flexible printed substrate generally 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. Above When the connection target member is a flexible printed substrate, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode or a copper electrode. In the case where the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode or a tungsten electrode. Further, in the case where the electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode having an aluminum layer on a surface layer of the metal oxide layer. Examples of the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, Ga, and the like.

Further, the above organic-inorganic hybrid particles can be preferably used as a separator for a liquid crystal display element. That is, the organic-inorganic hybrid particles can be preferably used to obtain a liquid crystal display element comprising: a pair of substrates constituting the liquid crystal cell, a liquid crystal sealed between the pair of substrates, and a pair of substrates disposed on the pair of substrates A spacer for a liquid crystal display element.

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

The liquid crystal display element 81 shown in FIG. 5 has a pair of transparent glass substrates 82. The transparent glass substrate 82 has an insulating film (not shown) on the opposite surface. Examples of the material of the insulating film include SiO ₂ and the like. A transparent electrode 83 is formed on the insulating film in the transparent glass substrate 82. As a material of the transparent electrode 83, ITO etc. are mentioned. The transparent electrode 83 can be formed, for example, by patterning by a photolithography method. 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. The interval between the pair of transparent glass substrates 82 is controlled by a plurality of organic-inorganic hybrid particles 11. A sealant 86 is disposed between the edges of the pair of transparent glass substrates 82. The liquid crystal 85 is prevented from flowing out to the outside by the sealant 86.

The arrangement density of the spacer for liquid crystal display elements per 1 mm ² in the liquid crystal display element is preferably 10/mm ² or more, and preferably 1000 / mm ² or less. If the above arrangement density is 10 pieces/mm ² or more, the cell gap becomes more uniform. When the above arrangement density is 1000/mm ² or less, the contrast of the liquid crystal display element becomes more favorable.

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

(Example 1) (1) Production of organic-inorganic hybrid particles

"Micropearl EX-0041" (particle size 4.1 μm) manufactured by Sekisui Chemical Industry Co., Ltd. was prepared as an organic core. 1 part by weight of the organic core, 0.4 parts by weight of cetyl ammonium bromide as a surfactant, and 0.8 part by weight of a 25 wt% aqueous ammonia solution were suspended in 18 parts by weight of ethanol (EtOH) and 2 parts by weight of water. A suspension is obtained. To the obtained suspension, 3 parts by weight of tetraethoxy decane was added, and tetraethoxy decane was formed into a shell on the surface of the above organic nucleus by a sol-gel method to obtain pre-sintered particles.

The obtained pre-sintered particles were heated in a sintering furnace at 250 ° C (sintering temperature) for 1 hour under a nitrogen atmosphere, and the shell was sintered to form an inorganic shell to obtain organic-inorganic hybrid particles.

(Example 2)

The organic-inorganic hybrid particles were obtained in the same manner as in Example 1 except that the sintering temperature was changed to 300 °C.

(Examples 3 and 4)

The organic core was changed to "Micropearl ELP-00375" (particle diameter 3.75 μm) manufactured by Sekisui Chemical Co., Ltd., and the amount of tetraethoxy decane was changed as shown in Table 1 below, and sintering was not performed. The organic-inorganic hybrid particles were obtained in the same manner as in Example 1 except for the same.

(Example 5)

"Micropearl EX-00375" (particle size 3.75 μm) manufactured by Sekisui Chemical Industry Co., Ltd. was prepared as an organic core. 1 part by weight of the above organic core, 10 as a surfactant 0.4 parts by weight of hexaalkylammonium bromide and 1.6 parts by weight of a 25% by weight aqueous ammonia solution were suspended in 18 parts by weight of acetonitrile (AN, acetonitrile) and 2 parts by weight of water to obtain a suspension. 6 parts by weight of tetraethoxy decane was added to the obtained suspension, and tetraethoxy decane was formed into a shell on the surface of the above organic nucleus by a sol-gel method to obtain organic-inorganic hybrid particles.

(Example 6)

The organic-inorganic hybrid particles were obtained in the same manner as in Example 5 except that the amount of the tetraethoxy decane was changed to 3 parts by weight.

(Example 7)

The organic-inorganic hybrid particles were obtained in the same manner as in Example 1 except that 18 parts by weight of ethanol was changed to 18 parts by weight of isopropyl alcohol (IPA).

(Example 8)

The organic-inorganic hybrid particles were obtained in the same manner as in Example 7 except that the sintering temperature was changed to 300 °C.

(Examples 9, 10)

The organic core was changed to "Micropearl ELP-00375" (particle diameter 3.75 μm) manufactured by Sekisui Chemical Co., Ltd., and the amount of tetraethoxy decane was changed as shown in Table 1 below, and sintering was not performed. The organic-inorganic hybrid particles were obtained in the same manner as in Example 7 except for the same.

(Comparative Example 1)

The organic-inorganic hybrid particles were obtained in the same manner as in Example 1 except that sintering was not performed. In Comparative Example 1, an inorganic shell as the above shell was formed.

(Comparative Example 2)

"Micropearl EX-0041" (particle diameter 4.1 μm) manufactured by Sekisui Chemical Co., Ltd. was used as the particles (organic particles) of Comparative Example 2.

(Comparative Example 3)

"Micropearl ELP-00375" (particle diameter 3.75 μm) manufactured by Sekisui Chemical Co., Ltd. was used as the particles (organic particles) of Comparative Example 3.

(Comparative Example 4)

The organic-inorganic hybrid particles were obtained in the same manner as in Example 1 except that the sintering temperature was changed to 350 °C. In Comparative Example 4, the organic nucleus was decomposed by sintering, and particles (inorganic particles) substantially formed only of an inorganic shell were obtained.

(Comparative Example 5)

"SI-GH038" (particle diameter: 3.8 μm) manufactured by Sekisui Chemical Co., Ltd. was used as the particles (inorganic particles) of Comparative Example 5.

(Comparative Example 6)

50 g of γ-methyl propylene methoxy propyl methyl dimethoxy decane, 10 g of tetraethoxy decane, 2, 2'- was added dropwise to a mixture containing 5 g of a 25% aqueous ammonia solution and 300 g of pure water. A mixture of 0.25 g of azobis(2,4-dimethylvaleronitrile) and 100 g of methanol was stirred for 1 hour. Next, 32 g of a 10% aqueous solution of polyoxyethylene alkylphenyl ether sulfate was added, and after radical polymerization at 75 ° C, the mixture was cooled to obtain organic-inorganic hybrid particles (particle diameter: 4.1 μm). The obtained organic-inorganic hybrid particles were designated as particles of Comparative Example 6.

(Comparative Example 7)

"Micropearl ELP-00375" (particle size 3.75 μm) manufactured by Sekisui Chemical Industry Co., Ltd. was prepared as an organic core. 1 part by weight of the above organic core, 0.4 parts by weight of cetyl ammonium bromide as a surfactant, and 0.8 part by weight of a 25 wt% aqueous ammonia solution were suspended in 18 parts by weight of ethanol and 2 parts by weight of water to obtain a suspension. . 6 parts by weight of tetraethoxy decane was added to the obtained suspension, and tetraethoxy decane was formed into a shell on the surface of the above organic nucleus by a sol-gel method to obtain organic-inorganic hybrid particles.

(Comparative Example 8)

The organic-inorganic hybrid particles were obtained in the same manner as in Comparative Example 7, except that the amount of water added was changed to 25 parts by weight.

(Comparative Example 9)

"Micropearl ELP-00375" (particle size 3.75 μm) manufactured by Sekisui Chemical Industry Co., Ltd. was prepared as an organic core. 1 part by weight of the above organic core, 0.4 parts by weight of cetyl ammonium bromide as a surfactant, and 0.2 part by weight of a 25% by weight aqueous ammonia solution were suspended in 18 parts by weight of acetonitrile and 2 parts by weight of water to obtain a suspension. . To the obtained suspension, 3 parts by weight of tetraethoxy decane was added, and tetraethoxy decane was formed into a shell on the surface of the above organic nucleus by a sol-gel method to obtain an organic-inorganic hybrid particle.

(Comparative Example 10)

"Micropearl ELP-00375" (particle size 3.75 μm) manufactured by Sekisui Chemical Industry Co., Ltd. was prepared as an organic core. 1 part by weight of the above organic core and 0.1 part by weight of a 25% by weight aqueous ammonia solution were suspended in 0.75 parts by weight of ethanol and 0.025 parts by weight of water to obtain a suspension. 0.02 parts by weight of tetraethoxy decane was added to the obtained suspension, and tetraethoxy decane was formed into a shell on the surface of the above organic nucleus by a sol-gel method to obtain organic-inorganic hybrid particles.

(Comparative Example 11)

The organic-inorganic hybrid particles were obtained in the same manner as in Example 7 except that sintering was not performed. In Comparative Example 1, an inorganic shell as the above shell was formed.

(Comparative Example 12)

The organic-inorganic hybrid particles were obtained in the same manner as in Example 7 except that the sintering temperature was changed to 350 °C. In Comparative Example 4, the organic nucleus was decomposed by sintering, and particles (inorganic particles) substantially formed only of an inorganic shell were obtained.

(Evaluation) (1) The above-mentioned compression elastic modulus of organic-inorganic hybrid particles, organic particles and inorganic particles (10% K value and 30% K value)

The above-mentioned method was used to measure the above-mentioned compressive elastic modulus (10% K value and the obtained organic-inorganic hybrid particles, obtained organic particles, and inorganic particles using a micro compression tester (Fischerscope H-100 manufactured by Fischer). 30% K value). Further, the 30% K value of the inorganic particles of Comparative Example 5 could not be measured because the inorganic particles were hard (substantially 30% K value exceeded 5000 mN/mm ² ).

(2) Ratio of the number of 矽 atoms directly bonded to four O-Si groups and four oxygen atoms of the above-mentioned -O-Si groups (the ratio of the number of Q4 (%) )

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

(3) Thickness of inorganic shell

Each of the particles of the examples and the comparative examples was imaged by a scanning electron microscope ("S-3500N" manufactured by Hitachi High-Technologie Co., Ltd.), and 50 particles in the obtained image were measured using a vernier caliper. The particle diameter was determined to be an average number of particles (1).

The particle diameter (particle diameter (2): see Table 1) was also measured by the same method as described above for the preparation of the core particles used in the preparation of the particles of the examples and the comparative examples. The difference between the particle diameter (1) and the particle diameter (2) is defined as the thickness of the inorganic shell.

(4) Connection resistance (1)

Production of conductive particles:

The organic and inorganic mixed particles of the obtained examples and comparative examples were washed and dried. Thereafter, 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.

Production of the connection structure:

10 parts by weight of bisphenol A type epoxy resin ("Epikote 1009" manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight: about 800,000), 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 Silicone Co., Ltd.) were added, and conductive particles were added so as to have a content of 3% by weight. It is dispersed to obtain a resin composition.

The obtained resin composition was applied to a PET (polyethylene terephthalate) film having a thickness of 50 μm which was subjected to release treatment on one side, and dried by hot air at 70 ° C for 5 minutes to produce an anisotropic direction. 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. The ITO electrode of a PET substrate (width: 3 cm, length: 3 cm) provided with ITO (height: 0.1 μm, L/S = 20 μm / 20 μm) having a conductive wire for electric resistance measurement was adhered to one of the anisotropic conductive films after the cutting. The approximate center of the side. Next, 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 (1). Further, a copper electrode was formed on the polyimide film, and the surface of the copper electrode was plated with a two-layer flexible printed substrate of Au.

The connection resistance between the opposing electrodes of the obtained connection structure (1) was measured by a four-terminal method. The connection resistance (1) was determined on the basis of the following criteria.

[Evaluation criteria for connection resistance (1)]

○: The connection resistance is 5 Ω or less

×: The connection resistance exceeds 5.0Ω

The results are shown in Table 1 below. Further, the aspect ratio of the organic-inorganic hybrid particles obtained in Examples 1 to 10 was 1.2 or less.

(5) Connection resistance (2)

In the evaluation of the connection resistance (1) of the above (4), the connection structure of the PET substrate and the two-layer flexible printed circuit board was changed to 7 N, 180 ° C, and 20 seconds, and the connection structure was obtained in the same manner. (2). The connection resistance between the opposing electrodes of the obtained connection structure (2) was measured by a four-terminal method. The connection resistance (2) was determined on the basis of the following criteria.

[Evaluation criteria for connection resistance (2)]

○: The connection resistance is 5 Ω or less

×: The connection resistance exceeds 5.0Ω

In addition, in the evaluation of the connection resistance (1), the evaluation results of Examples 1 to 10 and Comparative Examples 1 to 4, 11, and 12 were all "○". However, the connection resistances in Examples 1 to 10 were lower than those in Comparative Examples 1 to 4, 11, and 12. Further, in the evaluation of the connection resistance (2), the pressure of the pressure bonding condition was made lower than the evaluation of the connection resistance (1). It was confirmed that even if the pressure was low, the connection resistance was effectively lowered by using the organic-inorganic hybrid particles of Examples 1 to 10.

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

Production of STN (Super Twisted Nematic) type liquid crystal display element: The organic-inorganic hybrid particles of Examples 1 to 10 were used as spacers for liquid crystal display elements. The liquid crystal display of Examples 1 to 10 was added so as to have a solid content concentration of 2% by weight in 100% by weight of the obtained spacer dispersion in a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water. The element spacer (organic-inorganic hybrid particle) was stirred and stirred to obtain a spacer dispersion liquid for a liquid crystal display element.

On the surface of a pair of transparent glass plates (length 50 mm, width 50 mm, thickness 0.4 mm), the SiO ₂ film is deposited by CVD (Chemical Vapor Deposition), and then sputtered on the surface of the SiO ₂ film. The ITO film is integrally formed. The polyimine alignment film composition (manufactured by Nissan Chemical Co., Ltd., SE3510) was coated on the obtained ITO film-attached glass substrate by a spin coating method, and baked at 280 ° C for 90 minutes, thereby forming a polyimine. Orientation 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 interposed are disposed to face each other with the rubbing direction at 90°, and the two are bonded together. Thereafter, the sealant was hardened by treating at 160 ° C for 90 minutes to obtain an empty cell (a screen not filled with a liquid crystal). An STN liquid crystal (manufactured by DIC Corporation) containing a chiral agent was injected into the obtained empty cell, and then the injection port was sealed with a sealant, and then heat-treated at 120 ° C for 30 minutes to obtain an STN liquid crystal display device.

In the obtained liquid crystal display device, the interval between the substrates was favorably controlled by the spacers for liquid crystal display elements of Examples 1 to 10. 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 (11)

An organic-inorganic hybrid particle comprising an organic core and an inorganic shell disposed on a surface of the organic core, wherein the inorganic shell is formed of alkoxylated decane, and the total number of germanium atoms contained in the inorganic shell is 100 In %, the ratio of the number of germanium atoms directly bonded to four -O-Si groups and the four oxygen atoms of the four above-mentioned -O-Si groups is 50% or more, and when the compression is 10% The ratio of the compression elastic modulus to the compression elastic modulus at 30% compression is 1.3 or more and 10.0 or less. The organic-inorganic hybrid particle of claim 1, wherein the compression elastic modulus at a compression of 10% is 2000 N/mm ² or more, and the compression elastic modulus at a compression of 30% is 5000 N/mm ² or less. The organic-inorganic hybrid particle of claim 1, which forms a conductive layer on the 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 3, which forms a conductive layer on the surface for obtaining conductive particles having the above-mentioned conductive layer. The organic-inorganic hybrid particle of claim 2, which forms a conductive layer on the 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 5, which forms a conductive layer on the surface for obtaining conductive particles having the above-mentioned conductive layer. The organic-inorganic hybrid particle according to any one of claims 1 to 6, 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 6, wherein the organic core has a particle diameter of 0.5 μm or more and 100 μm or less. A conductive particle comprising the organic-inorganic hybrid particle according to any one of claims 1 to 8, and a conductive layer disposed on a surface of the organic-inorganic hybrid particle. A 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 8, and the conductive layer disposed on a surface of the organic-inorganic hybrid particle Floor. A connection structure comprising: 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 The connection portion is formed of conductive particles or formed of a conductive material containing the conductive particles and a binder resin, and the conductive particles include the organic-inorganic hybrid according to any one of claims 1 to 8. 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 by the conductive particles.