JP6266973B2 - Organic-inorganic hybrid particles, conductive particles, conductive materials, and connection structures - Google Patents

Description

  The present invention relates to a core-shell type organic-inorganic hybrid particle comprising an organic core and an inorganic shell disposed on the surface of the organic core. The present invention also relates to conductive particles, conductive materials and connection structures using the organic-inorganic hybrid particles.

  Anisotropic conductive materials such as anisotropic conductive pastes and anisotropic conductive films are widely known. In the anisotropic conductive material, conductive particles are dispersed in a binder resin.

  The anisotropic conductive material is used to electrically connect electrodes of various connection target members such as a flexible printed circuit (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure. ing. Moreover, as the conductive particles, conductive particles having base particles and a conductive layer disposed on the surface of the base particles may be used.

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

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

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

  In said formula (X), R1 shows a hydrogen atom or a methyl group, R2 shows the C1-C20 bivalent organic group which may have a substituent, R3 is C1-C5 R 4 represents an alkyl group or a phenyl group, and R 4 represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.

JP 2006-156068 A JP 2000-204119 A

  As described in Patent Document 2, the organic-inorganic hybrid particles have high heat resistance, and have the property that the hardness of the organic-inorganic hybrid particles is difficult to decrease even when exposed to high temperatures. However, because the composition and structure inside the particles are uniform, the compression characteristics are uniform with respect to strain. For example, organic / inorganic hybrid particles generally have such properties as being hard even when strain is small but hard when strain is large, soft when strain is small and soft when strain is large. For this reason, when the organic-inorganic hybrid particle is used as a spacer for a liquid crystal display element and disposed between the substrates to obtain a liquid crystal display element, a sufficient contact area between the liquid crystal display element spacer and the substrate cannot be secured. In addition, when conductive particles having a conductive layer formed on the surface of the organic-inorganic hybrid particles are used to obtain a connection structure by electrically connecting the electrodes, the conductive particles are sufficiently stuck into the electrodes. In addition, there is a problem that the connection resistance is increased without obtaining a sufficient amount of deformation.

  As described in Patent Document 1, in the conventional organic-inorganic hybrid particles in which the organic polymer is the core and the inorganic compound is the shell, the compression characteristics are different between when the distortion is small and when the compression characteristic is small by using the core-shell structure. Is trying to get. However, since the shell film is very thin, substantially only the characteristics of the organic polymer as the core are exhibited. That is, the organic-inorganic hybrid particles are flexible regardless of the magnitude of strain. Further, for the same reason, heat resistance cannot be obtained. As a result, when an organic-inorganic hybrid particle having such a core-shell structure is used as a spacer for a liquid crystal display element and disposed between the substrates to obtain a liquid crystal display element, the liquid crystal display element spacer is in sufficient contact with the substrate. Without sufficient contact area. In addition, when using conductive particles having a conductive layer formed on the surface of the organic-inorganic hybrid particles to obtain a connection structure by electrically connecting the electrodes, the high temperature when obtaining the connection structure, There are problems that the particles cannot withstand, the compression properties deteriorate, and the connection resistance increases.

  Thus, the heat resistance of the conventional organic-inorganic hybrid particles as described in Patent Literatures 1 and 2 is low, and when exposed to high temperatures, the flexibility of the organic-inorganic hybrid particles may be reduced. When the organic-inorganic hybrid particles are exposed to a high temperature and then the liquid crystal display element spacer and the conductive particles are used, the display quality of the obtained liquid crystal display element is deteriorated, or between the electrodes in the obtained connection structure. Connection resistance becomes high.

  Furthermore, the spacer for liquid crystal display elements and the conductive particles may be exposed to a high temperature not only during the manufacture of the liquid crystal display element and the connection structure but also after the manufacture. This also reduces the display quality in the obtained liquid crystal display element, and increases the connection resistance between the electrodes in the obtained connection structure.

  In recent years, the distance between electrodes connected by conductive particles has become narrower. In addition, when the electrodes having a small interval are electrically connected by conventional conductive particles as described in Patent Documents 1 and 2, a large problem is that the connection resistance is increased.

  An object of the present invention is to provide organic-inorganic hybrid particles that can maintain good compression deformation characteristics even when exposed to high temperatures, and conductive particles, conductive materials, and connection structures using the organic-inorganic hybrid particles. It is.

  A limited object of the present invention is to provide organic-inorganic hybrid particles capable of effectively reducing the connection resistance when the electrodes are electrically connected. Another object of the present invention is to provide conductive particles, conductive materials, and connection structures using the organic-inorganic hybrid particles.

  According to a wide aspect of the present invention, an organic core and an inorganic shell disposed on the surface of the organic core are provided, and when the weight of the organic-inorganic hybrid particles at 100 ° C. is 100% by weight, 100 ° C. The organic-inorganic hybrid particles have a weight of 85% by weight or more when the temperature is increased from 300 to 300 ° C. at 10 ° C./min and reaches 300 ° C., and the ratio of the thickness of the inorganic shell to the radius of the organic core is Organic-inorganic hybrid particles having a particle size of 0.05 to 0.70 are provided.

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

  In a specific aspect of the organic-inorganic hybrid particle according to the present invention, no chemical bond is formed between the organic core and the inorganic shell.

  On the specific situation with the organic-inorganic hybrid particle | grains which concern on this invention, the thickness of the said inorganic shell is 50 nm or more and 2000 nm or less.

  On the specific situation with the organic-inorganic hybrid particle | grains which concern on this invention, the particle size of the said organic core is 0.5 micrometer or more and 100 micrometers or less.

In a specific aspect of the organic-inorganic hybrid particle according to the present invention, the compression elastic modulus when compressed by 10% is 5000 N / mm ² or more.

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

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

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

  In the organic-inorganic hybrid particles according to the present invention, an inorganic shell is disposed on the surface of the organic core, and when the weight of the organic-inorganic hybrid particles at 100 ° C. is 100% by weight, from 100 ° C. to 300 ° C. The organic / inorganic hybrid particles have a weight of 85% by weight or more when heated to 10 ° C./min and reach 300 ° C., and the ratio of the thickness of the inorganic shell to the radius of the organic core is 0.05. Since it is above and below 0.70, even if it exposes to high temperature, a favorable compression deformation characteristic can be maintained.

FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention. FIG. 3 is a cross-sectional view showing conductive particles according to the 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 the organic-inorganic hybrid particles according to one embodiment of the present invention as a spacer for a liquid crystal display element.

  Details of the present invention will be described below.

(Organic inorganic hybrid particles)
The organic-inorganic hybrid particle according to the present invention includes an organic core and an inorganic shell disposed on the surface of the organic core. In the organic-inorganic hybrid particles according to the present invention, when the weight of the organic-inorganic hybrid particles at 100 ° C. was 100% by weight, the temperature was increased from 100 ° C. to 300 ° C. at 10 ° C./min and reached 300 ° C. The weight of the organic / inorganic hybrid particles is 85% by weight or more. That is, with respect to the organic-inorganic hybrid particles at 100 ° C., the pyrolysis residue after heating to 300 ° C. is 85% by weight or more. The temperature is increased from 100 ° C. to 300 ° C. at a rate of 10 ° C./min, and the weight of the organic-inorganic hybrid particles after heating when reaching 300 ° C. is generally 100% by weight or less. The organic / inorganic hybrid particles at 100 ° C. are organic / inorganic hybrid particles when the temperature is increased from 23 ° C. to 100 ° C. at 10 ° C./min and reaches 100 ° C. In order to obtain organic / inorganic hybrid particles at 300 ° C., the organic / inorganic hybrid particles at 100 ° C. are used.

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

  In the organic-inorganic hybrid particle according to the present invention, since the inorganic shell is disposed on the surface of the organic core, the flexibility of the organic-inorganic hybrid particle is enhanced by the core being the organic core, particularly in the core-shell type particle. be able to. For this reason, the organic-inorganic hybrid particles are used as spacers for liquid crystal display elements, and are arranged between substrates, or the electrodes are electrically connected using conductive particles in which a conductive layer is formed on the surface of the organic-inorganic hybrid particles. In such a case, the spacer for liquid crystal display element or the conductive particles is efficiently arranged between the substrates or between the electrodes. Furthermore, the contact area between the spacer for liquid crystal display element or conductive particles and the substrate or electrode can be increased. For this reason, the display quality in a liquid crystal display element becomes favorable, and also the connection resistance between electrodes becomes low.

  Furthermore, in the organic-inorganic hybrid particles according to the present invention, an inorganic shell is disposed on the surface of the organic core, and the weight of the organic-inorganic hybrid particles after heating in the heating test described above is 85% by weight or more, and Since 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 flexibility can be maintained well even when the organic-inorganic hybrid particles are exposed to a high temperature. For this reason, even if the organic-inorganic hybrid particles exposed to a high temperature are used, the display quality in the liquid crystal display element is improved and the connection resistance between the electrodes is further reduced. Furthermore, even when a liquid crystal display element using spacers for liquid crystal display elements and a connection structure using conductive particles are exposed to high temperatures, good display quality in the liquid crystal display element can be maintained, and the connection resistance between the electrodes can be maintained. Can be kept low.

  In the heating test described above, a TG / DTA apparatus can be used to measure the weight change of the organic-inorganic hybrid particles before and after heating. The pyrolysis residue is 85% by weight or more, and preferably 90% by weight or more.

  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 ratio (inorganic shell thickness / organic core radius) is preferably 0.10 or more, and preferably 0.60 or less. When the ratio is above the lower limit and below the upper limit, good compression deformation characteristics can be maintained even when exposed to high temperatures. Moreover, the connection resistance between the electrodes electrically connected by the conductive particles can be lowered, and the insulation reliability can be increased.

  In 100% by weight of the organic core, the content of silicon atoms contained in the organic core is preferably 10% by weight or less, more preferably 5% by weight or less. The organic core may not contain silicon atoms. The organic core preferably contains no silicon atom. The content of carbon atoms contained in the organic core in 100% by weight of the organic core is preferably 50% by weight or more, more preferably 60% by weight or more, and further preferably 65% by weight or more. The smaller the silicon atom content in the organic core and the greater the carbon atom content in the organic core, the higher the flexibility of the organic-inorganic hybrid particles derived from the organic core.

  In 100% by weight of the inorganic shell, the content of silicon atoms contained in the inorganic shell is preferably 50% by weight or more, more preferably 54% by weight or more, and still more preferably 56% by weight or more. In 100% by weight of the inorganic shell, the content of carbon atoms contained in the inorganic shell is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less. The inorganic shell preferably does not contain carbon atoms. The higher the silicon atom content in the inorganic shell and the lower the carbon atom content in the inorganic shell, the better the hardness at the initial compression due to the inorganic shell.

  The contents of silicon atoms and carbon atoms in the organic core and inorganic shell in the organic-inorganic hybrid particle can be measured by line analysis using a TEM / EDS method.

  The use of the organic-inorganic hybrid particles is not particularly limited. The organic-inorganic hybrid particles are suitably used for various applications. The organic-inorganic hybrid particles are preferably used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer, or used as spacers for liquid crystal display elements. The organic-inorganic hybrid particles according to the present invention are preferably used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer. The organic / inorganic hybrid particles are preferably used as spacers for liquid crystal display elements. Since the organic-inorganic hybrid particles have good compression deformation characteristics, the organic-inorganic hybrid particles are used as spacers for liquid crystal display elements and disposed between substrates, or a conductive layer is formed on the surface to be used as conductive particles. When the electrodes are electrically connected, the spacers for liquid crystal display elements or the conductive particles are efficiently arranged between the substrates or between the electrodes. Furthermore, when an impact is applied to the liquid crystal display element using the liquid crystal display element spacer and the connection structure using the conductive particles, the spacer for the liquid crystal display element corresponds to the variation in the distance between the substrates or the electrodes. Alternatively, the conductive particles are likely to follow and deform easily. For this reason, it is hard to produce the dispersion | variation in the space | interval between board | substrates or electrodes, and it becomes difficult to produce the connection failure between electrodes.

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

Compression modulus when the organic-inorganic hybrid particles 10% compressive deformation (10% K value) is preferably 2000N / mm ² or more, more preferably 3000N / mm ² or more, more preferably 4000 N / mm ² or more, particularly preferably 5000N / mm ² or more, most preferably 6000 N / mm ² or more, preferably 15000 N / mm ² or less, more preferably 10000 N / mm ^2, more preferably not more than 8500N / mm ^2. The organic-inorganic hybrid particles having the 10% K value of not less than the above lower limit and not more than the above upper limit have good compression deformation characteristics. If the 10% K value is 5000 N / mm ² or more, the connection resistance is considerably low.

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

  Since good compression deformation characteristics can be obtained, the compression elastic modulus (10% K value) when the organic-inorganic hybrid particles are compressed by 10%, the compression elastic modulus when the organic-inorganic hybrid particles are compressed by 30% ( 30% K value) (10% K value / 30% K value) is preferably 1 or more, more preferably 1.3 or more, still more preferably 1.8 or more, particularly preferably 2.0 or more, preferably 10.0 or less, more preferably 5.0 or less, still more preferably 4.4 or less.

  The compression elastic modulus (10% K value and 30% K value) of the organic-inorganic hybrid particles can be measured as follows.

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

K value (N / mm ² ) = (3/2 ^1/2 ) · F · S ⁻³ / ² · R ^−1/2
F: Load value when organic-inorganic hybrid particles are 10% or 30% compressively deformed (N)
S: Compression displacement (mm) when organic-inorganic hybrid particles are 10% or 30% compressively deformed
R: Radius of organic / inorganic hybrid particles (mm)

  The compression elastic modulus universally and quantitatively represents the hardness of the organic-inorganic hybrid particles. By using the compression elastic modulus, the hardness of the organic-inorganic hybrid particles can be expressed quantitatively and uniquely.

  The organic core is preferably organic particles. Various organic materials are suitably used as a material for forming the organic core. Examples of the material for forming the organic core include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Polymerize one or more of polyalkylene terephthalate, polysulfone, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, and various polymerizable monomers having ethylenically unsaturated groups The polymer obtained by making it use is used. It is possible to design and synthesize organic-inorganic hybrid particles having physical properties at the time of compression suitable for conductive materials by polymerizing one or more of various polymerizable monomers having an ethylenically unsaturated group. Easy.

  When the organic core is obtained by polymerizing a monomer having an ethylenically unsaturated group, the monomer having an ethylenically unsaturated group may be a non-crosslinkable monomer or a crosslinkable monomer. And a polymer.

  Examples of the non-crosslinkable monomer include styrene monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylates such as meth) acrylate and isobornyl (meth) acrylate; oxygen such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate (Meth) acrylates; nitrile-containing monomers such as (meth) acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether; vinyl acids such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate Esters; Unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; Halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride and chlorostyrene Is mentioned.

  Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanure And silane-containing monomers such as triallyl trimellitate, divinylbenzene, diallyl phthalate, diallylacrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane It is done.

  The organic core can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.

  From the viewpoint of suppressing deformation of the organic core during formation of the inorganic shell and use of the organic-inorganic hybrid particles, the decomposition temperature of the organic core is preferably more than 200 ° C, more preferably more than 250 ° C, and still more preferably. Exceeds 300 ° C. The decomposition temperature of the organic core may exceed 400 ° C., may exceed 500 ° C., may exceed 600 ° C., and may exceed 800 ° C.

  The particle size of the organic core is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 500 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, particularly preferably 20 μm or less, and most preferably 10 μm or less. is there. When the particle size 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 are even more suitable values, and the organic-inorganic hybrid particles are used as conductive particles and liquid crystal display element spacers. It becomes possible to use suitably for the use of. For example, when the particle diameter of the organic core is not less than the lower limit and not more than the upper limit, when the electrodes are connected using the conductive particles, the contact area between the conductive particles and the electrodes is sufficiently large, And it becomes difficult to form the agglomerated conductive particles when forming the conductive layer. Moreover, the space | interval between the electrodes connected via the electroconductive particle does not become large too much, and it becomes difficult for a conductive layer to peel from the surface of an organic inorganic hybrid particle.

  The particle diameter of the organic core means a diameter when the organic core is a true sphere, and means a maximum diameter when the organic core has a shape other than a true sphere. Moreover, in this invention, a particle size means the average value which observed the organic core using the scanning electron microscope, and measured the particle size of 50 organic cores selected arbitrarily with a caliper.

  The 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 preferably contains 50% by weight or more of silicon atoms. In this case, the inorganic shell is an inorganic shell containing silicon atoms as a main component. The inorganic shell may contain carbon atoms, but even if it contains carbon atoms, it is called an inorganic shell if silicon atoms are the main component.

  The inorganic shell is preferably formed on the surface of the organic core by forming a metal alkoxide into a shell-like material by a sol-gel method and then firing the shell-like material. In the sol-gel method, it is easy to dispose a shell-like material on the surface of the organic core. When performing the firing, in the organic-inorganic hybrid particles, the organic core remains without being removed by volatilization or the like after firing. The organic-inorganic hybrid particles include the organic core after firing. If the organic core is removed by volatilization or the like after firing, the 10% K value becomes considerably low.

  As a specific method of the sol-gel method, an interface sol is prepared by coexisting an inorganic monomer such as tetraethoxysilane in a dispersion containing an organic core, a solvent such as water or alcohol, a surfactant, and a catalyst such as an aqueous ammonia solution. Examples include a method of performing a reaction and a method of heteroaggregating a sol-gel reactant on an organic core after performing a sol-gel reaction with an inorganic monomer such as tetraethoxysilane coexisting with a solvent such as water or alcohol and an aqueous ammonia solution. . In the sol-gel method, the metal alkoxide is preferably hydrolyzed and polycondensed.

  In the sol-gel method, it is preferable to use a surfactant. In the presence of a surfactant, the metal alkoxide is preferably made into a shell by a sol-gel method. The surfactant is not particularly limited. The surfactant is appropriately selected and used so as to form a good shell. Examples of the surfactant include a cationic surfactant, an anionic surfactant, and a nonionic surfactant. Among these, a cationic surfactant is preferable because a good inorganic shell can be formed.

  Examples of the cationic surfactant include quaternary ammonium salts and quaternary phosphonium salts. Specific examples of the cationic surfactant include hexadecyl ammonium bromide.

  In order to form the inorganic shell on the surface of the organic core, the shell-like material is preferably baked. The degree of crosslinking in the inorganic shell can be adjusted by the firing conditions. In addition, by performing the firing, the 10% K value and the 30% K value of the organic-inorganic hybrid particles are more preferable than those in the case where the firing is not performed. In particular, the 10% K value can be sufficiently increased by increasing the degree of crosslinking.

  The inorganic shell is preferably formed on the surface of the organic core by forming a metal alkoxide into a shell-like material by a sol-gel method and then firing the shell-like material at 100 ° C. or higher (firing temperature). . The firing temperature is more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher. When the firing temperature is equal to or higher than the lower limit, the degree of cross-linking in the inorganic shell becomes more appropriate, and the 10% K value and the 30% K value show even more suitable values. The liquid crystal display element spacer can be used more suitably depending on the application.

  The inorganic shell is formed on the surface of the organic core by forming a metal alkoxide into a shell-like material by a sol-gel method, and then firing the shell-like material at a temperature lower than the decomposition temperature (firing temperature) of the organic core. Preferably it is. The firing temperature is preferably 5 ° C. or more lower than the decomposition temperature of the organic core, and more preferably 10 ° C. or more lower than the decomposition temperature of the organic core. Moreover, the said calcination temperature becomes like this. Preferably it is 800 degrees C or less, More preferably, it is 600 degrees C or less, More preferably, it is 500 degrees C or less. When the firing 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 exhibiting favorable values of 10% K value and 30% K value can be obtained.

  Examples of the metal alkoxide include silane alkoxide, titanium alkoxide, zirconium alkoxide, and aluminum alkoxide. From the viewpoint of forming a good inorganic shell, the metal alkoxide is preferably silane alkoxide, titanium alkoxide, zirconium alkoxide or aluminum alkoxide, more preferably silane alkoxide, titanium alkoxide or zirconium alkoxide, and silane alkoxide. More preferably. From the viewpoint of forming a good inorganic shell, the metal atom in the metal alkoxide is preferably a silicon atom, a titanium atom, a zirconium atom or an aluminum atom, more preferably a silicon atom, a titanium atom or a zirconium atom. More preferably, it is a silicon atom. As for the said metal alkoxide, only 1 type may be used and 2 or more types may be used together.

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

M (R1) _n (OR2) _4-n (1)
In said formula (1), M is a silicon atom, a titanium atom, or a zirconium atom, R1 is a phenyl group, a C1-C30 alkyl group, a C1-C30 organic group which has a polymerizable double bond, or A C1-C30 organic group which has an epoxy group is represented, R2 represents a C1-C6 alkyl group, and n represents the integer of 0-2. When n is 2, the plurality of R1s may be the same or different. Several R2 may be the same and may differ.

  From the viewpoint of forming a good inorganic shell, the metal alkoxide is preferably a silane alkoxide represented by the following formula (1A).

Si (R1) _n (OR2) _4-n Formula (1A)
In the above formula (1A), R1 represents a phenyl group, an alkyl group having 1 to 30 carbon atoms, an organic group having 1 to 30 carbon atoms 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, the plurality of R1s may be the same or different. Several R2 may be the same and may differ. In order to effectively increase the content of silicon atoms contained in the inorganic shell, n in the above formula (1A) preferably represents 0 or 1, and more preferably represents 0. When the content of silicon atoms contained in the inorganic shell is high, the effect of the present invention is further improved.

  When 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, n-octyl group, And n-decyl group. This alkyl group preferably has 10 or less carbon atoms, more preferably 6 or less. The alkyl group includes a cycloalkyl group.

  Examples of the polymerizable double bond include a carbon-carbon double bond. When R1 is an organic group having 1 to 30 carbon atoms having a polymerizable double bond, specific examples of R1 include a vinyl group, an allyl group, an isopropenyl group, and a 3- (meth) acryloxyalkyl group. Etc. Examples of the (meth) acryloxyalkyl group include a (meth) acryloxymethyl group, a (meth) acryloxyethyl group, and a (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, preferably 30 or less, more preferably 10 or less. The above “(meth) acryloxy” means methacryloxy or acryloxy.

  When R1 is an organic group having 1 to 30 carbon atoms having an epoxy group, specific examples of R1 include 1,2-epoxyethyl group, 1,2-epoxypropyl group, 2,3-epoxypropyl group, Examples include 3,4-epoxybutyl group, 3-glycidoxypropyl group, and 2- (3,4-epoxycyclohexyl) ethyl group. The carbon number of the C1-C30 organic group having the epoxy group is preferably 8 or less, more preferably 6 or less. In addition, the C1-C30 organic group which has the said epoxy group is group containing the oxygen atom derived from an epoxy group in addition to a carbon atom and a hydrogen atom.

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

  Specific examples of the silane alkoxide include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxy. Examples include silane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, and diisopropyldimethoxysilane. Silane alkoxides other than these may be used.

  In order to effectively increase the content of silicon atoms contained in the inorganic shell, it is preferable to use tetramethoxysilane or tetraethoxysilane as the material of the inorganic shell. In 100% by weight of the inorganic shell material, the total content of tetramethoxysilane and tetraethoxysilane is preferably 50% by weight or more (or the total amount may be sufficient). In 100% by weight of the inorganic shell, the total content of the skeleton derived from tetramethoxysilane and the skeleton derived from tetraethoxysilane is preferably 50% by weight or more (or the total amount may be sufficient).

  Specific examples of the titanium alkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, and the like. Titanium alkoxides other than these may be used.

  Specific examples of the zirconium alkoxide include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium tetrabutoxide and the like. Other zirconium alkoxides may be used.

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

M (OR2) ₄ Formula (1a)
In said formula (1a), M is a silicon atom, a titanium atom, or a zirconium atom, R2 represents a C1-C6 alkyl group. Several R2 may be the same and may differ.

  The metal alkoxide preferably includes a silane alkoxide having a structure in which four oxygen atoms are directly bonded to a silicon atom. In this silane alkoxide, generally, four oxygen atoms are bonded to a silicon atom by a single bond. The metal alkoxide preferably includes a silane alkoxide represented by the following formula (1Aa).

Si (OR2) ₄ Formula (1Aa)
In said formula (1Aa), R2 represents a C1-C6 alkyl group. Several R2 may be the same and may differ.

  From the viewpoint of effectively increasing the 10% K value and effectively lowering the 30% K value, in the 100 mol% of the metal alkoxide used to form the inorganic shell, four oxygen atoms exist in the metal atom. A metal alkoxide having a structure in which is directly bonded, a metal alkoxide represented by the above formula (1a), a silane alkoxide having a structure in which four oxygen atoms are directly bonded to the silicon atom, or the above formula (1Aa) The content of each of the silane alkoxides represented by is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 55 mol% or more, and particularly preferably 60 mol%. As mentioned above, it is 100 mol% or less. The total amount of metal alkoxide used to form the inorganic shell is a metal alkoxide having a structure in which four oxygen atoms are directly bonded to the metal atom, the metal alkoxide represented by the formula (1a), the silicon atom May be a silane alkoxide having a structure in which four oxygen atoms are directly bonded to each other, or a silane alkoxide represented by the above formula (1Aa).

  From the viewpoint of effectively increasing the 10% K value and effectively decreasing the 30% K value, four oxygen atoms out of 100% of the total number of metal atoms derived from the metal alkoxide contained in the inorganic shell. The ratio of the number of metal atoms to which atoms are directly bonded The number of silicon atoms to which four -O-Si groups are directly bonded and four oxygen atoms in the four -O-Si groups are directly bonded The number ratio is preferably 20% or more, more preferably 40% or more, still more preferably 50% or more, still more preferably 55 mol% or more, and particularly preferably 60% or more.

  From the viewpoint of effectively increasing the 10% K value and effectively reducing the 30% K value, four oxygen atoms are present in 100% of the total number of metal atoms contained in the inorganic shell. The ratio of the number of directly bonded metal atoms is preferably 20% or more, more preferably 40% or more, still more preferably 50% or more, still more preferably 55 mol% or more, and particularly preferably 60% or more. . From the viewpoint of effectively increasing the 10% K value and effectively reducing the 30% K value, the metal alkoxide is a silane alkoxide and the total number of silicon atoms contained in the inorganic shell is 100. %, The ratio of the number of silicon atoms in which four —O—Si groups are directly bonded and the four oxygen atoms in the four —O—Si groups are directly bonded is preferably 20% or more, More preferably, it is 40% or more, further preferably 50% or more, and particularly preferably 60% or more.

  Note that a silicon atom in which four —O—Si groups are directly bonded and four oxygen atoms in the four —O—Si groups are directly bonded is represented by, for example, the following formula (11). It is a silicon atom in the structure. Specifically, it is a silicon atom indicated by an arrow A in the structure represented by the following formula (11X).

  The oxygen atom in the above formula (11) generally forms a siloxane bond with the adjacent silicon atom.

  The ratio of the number of silicon atoms in which the four —O—Si groups are directly bonded and the four oxygen atoms in the four —O—Si groups are directly bonded (the ratio of the number of Q4 (%)). As a measuring method, for example, using an NMR spectrum analyzer, Q4 (four -O-Si groups are directly bonded and four oxygen atoms in the four -O-Si groups are directly bonded). The peak area of silicon atoms) and Q1 to Q3 (1 to 3 —O—Si groups are directly bonded, and 1 to 3 oxygen atoms in 1 to 3 —O—Si groups are directly bonded to each other. And a peak area of silicon atoms). By this method, in the total number of 100% of silicon atoms contained in the inorganic shell, four —O—Si groups are directly bonded, and four oxygen atoms in the four —O—Si groups are directly bonded. The ratio of the number of bonded silicon atoms (the ratio of the number of Q4) can be obtained.

  The thickness of the inorganic shell is preferably 1 nm or more, more preferably 10 nm or more, still more preferably 50 nm or more, particularly preferably 100 nm or more, preferably 100,000 nm or less, more preferably 10,000 nm or less, still more preferably 2000 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 exhibit even more suitable values, and the organic / inorganic hybrid particles are used as conductive particles and liquid crystal display element spacers. It becomes possible to use suitably for a use. The thickness of the inorganic shell is an average thickness per organic-inorganic hybrid particle. The thickness of the inorganic shell can be controlled by controlling the sol-gel method.

  In the present invention, the thickness of the inorganic shell is determined by observing the organic-inorganic hybrid particles using a scanning electron microscope, and measuring the average particle size of 50 arbitrarily selected organic-inorganic hybrid particles with calipers, and the organic core. It can obtain | require from the difference with the average value of the particle size of this. The particle diameter of the organic-inorganic hybrid particles means a diameter when the organic-inorganic hybrid particles are true spherical, and means a maximum diameter when the organic-inorganic hybrid particles have a shape other than the true spherical shape.

  The aspect ratio of the organic-inorganic hybrid particles is preferably 2 or less, more preferably 1.5 or less, and still more preferably 1.2 or less. The aspect ratio indicates a major axis / minor axis.

  It is preferable that there is no chemical bond between the organic core and the inorganic shell. When the organic core and the inorganic shell are not chemically bonded, the inorganic shell is not easily cracked excessively, and the contact area of the electrode and the conductive particles to the connection target member can be increased. The connection resistance between the electrodes can be further reduced.

  It is preferable that the organic core and the inorganic shell are not chemically bonded, but may be chemically bonded. As a method of chemically bonding between the organic core and the inorganic shell, a functional group capable of reacting with a functional group of the material constituting the inorganic shell is introduced on the surface of the organic core, Examples thereof include a method of forming an inorganic shell with the material constituting the inorganic shell. Specifically, the surface of the organic core is surface-treated with a coupling agent, and then a metal alkoxide is formed into a shell-like material by a sol-gel method on the surface of the organic core.

(Conductive particles)
The conductive particles include the organic-inorganic hybrid particles described above and a conductive layer disposed on the surface of the organic-inorganic hybrid particles.

  In FIG. 1, the electroconductive particle which concerns on the 1st Embodiment of this invention is shown with sectional drawing.

  A conductive particle 1 shown in FIG. 1 includes 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 particle 11. The conductive particle 1 is a coated particle in which the surface of the organic-inorganic hybrid particle 11 is coated with the conductive layer 2.

  The organic / inorganic hybrid particle 11 includes an organic core 12 and an inorganic shell 13 disposed on the surface of the organic core 12. The inorganic shell 13 covers 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 covers the surface of the inorganic shell 13.

  In FIG. 2, the electroconductive particle which concerns on the 2nd Embodiment of this invention is shown with sectional drawing.

  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 includes a first conductive layer 22A that is an inner layer and a second conductive layer 22B that is an outer layer. On the surface of the organic / inorganic hybrid particle 11, the first conductive layer 22 </ b> A is disposed. On the surface of the inorganic shell 13, the first conductive layer 22A is disposed. A second conductive layer 22B is disposed on the surface of the first conductive layer 22A.

  In FIG. 3, the electroconductive particle which concerns on the 3rd Embodiment of this invention is shown with sectional drawing.

  The conductive particles 31 shown in FIG. 3 include the organic / inorganic hybrid particles 11, the conductive layer 32, a plurality of core substances 33, and a plurality of insulating substances 34.

  The conductive layer 32 is disposed on the surface of the organic / inorganic hybrid particle 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 conductive surface. The conductive layer 32 has a plurality of protrusions 32a on the outer surface. Thus, the conductive particles may have protrusions on the conductive surface 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 arranged on the surface of the inorganic shell 13. The plurality of core materials 33 are embedded in the conductive layer 32. The core substance 33 is disposed inside the protrusions 31a and 32a. The conductive layer 32 covers a plurality of core materials 33. The outer surface of the conductive layer 32 is raised by the plurality of core materials 33, and protrusions 31a and 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 part of the outer surface of the conductive layer 32 is covered with an insulating material 34. The insulating substance 34 is made of an insulating material and is an insulating particle. Thus, the said electroconductive particle may have the insulating substance arrange | positioned on the outer surface of a conductive layer.

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

  Like the conductive particles 1 and 31, the conductive layer may be formed of a single layer. Like the conductive particles 21, the conductive layer may be formed of a plurality of layers. That is, the conductive layer may have a stacked structure of two or more layers. When the conductive layer is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and is a gold layer. Is more preferable. When the outermost layer is these preferred conductive layers, the connection resistance between the electrodes is further reduced. Moreover, when the outermost layer is a gold layer, the corrosion resistance is further enhanced.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The connection structure 51 shown in FIG. 4 is a connection that connects the first connection target member 52, the second connection target member 53, and the first connection target member 52 and the second connection target member 53. Part 54. The connection part 54 is formed of a conductive material containing the conductive particles 1 and a binder resin. In FIG. 4, the conductive particles 1 are schematically shown for convenience of illustration. Instead of the conductive particles 1, other conductive particles such as the conductive particles 21 and 31 may be used.

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

The manufacturing method of the connection structure is not particularly limited. As an example of a method of manufacturing a connection structure, a method of placing the conductive material between a first connection target member and a second connection target member to obtain a laminate, and then heating and pressurizing the laminate Etc. The pressure of the said pressurization is about 9.8 * 10 < ⁴ > -4.9 * 10 < ⁶ > Pa. The temperature of the said heating is about 120-220 degreeC. The pressure of the pressurization for connecting the electrode of the flexible printed board, the electrode arranged on the resin film, and the electrode of the touch panel is about 9.8 × 10 ^{4 to} 1.0 × 10 ⁶ Pa.

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

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

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

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

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

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

  A liquid crystal 85 is sealed between the pair of transparent glass substrates 82. A plurality of organic-inorganic hybrid particles 11 are disposed between the pair of transparent glass substrates 82. The organic / inorganic hybrid particle 11 is used as a spacer for a liquid crystal display element. The space between the pair of transparent glass substrates 82 is regulated by the plurality of organic-inorganic hybrid particles 11. A sealing agent 86 is disposed between the edges of the pair of transparent glass substrates 82. Outflow of the liquid crystal 85 to the outside is prevented by the sealing agent 86.

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

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

Example 1
(1) Preparation of organic-inorganic hybrid particles “Micropearl EYP-00375” (acrylic polymer, average particle size 3.75 μm) manufactured by Sekisui Chemical Co., Ltd. was prepared as an organic core. 100 parts by weight of this organic core and 40 parts by weight of hexadecyltrimethylammonium bromide as a surfactant were 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 25% by weight aqueous ammonia solution was added and stirred while applying ultrasonic waves. A solution prepared by dissolving 600 parts by weight of tetraethoxysilane in 1200 parts by weight of ethanol was added and stirred at 25 ° C. for 24 hours while applying ultrasonic waves. The reaction solution is taken out, suction filtered through a membrane filter made of PTFE (polytetrafluoroethylene), washed with ethanol twice, dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles are removed. Obtained.

(2) Production of conductive particles After washing and drying the obtained organic-inorganic hybrid particles, a nickel layer is formed on the surface of the obtained organic-inorganic hybrid particles by an electroless plating method. Produced. The nickel layer had a thickness of 0.1 μm.

(Example 2)
The organic core was changed to Sekisui Chemical Co., Ltd. “Micropearl ELP-00375” (styrene / acrylic copolymer, average particle size 3.75 μm), ethanol was changed to isopropanol, and the amount of tetraethoxysilane added was 900 wt. Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the part was changed to the part.

(Example 3)
The organic core was changed to Sekisui Chemical Co., Ltd. “Micropearl ELP-00375” (styrene / acrylic copolymer, average particle size 3.75 μm), ethanol was changed to isopropanol, and the addition amount of tetraethoxysilane was 1200 weight Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the part was changed to the part.

Example 4
Example 1 except that the organic core was changed to “Micropearl EX-00375” (styrene polymer, average particle size 3.75 μm) manufactured by Sekisui Chemical Co., Ltd., and the addition amount of tetraethoxysilane was changed to 300 parts by weight. In the same manner, organic-inorganic hybrid particles and conductive particles were obtained.

(Example 5)
Example 1 except that the organic core was changed to “Micropearl EX-00375” (styrene polymer, average particle size 3.75 μm) manufactured by Sekisui Chemical Co., Ltd., and the addition amount of tetraethoxysilane was changed to 100 parts by weight. In the same manner, organic-inorganic hybrid particles and conductive particles were obtained.

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

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

(3) Electroless nickel plating step In the same manner as in Example 1, a nickel layer was formed on the surface of the organic-inorganic hybrid particles to produce conductive particles. The nickel layer had a thickness of 0.1 μm.

(Example 7)
(1) Production of insulating particles A 1000 mL separable flask equipped with a four-neck separable cover, a stirring blade, a three-way cock, a condenser tube and a temperature probe was charged with 100 mmol methyl methacrylate and N, N, N-trimethyl. Ion-exchanged water containing a monomer composition containing 1 mmol of -N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2'-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.

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

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

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

(Example 8)
Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that ethanol was changed to acetonitrile.

(Comparative Example 1)
“Micropearl SI-GH038” (silica, average particle size 3.80 μm) manufactured by Sekisui Chemical Co., Ltd., which is silica particles, was used as particles (inorganic particles) of Comparative Example 1. Using these particles, conductive particles were obtained in the same manner as in Example 1.

(Comparative Example 2)
1600 parts by weight of ion exchange water was placed in a separable flask. 10 parts by weight of 25% by weight aqueous ammonia solution was added and gently stirred. To the upper layer, 100 parts by weight of methyltrimethoxysilane was slowly added so as not to disturb the interface. After disappearance of the oil / water interface, 30 parts by weight of 25% by weight aqueous ammonia solution was added, and the mixture was further stirred for 24 hours. The reaction solution was taken out, suction filtered through a PTFE membrane filter, washed with ethanol twice, and then dried in a vacuum dryer at 50 ° C. for 24 hours to obtain non-core-shell type organic-inorganic hybrid particles. . Using the obtained organic / inorganic hybrid particles, conductive particles were obtained in the same manner as in Example 1.

(Comparative Example 3)
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, followed by reaction at 120 ° C. for 5 hours under reflux of toluene. Thereafter, it is cooled to room temperature, 0.35 part by weight of ethylenediamine and 0.1 part by weight of an amino silane coupling agent (“KBM-9103” manufactured by Shin-Etsu Chemical Co., Ltd.) are added, and the reaction is carried out at 60 ° C. for 5 hours. went. Next, toluene was distilled off under reduced pressure to obtain a polyurethane resin having hydroxyl groups at both ends and having a urethane bond and a urea bond.

  400 parts by weight of the obtained polyurethane resin, 12 parts by weight of yellow iron oxide, and 380 parts by weight of ethyl acetate were mixed to obtain a mixture. The obtained mixture was dispersed while being dropped into 2000 parts by weight of a 0.5% by weight aqueous solution of polyvinyl alcohol to obtain a resin. The obtained resin was filtered through filter paper, taken out from water, and dried in a vacuum dryer at 50 ° C. for 24 hours to obtain polyurethane fine particles bound with a silane coupling agent.

  100 parts by weight of the obtained polyurethane fine particles are placed in a 1 L flask, and tetraethoxysilane containing 75 parts by weight of methanol, 25 parts by weight of water, 2 parts by weight of tetraethoxysilane, and 10 parts by weight of a 25% by weight aqueous ammonia solution. The liquid was added and reacted under stirring for 2 hours. After filtration and washing, the obtained particles were again subjected to the same treatment with the same treatment liquid as the tetraethoxysilane liquid. The reaction solution was taken out, suction filtered with a PTFE membrane filter, washed with ethanol twice, and then dried for 24 hours in a vacuum dryer at 50 ° C. to obtain organic-inorganic hybrid particles. Using the obtained organic / inorganic hybrid particles, conductive particles were obtained in the same manner as in Example 1.

(Comparative Example 4)
Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Comparative Example 3 except that the amount of tetraethoxysilane added was 20 parts by weight.

(Comparative Example 5)
100 parts by weight of isophthalic acid chloride, 90 parts by weight of hexamethylenediamine, 10 parts by weight of an amino silane coupling agent (“KBM-9103” manufactured by Shin-Etsu Chemical Co., Ltd.) and 120 parts by weight of MEK (methyl ethyl ketone) are mixed and dissolved. This solution was used as the oil phase. 10 parts by weight of a polycarboxylic acid type emulsifier was dissolved in 800 parts by weight of ion-exchanged water to obtain an aqueous phase. The aqueous phase and the oil phase were mixed and emulsified and dispersed using a homomixer to obtain a dispersion. This dispersion was reacted at 60 ° C. for 10 hours to obtain a resin. The obtained resin was filtered through filter paper, taken out from water, and dried in a vacuum dryer at 50 ° C. for 24 hours to obtain polyamide fine particles bound with a silane coupling agent.

  100 parts by weight of the obtained polyamide fine particles are put in a 1 L flask, and a tetraethoxysilane liquid containing 75 parts by weight of methanol, 25 parts by weight of water, 2 parts by weight of tetraethoxysilane, and 10 parts by weight of a 25% by weight aqueous ammonia solution. Was added and reacted under stirring for 2 hours. After filtration and washing, the obtained particles were again subjected to the same treatment with the same treatment liquid as the tetraethoxysilane liquid. The reaction solution was taken out, suction filtered with a PTFE membrane filter, washed with ethanol twice, and then dried for 24 hours in a vacuum dryer at 50 ° C. to obtain organic-inorganic hybrid particles. Using the obtained organic / inorganic hybrid particles, conductive particles were obtained in the same manner as in Example 1.

(Evaluation)
(1) Weight of organic-inorganic hybrid particles (other particles) after heating (300 ° C. combustion residue)
The obtained organic-inorganic hybrid particles (other particles) were set to 100 ° C. The weight of the organic-inorganic hybrid particles at 100 ° C. was measured. Next, using a TG / DTA apparatus, the organic / inorganic hybrid particles are heated from 100 ° C. to 300 ° C. at a rate of 10 ° C./minute, and then when the temperature reaches 300 ° C., the weight of the organic / inorganic hybrid particles after heating is increased. It was measured. When the weight of the organic-inorganic hybrid particles at 100 ° C. was 100% by weight, the weight of the organic-inorganic hybrid particles after heating to 300 ° C. (300 ° C. combustion residue) was determined.

(2) Particle size of organic-inorganic hybrid particles (other particles), organic core particle size, and inorganic shell thickness The obtained organic-inorganic hybrid particles (other particles) were scanned using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation). "S-3500N")) was taken at a magnification of 3000 times, the particle size of 50 particles in the obtained image was measured with calipers, the number average was obtained, and the organic-inorganic hybrid particles (other particles) The particle size was determined.

  The particle size of the organic core used for preparing 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 size of the organic-inorganic hybrid particle and the particle size of the organic core.

(3) The above-mentioned compression elastic modulus (10% K value and 30% K value) of organic-inorganic hybrid particles (other particles)
The above-mentioned compression elastic modulus (10% K value and 30% K value) of the obtained organic-inorganic hybrid particles (other particles) before heating is measured by the above-described method using a micro compression tester (Fischer Scope H manufactured by Fischer). -100 ").

(4) Connection resistance Fabrication of connection structure:
10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and a microcapsule type curing agent (Asahi Kasei Chemicals) "HX3941HP" manufactured by 50 parts by weight and 2 parts by weight of silane coupling agent ("SH6040" manufactured by Toray Dow Corning Silicone Co., Ltd.) were mixed, and the resulting conductive particles (using organic-inorganic hybrid particles before heating) Was added and dispersed so that the content was 3% by weight to obtain a resin composition.

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

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

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

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

(5) Heat resistance 1
The obtained organic-inorganic hybrid particles were heated at 200 ° C. for 6 hours. The above-mentioned compression elastic modulus (10% K value) of the organic-inorganic hybrid particles (other particles) after heating is measured by the above-described method using a micro-compression tester (“Fischer Scope H-100” manufactured by Fischer). did. The heat resistance 1 of the organic / inorganic hybrid particles was determined according to the following criteria.

[Criteria for heat resistance 1]
○ ○: 10% K value of particles after heating is 95% or more of 10% K value of particles before heating ○: 10% K value of particles after heating is 10% K value of particles before heating 90% or more and less than 95% Δ: 10% K value of particles after heating is 80% or more of particle 10% before heating and less than 90% ×: 10% K value of particles after heating Less than 80% of 10% K value of particles before heating

(6) Heat resistance 2
A connection structure X obtained by the above (4) evaluation of connection resistance was prepared. The connection structure X was heated at 200 ° C. for 6 hours to obtain a connection structure Z. The connection resistance of the connection structure Z was evaluated in the same manner as the evaluation of (4) connection resistance. The heat resistance 2 of the connection structure Z was determined according to the following criteria.

[Criteria for heat resistance 2]
◯: The connection resistance of the connection structure Z after heating is 90% or more and less than 110% of the connection resistance of the connection structure X before heating. ○: The connection resistance of the connection structure Z after heating is before the heating. 110% or more and less than 120% of connection resistance of connection structure X Δ: Connection resistance of connection structure Z after heating is 120% or more and less than 130% of connection resistance of connection structure X before heating ×: Heating The connection resistance of the subsequent connection structure Z is 130% or more of the connection resistance of the connection structure X before heating.

  The results are shown in Tables 1 and 2 below. The aspect ratio of the organic-inorganic hybrid particles obtained in Examples 1 to 5 and 8 was 1.2 or less. In addition, although the evaluation results of the connection resistance in Examples 1 to 3, 6, and 7 are all “◯”, the value of the connection resistance in Examples 6 and 7 is larger than the value of the connection resistance in Examples 1 to 3. The connection resistance value in Example 6 was lower than the connection resistance value in Example 7. Protrusions are thought to be influencing.

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

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

  In the obtained liquid crystal display element, the space | interval between board | substrates was favorably controlled by the spacer for liquid crystal display elements before the heating of Examples 1-5. Moreover, the liquid crystal display element showed favorable display quality. Moreover, the liquid crystal display element using the spacer for liquid crystal display elements of Examples 1-5 was heated at 80 degreeC for 5 hours. The display quality of the liquid crystal display element after heating was maintained satisfactorily.

DESCRIPTION OF SYMBOLS 1 ... Conductive particle 2 ... Conductive layer 11 ... Organic-inorganic hybrid particle 12 ... Organic core 13 ... Inorganic shell 21 ... Conductive particle 22 ... Conductive layer 22A ... First conductive layer 22B ... Second conductive layer 31 ... Conductive Particle 31a ... Protrusion 32 ... Conductive layer 32a ... Protrusion 33 ... Core material 34 ... Insulating material 51 ... Connection structure 52 ... First connection target member 52a ... First electrode 53 ... Second connection target member 53a ... First 2. Electrode 54 ... Connection part 81 ... Liquid crystal display element 82 ... Transparent glass substrate 83 ... Transparent electrode 84 ... Alignment film 85 ... Liquid crystal 86 ... Sealing agent

Claims (10)

A conductive layer is formed on the surface and is an organic-inorganic hybrid particle used for obtaining conductive particles having the conductive layer, or an organic-inorganic hybrid particle used as a gap control material,
Comprising an organic core and an inorganic shell disposed on the surface of the organic core;
When the weight of the organic / inorganic hybrid particles at 100 ° C. is 100% by weight, the temperature is increased from 100 ° C. to 300 ° C. at 10 ° C./min. % By weight,
Organic-inorganic hybrid particles, wherein 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 according to claim 1, wherein there is no chemical bond between the organic core and the inorganic shell. The organic-inorganic hybrid particle according to claim 1 or 2 , wherein the thickness of the inorganic shell is 50 nm or more and 2000 nm or less. The organic-inorganic hybrid particle according to any one of claims 1 to 3 , wherein a particle diameter of the organic core is 0.5 µm or more and 100 µm or less. The organic-inorganic hybrid particle according to any one of claims 1 to 4 , wherein a compression elastic modulus when compressed by 10% is 5000 N / mm ² or more. The organic-inorganic hybrid particle according to any one of claims 1 to 5, wherein a conductive layer is formed on a surface and used to obtain conductive particles having the conductive layer. The organic-inorganic hybrid particle according to any one of claims 1 to 5, wherein the gap control material is a spacer for a liquid crystal display element. Organic-inorganic hybrid particles according to any one of claims 1 to 6 ,
A conductive particle comprising a conductive layer disposed on a surface of the organic-inorganic hybrid particle. Containing conductive particles and a binder resin,
A conductive material, wherein the conductive particles include the organic-inorganic hybrid particles according to any one of claims 1 to 6 and a conductive layer disposed on a surface of the organic-inorganic hybrid particles. A first connection object member having a first electrode on its surface;
A second connection target member having a second electrode on its surface;
A connection portion connecting the first connection target member and the second connection target member;
The connecting portion is formed of conductive particles or formed of a conductive material containing the conductive particles and a binder resin;
The said electroconductive particle is equipped with the organic inorganic hybrid particle of any one of Claims 1-6 , and the electroconductive layer arrange | positioned on the surface of the said organic inorganic hybrid particle,
A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles.

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