JP6188392B2 - 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 particle and an inorganic shell disposed on the surface of the organic core particle. 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, and a semiconductor chip to obtain a connection structure. 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, Patent Document 1 discloses an organic polymer in which the core is an organic polymer having a flexible skeleton, the shell is an organic polymer having a hard skeleton, and the core is covered with the shell. Polymer particles are disclosed. Patent Document 2 discloses organic polymer particles (organic-inorganic hybrid particles) in which the shell is an inorganic compound, the core is an organic polymer, and the core is covered with the shell. Patent Document 2 also discloses conductive particles in which organic polymer particles are coated with a conductive metal.

  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.

  The organic polymer particles described in Patent Document 1 can also be used as a spacer of a liquid crystal display element.

Japanese Patent No. 4107769 JP 2006-156068 A

  When the connection structure was obtained by electrically connecting the electrodes using conductive particles having a conductive layer formed on the surface of the organic-inorganic hybrid particles, the organic inorganic hybrid particles were composed of the organic polymer described in Patent Document 1. In the core-shell particles, the hardness of the particle surface is insufficient, so that the conductive particles do not penetrate into the inside of the electrodes, and the connection state is high in the connection structure in which the electrodes are electrically connected. Become. Further, in the organic-inorganic hybrid particle of Patent Document 2, when the inorganic shell is thin, only the compressive deformation characteristic of the organic core particle is expressed, and the particle surface is insufficient in hardness. The connection state is not increased because the electrode is not pierced, and the connection resistance is increased in the connection structure in which the electrodes are electrically connected. In addition, in a state where the inorganic shell is thick, a conductive connection state can be obtained by piercing the inside of the electrode, but the organic core particle is destroyed at a low load, and the organic core particle is destroyed. Since they are connected, gap followability between the electrodes is lost, and as a result, there is a problem that connection reliability is lowered.

  When the conventional organic-inorganic hybrid particles as described in Patent Document 2 are used as spacers for a liquid crystal display element and are arranged between substrates to obtain a liquid crystal display element, the organic core particles are compressed in a thin inorganic shell. Since only the deformation characteristics are manifested and the hardness of the particle surface is insufficient, the gap (gap) between the substrates cannot be kept constant, gap unevenness occurs, and display defects such as light leakage occur. There is a problem. On the other hand, when the inorganic shell is thick, the hardness of the particle surface can be obtained. However, since the inorganic shell is too hard, there is a problem that the substrate is damaged and display defects such as light leakage occur.

  Therefore, the object of the present invention is to form a conductive layer on the surface and use as conductive particles, and when the electrodes are electrically connected, the compression elastic modulus at the initial compression of the organic-inorganic hybrid particles is high, In addition, since the compressive deformation characteristics with respect to the strain of the organic core particles are also high, the conductive particles are deformed well while penetrating the surface between the electrodes, and the organic-inorganic hybrid particles that are difficult to break the organic core particles with a low load, and It is to provide conductive particles, conductive materials, and connection structures using the organic-inorganic hybrid particles.

  In addition, when used as a spacer for a liquid crystal display element and disposed between substrates, the organic-inorganic hybrid particles have a high compressive elastic modulus at the time of initial compression, and can maintain a constant gap (gap) between the substrates. An object of the present invention is to provide organic / inorganic hybrid particles (liquid crystal display element spacers) that are resistant to damage to the substrate because of their high compressive deformation characteristics against strain of the inorganic hybrid particles.

According to a wide aspect of the present invention, the organic core particle and an inorganic shell disposed on the surface of the organic core particle are provided, and the specific gravity of the inorganic shell is 1.8 g / cm ³ or more and 2.3 g / cm. ³ or less, the thickness of the inorganic shell, the ratio to the radius of the organic core particles are 0.05 or more and 0.70 or less, an organic inorganic hybrid particle is provided.

In a specific aspect of the organic-inorganic hybrid particle according to the present invention, the organic-inorganic hybrid particle does not include or includes pores, and the pore volume of the organic-inorganic hybrid particle is 0.01 cm ³ / g or less.

  On the specific situation with the organic-inorganic hybrid particle | grains which concern on this invention, the said organic-inorganic hybrid particle | grain does not contain a pore or contains it, and the pore diameter of the said organic-inorganic hybrid particle | grain is 10 nm or less.

In a specific aspect of the organic-inorganic hybrid particle according to the present invention, the organic-inorganic hybrid particle has a compressive elastic modulus at 10% compression of 2000 mN / mm ² or more and 15000 mN / mm ² or less, and when compressed by 10%. The ratio of the compression elastic modulus to the compression elastic modulus when compressed by 30% is 1.0 or more, and the load required when the organic-inorganic hybrid particles are distorted by 65% is 2.5 mN 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 particle according to the present invention, an inorganic shell is disposed on the surface of the organic core particle, and the specific gravity of the inorganic shell is 1.8 g / cm ³ or more and 2.3 g / cm ³ or less, Since the ratio of the thickness of the inorganic shell to the radius of the organic core particle is 0.05 or more and 0.70 or less, the organic-inorganic hybrid particle has a high compressive elastic modulus at the initial compression, and the strain of the organic core particle Since the organic core particles are not destroyed at low loads due to high compression deformation characteristics, the conductive particles are formed between the electrodes when the electrodes are electrically connected by forming a conductive layer on the surface and using them as conductive particles. It is possible to dispose the conductive particles on the surface between the electrodes while penetrating into the surface of the electrode, deforming well without losing the gap followability between the electrodes, and maintaining a wide contact area. Furthermore, when an impact is applied to the connection structure using the conductive particles, the conductive particles are sufficiently followed and deformed in response to fluctuations in the distance between the electrodes. For this reason, poor connection between the electrodes hardly occurs, and high connection reliability can be obtained.

  In addition, when used as a spacer for a liquid crystal display element and disposed between substrates, the organic-inorganic hybrid particles have a high compressive elastic modulus at the time of initial compression, and can maintain a constant gap (gap) between the substrates. Since the compressive deformation characteristic with respect to the strain of the inorganic hybrid particles is high, a liquid crystal display element in which the substrate is hardly damaged can be obtained.

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. FIG. 6 is a diagram showing an example of a compression deformation curve of the organic-inorganic hybrid particle according to the present invention.

  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 particle and an inorganic shell disposed on the surface of the organic core particle. The specific gravity of the inorganic shell of the organic-inorganic hybrid particle according to the present invention is 1.8 g / cm ³ or more and 2.3 g / cm ³ or less. The ratio of the thickness of the inorganic shell of the organic-inorganic hybrid particle according to the present invention to the radius of the organic core particle is 0.05 or more and 0.70 or less.

  Since the organic-inorganic hybrid particles according to the present invention are provided with the above-described configuration, a thin and hard inorganic shell can be formed, the initial hard and soft later, and the compression deformation characteristics against strain at the time of compression are high. In the connection structure connected to, the conductive particles can be satisfactorily penetrated into the surface between the electrodes. In addition, since the organic-inorganic hybrid particles are hard initially and soft, and have high compression deformation characteristics against strain during compression, the broken pieces of the inorganic shell do not pierce the organic core particles, so compression deformation characteristics against strain of the organic core particles Can be kept high, and the contact area becomes sufficiently large because the organic-inorganic hybrid particles are sufficiently deformed. For this reason, connection resistance can be lowered in the connection structure in which the electrodes are electrically connected.

When the organic / inorganic hybrid particles are used as the spacer for the liquid crystal display element, the spacer for the liquid crystal display element is added to the binder resin for, for example, wet spraying. In the organic-inorganic hybrid particle according to the present invention, an inorganic shell is disposed on the surface of the organic core particle, and the specific gravity of the inorganic shell is 1.8 g / cm ³ or more and 2.3 g / cm ³ or less. Since the ratio of the thickness of the shell to the radius of the organic core particles is 0.05 or more and 0.70 or less, organic / inorganic hybrid particles (such as spacers for liquid crystal display elements) are dispersed in the binder resin to obtain a connection structure. The compression deformation characteristics of the organic / inorganic hybrid particles are not impaired. That is, in the binder resin, the compression deformation characteristics of the organic-inorganic hybrid particles can be kept high, and the initial hard property and the later soft property can be expressed. Therefore, when the organic / inorganic hybrid particles are used as a spacer for a liquid crystal display element, the distance between the substrates (gap) can be kept constant, and the compression / deformation characteristics with respect to the strain of the organic / inorganic hybrid particles are high. It is difficult to stick, and organic-inorganic hybrid particles can be disposed on the surface of the substrate. For this reason, display quality is unlikely to deteriorate in the liquid crystal display device.

  Moreover, when using organic-inorganic hybrid particles as a conductive material containing conductive particles and a binder resin, for example, the conductive particles are often added to the binder resin and used in the form of a conductive paste or a conductive film. .

In the organic-inorganic hybrid particle, an inorganic shell is disposed on the surface of the organic core particle, and the specific gravity of the inorganic shell is 1.8 g / cm ³ or more and 2.3 g / cm ³ or less, and the thickness of the inorganic shell Since the ratio of the organic core particles to the radius is 0.05 or more and 0.70 or less, when the conductive particles are dispersed in the binder resin to form a connection structure, the conductive particles are compressed and deformed. It is possible to develop properties that are initially hard and soft later without damaging the properties. Accordingly, the conductive particles can be disposed on the surface between the electrodes while being well deformed while penetrating the surface between the electrodes and maintaining a wide contact area. For this reason, connection resistance becomes low in the connection structure in which the conductive material electrically connects the electrodes. Furthermore, connection reliability can be improved in the connection structure in which the electrodes are electrically connected. Further, from the viewpoint of increasing the compression elastic modulus at the time of initial compression of the organic-inorganic hybrid particles and increasing the compressive deformation characteristics with respect to strain, the organic-inorganic hybrid particles do not include or include pores, and the organic-inorganic hybrid The pore volume of the particles is preferably 0.01 cm ³ / g or less. When the pore volume of the organic-inorganic hybrid particles is 0.01 cm ³ / g or less, stress strain at the time of compressive deformation is not applied, and the hardness is further improved as an inorganic shell.

  Moreover, it is preferable that the said organic-inorganic hybrid particle does not contain a pore, or contains, and the pore diameter of the said organic-inorganic hybrid particle is 10 nm or less. When the pore diameter of the organic-inorganic hybrid particles is 10 nm or less, stress strain at the time of compressive deformation is not applied, and the hardness is further improved as an inorganic shell.

When the specific gravity of the inorganic shell is in the above range, and the ratio of the thickness of the inorganic shell to the radius of the organic core particle is in the above range, the organic-inorganic hybrid particles (for liquid crystal display elements) in the connection structure As a preferable compressive deformation characteristic of the conductive fine particles or spacers), the organic-inorganic hybrid particles preferably have a compressive elastic modulus at 10% compression of 2000 mN / mm ² or more and 15000 mN / mm ² or less, and compressed by 10%. The ratio of the compression elastic modulus to the compression elastic modulus when compressed at 30% is preferably 1.0 or more, and the load required when the organic-inorganic hybrid particles are distorted by 65% is 2.5 mN or more. preferable.

  Further, from the viewpoint of increasing the compression elastic modulus at the time of initial compression of the organic-inorganic hybrid particles and increasing the compressive deformation characteristics with respect to strain, the organic-inorganic hybrid particles are used during the sol-gel reaction, after the sol-gel reaction, or the sol-gel method. After drying the organic-inorganic hybrid particles obtained by the above, it is preferable to perform post-treatment such as acid treatment, alkali treatment, ultraviolet treatment, microwave heating treatment, millimeter wave treatment, or drying at low temperature for a long time. Although it does not specifically limit as an acid used for the said acid treatment, Hydrochloric acid, an acetic acid, nitric acid, etc. are mentioned. Although it does not specifically limit as an alkali used for the said acid treatment, Sodium hydroxide, ammonia water, etc. are mentioned. Although it does not specifically limit as a light source used for the said ultraviolet treatment, A low pressure mercury UV lamp, a high pressure mercury UV lamp, a metal halide UV lamp, an excimer lamp, etc. are mentioned, As a wavelength, it is preferable to process by 185 nm or more and 400 nm or less. . Although it does not specifically limit as said microwave heat processing, It is preferable to heat at the temperature lower than the decomposition temperature of the said organic core particle, As heat time, it is preferable to process for 0.5 hours or more and 24 hours or less. . As the conditions for the above-mentioned drying at low temperature for a long time, it is preferable that the drying temperature is from room temperature to 100 ° C. and the drying time is 12 hours or more and 48 hours or less. By performing the post-treatment, the inorganic shell of the organic-inorganic hybrid particles becomes denser and an inorganic shell having a higher specific gravity can be obtained.

  The use of the organic-inorganic hybrid particles is not particularly limited. The organic-inorganic hybrid particles are suitably used for various applications that are used by being added to a binder resin. 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. Since the inorganic shell layer of the organic / inorganic hybrid particle according to the present invention has a high specific gravity, the organic / inorganic hybrid particle has an initial hard property and a soft property at the later stage, and the organic core particle is not broken even under a high load. When the particles are disposed between the substrates using the liquid crystal display element spacers, or when the conductive layer is formed on the surface and used as the conductive particles to electrically connect the electrodes, the liquid crystal display element spacers or The conductive particles can be disposed on the surface between the electrodes while being deformed well while maintaining a large contact area while penetrating the surface 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 shock absorber or a vibration absorber. For example, the organic-inorganic hybrid particles can be used as an alternative such as rubber or spring.

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

  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.

  For example, the compression deformation curve when the particle size of the organic-inorganic hybrid particles is 4.6 μm is shown. In addition, when the particle diameter of the organic-inorganic hybrid particles is 4.6 μm, the load required for 65% distortion (particle diameter of the organic-inorganic hybrid particles: 4.6 μm × 65% = 2.99 μm) is 7.5 mN. It becomes.

  FIG. 6 shows an example of the compression deformation curve of the organic-inorganic hybrid particle according to the present invention.

  In the organic-inorganic hybrid particles, the pore distribution (pore volume, pore diameter) and specific surface area can be determined by the BET method using nitrogen gas adsorption / desorption, and JIS Z 8831-2 and JIS Z 8831-3 (powder ( The pore distribution (pore volume, pore diameter) and specific surface area can be measured based on (solid) pore diameter distribution and pore characteristics). The BET method is a method of adsorbing gas molecules whose adsorption occupation area is known on the surface of powder particles, obtaining the specific surface area of the sample from the amount, or measuring the pore distribution from condensation of gas molecules. It is. For example, using “BELSORP-mini” manufactured by Nippon Bell Co., Ltd., the pretreatment condition is vacuum degassing at 80 ° C., the type of gas is nitrogen, and the analysis method is the BET multipoint method (total pore volume P / P0). = 0.98), and the BET method by nitrogen gas adsorption / desorption can be used.

(Organic core particles)
Various organic materials are suitably used as the material for the organic core particles. Examples of materials for forming the organic core particles include polyolefins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Terephthalate, polysulfone, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, and various polymerizable monomers having an ethylenically unsaturated group are polymerized by one or more kinds. The resulting polymer 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 particle 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 di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanurate, tria Rutorimeriteto, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, .gamma. (meth) acryloxy propyl trimethoxy silane, trimethoxy silyl styrene, include silane-containing monomers such as vinyltrimethoxysilane.

  The organic core particles 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.

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

  The particle diameter of the organic core particles is preferably 0.5 μm or more, and preferably 500 μm or less. When the particle diameter of the organic core particles is less than 0.5 μm, when the electrodes are connected using the conductive particles, the contact area between the conductive particles and the electrodes becomes too small, and a conductive layer is formed. When it does, it becomes easy to form the aggregated electroconductive particle. When the particle diameter of the organic core particles exceeds 500 μm, the distance between the electrodes connected via the conductive particles becomes too large, and the conductive layer easily peels from the surface of the organic-inorganic hybrid particles.

  The particle diameter of the organic core particle means a diameter when the organic core particle is a true sphere, and means a maximum diameter when the organic core particle is a shape other than a true sphere.

It is preferable to use organic core particles having a compressive modulus at 10% compression of the organic core particles of preferably 1000 mN / mm ² or more, and preferably 10,000 mN / mm ² or less. It is preferable to use organic core particles having a compression elastic modulus at 30% compression of the organic core particles of preferably 150 mN / mm ² or more, and preferably 500 mN / mm ² or less.

When the organic core particles have a compression elastic modulus at 10% compression of 1000 mN / mm ² or more, when the organic-inorganic hybrid particles in which the organic core particles are coated with the inorganic shell are compressed and deformed, the organic-inorganic hybrid The compression elastic modulus at 10% compression of the particles becomes even better. When the organic core particles have a compression elastic modulus at 30% compression of 150 mN / mm ² or more, when the organic-inorganic hybrid particles in which the organic core particles are coated with the inorganic shell are compression-deformed, the organic-inorganic hybrid The repulsive force of the particles is increased, the gap followability between the electrodes is increased, and the connection reliability is further improved.

(Inorganic shell)
As a specific method for preparing the inorganic shell of the organic-inorganic hybrid particle, a dispersion liquid containing an organic core particle, a solvent such as water, alcohol or aprotic solvent, a surfactant, and a catalyst such as an aqueous ammonia solution may be used. A method of performing an interfacial sol-gel reaction in the presence of an inorganic monomer such as ethoxysilane, and a sol-gel reaction with an inorganic monomer such as tetraethoxysilane coexisting with water, an alcoholic solvent, an aprotic solvent, or an aqueous ammonia solution. Thereafter, a method of heteroaggregating the sol-gel reactant on the organic core particles may be mentioned. 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 the sol-gel method, it is preferable to use a solvent such as alcohol or aprotic.

  From the viewpoint of forming a good inorganic shell, it is preferable that the solubility parameter (SP value) of an alcohol-based solvent or a non-proton-based solvent used in the sol-gel method is in the range of 9-14. The alcohol solvent is not particularly limited, but ethanol (SP value 12.7), isopropyl alcohol (SP value 11.4), 1-propyl alcohol (SP value 11.9), and 1-butanol (SP value 10). .5) and the like. The aprotic solvent is not particularly limited, but tetrahydrofuran (SP value 9.1), acetone (SP value 9.9), acetonitrile (SP value 11.9), and N, N-dimethylformaldehyde (SP value). 12.1) and the like. Alcohol-based and aprotic solvents used in the sol-gel method may be used in combination as appropriate.

  Among the above solvents, an aprotic solvent having a solubility parameter (SP value) in the range of 9 to 14 is particularly preferable. Of these, acetone (SP value 9.9), acetonitrile (11.9), and N, N-dimethylformaldehyde (SP value 12.1) are particularly preferable.

The solubility parameter (also referred to as SP value) is defined as “F, Δv of various atomic groups by Okitsu described in Toshinao Okitsu,“ Adhesion ”, Kobunshi Kyokai, Vol. 40, No. 8 (1996) p342-350. The value is used to mean the solubility parameter δ calculated by the following formula (X). In the case of a mixture or copolymer, the solubility parameter δ _mix calculated by the following formula (Y) is meant.

δ = ΣΔF / ΣΔv (X)
δ _mix = φ ₁ δ ₁ + φ ₂ δ ₂ +... φ _n δ _n (Y)

In the above formulas (X) and (Y), ΔF and Δv respectively represent ΔF and molar volume Δv of various atomic groups by Okitsu. φ represents a volume fraction or a mole fraction, and φ ₁ + φ ₂ +... φ _n = 1.

  Examples of the inorganic monomer include metal alkoxides such as silane alkoxide, titanium alkoxide, zirconium alkoxide and aluminum alkoxide, acetates and other carboxylates, β-diketonates such as acetylacetonate, and general inorganic salts such as nitrate. 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. From the viewpoint of forming a good inorganic shell, the metal alkoxide is a silane alkoxide, and the metal atom in the metal alkoxide 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.

  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 (meth) acryloxyalkyl group. Can be mentioned. 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. Carbon number of the C1-C30 organic group which has the said epoxy group becomes like this. Preferably it is 8 or less, More preferably, it is 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.

  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.

  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, and n represents the integer of 0-2. 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. 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 increasing the compression elastic modulus at the time of initial compression of the organic-inorganic hybrid particles and enhancing the compressive deformation characteristics with respect to strain, 4% of the metal atoms are contained in 100 mol% of the metal alkoxide used for forming the inorganic shell. A metal alkoxide having a structure in which two oxygen atoms are 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) Each content of the represented silane alkoxide is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, and particularly preferably 60 mol% or more and 100 mol% or less. The total amount of the metal alkoxide used to form the inorganic shell is such that the 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), and 4 to the silicon atom. It may be a silane alkoxide having a structure in which two oxygen atoms are directly bonded, or a silane alkoxide represented by the above formula (1Aa).

  Further, from the viewpoint of increasing the compression elastic modulus at the time of initial compression of the organic-inorganic hybrid particles and enhancing the compression deformation characteristics against strain, the total number of metal atoms derived from the metal alkoxide contained in the inorganic shell is 100%. Among them, the ratio of the number of metal atoms directly bonded to four oxygen atoms is preferably the ratio of the number of silicon atoms directly bonded to four oxygen atoms is preferably 20% or more, more preferably 40% or more, and still more preferably 50% or more, particularly preferably 60% or more.

  Further, from the viewpoint of increasing the compressive elastic modulus at the initial compression of the organic-inorganic hybrid particles and enhancing the compressive deformation characteristics with respect to strain, four out of 100% of the total number of metal atoms contained in the inorganic shell. The ratio of the number of metal atoms to which oxygen atoms are directly bonded is preferably 20% or more, more preferably 40% or more, still more preferably 50% or more, and particularly preferably 60% or more. From the viewpoint of effectively increasing the 10% K value and effectively decreasing 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 to which four oxygen atoms are directly bonded is preferably 20% or more, more preferably 40% or more, still more preferably 50% or more, and particularly preferably 60% or more.

  In addition, the silicon atom which four silicon atoms couple | bonded directly is a silicon atom in the structure represented by following formula (11), for example.

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

The specific gravity of the inorganic shell is 1.8 g / cm ³ or more and 2.3 g / cm ³ or less. When the specific gravity of the inorganic shell is less than 1.8 g / cm ³ , the inorganic shell becomes soft and the conductive particles may not penetrate into the surface between the electrodes. When the specific gravity of the inorganic shell exceeds 2.3 g / cm ³ , the inorganic shell becomes too hard and the compression deformation characteristics of the organic core particles may not be exhibited.

  The ratio of the thickness of the inorganic shell to the radius of the organic core particle (the thickness of the inorganic shell / the radius of the organic core particle) is 0.05 or more and 0.70 or less. When the ratio is less than 0.05, the strength of the inorganic shell cannot be maintained, and the conductive particles may not penetrate into the surface between the electrodes. If the ratio exceeds 0.70, the broken pieces of the inorganic shell may pierce the organic core particles, and the breaking load of the organic core particles may be reduced.

When the specific gravity of the inorganic shell is within the above range, and the ratio of the thickness of the inorganic shell to the radius of the organic core particle is within the above range, the organic-inorganic hybrid particles (liquid crystal display) in the connection structure As a preferable compressive deformation characteristic of the element spacer or the like or the conductive fine particles, the organic-inorganic hybrid particles have a compressive elastic modulus at 10% compression of 2000 mN / mm ² or more and 15000 mN / mm ² or less and 10% compression. The ratio of the compressive elastic modulus to the compressive elastic modulus when compressed at 30% is 1.0 or more, and organic-inorganic hybrid particles having a load required when the organic-inorganic hybrid particles are distorted by 65% are 2.5 mN or more. It is easy to be done.

  The specific gravity of the inorganic shell is a value measured at 25 ° C. by measuring the organic core particles at 15 to 25 ° C. and He gas using a specific gravity bottle method density measuring device such as “Accupyc 1330” manufactured by Shimadzu Corporation. Is the specific gravity of the inorganic shell. Next, the specific gravity of the organic-inorganic hybrid particles is measured in the same manner as described above, and the value obtained by subtracting the specific gravity of the organic core particles from the specific gravity of the organic-inorganic hybrid particles is defined as the specific gravity of the inorganic shell. The calculation method is shown below.

In the above formula (21), r represents the radius (μm) of the organic core particle, T represents the thickness of the inorganic shell, H represents the specific gravity (g / cm ³ ) of the organic-inorganic hybrid particle, and C represents the organic core. It represents the specific gravity (g / cm ³ ) of the particles.

  The radius of the organic core particle means a half of the diameter when the organic core particle is a true sphere, and means a half of the maximum diameter when the organic core particle has a shape other than the true sphere. In the present invention, the radius of the organic core particle means an average value obtained by observing the organic core particle using a scanning electron microscope and measuring the particle diameter of 50 organic core particles arbitrarily selected with a caliper. And half the diameter of the average value of the organic core particles.

  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 particles. Half the difference from the average particle size.

  The ratio of the thickness of the inorganic shell to the radius of the organic core particle (the thickness of the inorganic shell / the radius of the organic core particle) is an average value of the radius of the organic core particle and the thickness of the inorganic shell.

(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 particle 12 and an inorganic shell 13 disposed on the surface of the organic core particle 12. The inorganic shell 13 covers the surface of the organic core particle 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 surface. The conductive layer 32 has a plurality of protrusions 32a on the outer surface. As described above, the conductive particles may have protrusions on the surface of the conductive particles, 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 (when the conductive layer is a multilayer, the total 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, Preferably it is 0.5 micrometer or less, Most preferably, it is 0.3 micrometer or less. 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, the thinner the gold layer when the outermost layer is a gold layer, the lower the cost.

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

  The conductive particles may have protrusions on the outer surface of the conductive layer. It is preferable that 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 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 connection 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 a semiconductor chip, a capacitor, and a diode, and circuit components such as a printed board, a flexible printed board, and a glass board. 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 ELP-00375” (styrene / acrylic copolymer, average particle size of 3.75 μm) manufactured by Sekisui Chemical Co., Ltd. was prepared as organic core particles. 100 parts by weight of the organic core particles and 40 parts by weight of a surfactant hexadecyltrimethylammonium bromide are dispersed in a mixed solvent of 1800 parts by weight of isopropyl alcohol (SP value 11.4) and 200 parts by weight of water. 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 isopropyl alcohol was added, and the mixture was stirred at 25 ° C. for 24 hours while applying ultrasonic waves. The reaction solution is taken out, filtered with suction through a membrane filter made of PTFE (polytetrafluoroethylene), washed twice with isopropyl alcohol, then dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles A was obtained.

  100 parts by weight of the obtained organic-inorganic hybrid particles A and 1000 parts by weight of hydrochloric acid were placed in a beaker and stirred at 60 ° C. for 9 hours using a stirring and heating type hot stirrer. The reaction solution is taken out, filtered with suction through a membrane filter made of PTFE (polytetrafluoroethylene), washed twice with isopropyl alcohol, then dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles B was obtained.

(Example 2)
A solution obtained by appropriately mixing 10 parts by weight of the organic-inorganic hybrid particles A obtained in Example 1 and 100 parts by weight of ultrapure water was placed in a “Speed wave 2” (microwave high-speed decomposition system) apparatus manufactured by Actac Co., Ltd. It was heated for 1 hour at 200 ° C. with a wave frequency of 2.45 MHz. The reaction solution is taken out, filtered with suction through a membrane filter made of PTFE (polytetrafluoroethylene), washed twice with isopropyl alcohol, then dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles C was obtained.

(Example 3)
The organic / inorganic hybrid particles A obtained in Example 1 were irradiated with ultraviolet rays from a distance of 20 cm for 180 seconds using a 120 W high-pressure mercury lamp to obtain organic / inorganic hybrid particles D.

Example 4
As the organic core particles, “Micropearl ELP-00375” (styrene / acrylic copolymer, average particle diameter of 3.75 μm) manufactured by Sekisui Chemical Co., Ltd. was prepared. Disperse 100 parts by weight of the organic core particles and 40 parts by weight of hexadecyltrimethylammonium bromide as a surfactant in a mixed solvent of 1800 parts by weight of acetone (SP value 9.9) and 200 parts by weight of water, 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 acetone was added, and the mixture was stirred at 25 ° C. for 24 hours while applying ultrasonic waves. The reaction solution is taken out, filtered with suction through a PTFE (polytetrafluoroethylene) membrane filter, washed with acetone twice, dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles A1 Got.

(Example 5)
As the organic core particles, “Micropearl ELP-00375” (styrene / acrylic copolymer, average particle diameter of 3.75 μm) manufactured by Sekisui Chemical Co., Ltd. was prepared. 100 parts by weight of the organic core particles and 40 parts by weight of hexadecyltrimethylammonium bromide as a surfactant are dispersed in a mixed solvent of 1800 parts by weight of acetonitrile (SP value 11.9) and 1200 parts by weight of water, 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 200 parts by weight of acetonitrile was added, and the mixture was stirred at 25 ° C. for 24 hours while applying ultrasonic waves. The reaction solution is taken out, filtered with suction through a PTFE (polytetrafluoroethylene) membrane filter, washed twice with acetonitrile, then dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles A2 Got.

(Example 6)
As the organic core particles, “Micropearl ELP-00375” (styrene / acrylic copolymer, average particle diameter of 3.75 μm) manufactured by Sekisui Chemical Co., Ltd. was prepared. 100 parts by weight of the organic core particles and 40 parts by weight of hexadecyltrimethylammonium bromide as a surfactant were mixed with 900 parts by weight of acetonitrile (SP value 11.9) and N, N-dimethylformaldehyde (SP value 12.1). ) It was dispersed in a mixed solvent of 900 parts by weight 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 600 parts by weight of acetonitrile and 600 parts by weight of N, N-dimethylformaldehyde was added and stirred at 25 ° C. for 24 hours while applying ultrasonic waves. The reaction solution was taken out, suction filtered through a PTFE (polytetrafluoroethylene) membrane filter, washed twice with acetonitrile, then dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles A3 Got.

(Example 7)
As the organic core particles, “Micropearl ELP-00375” (styrene / acrylic copolymer, average particle diameter of 3.75 μm) manufactured by Sekisui Chemical Co., Ltd. was prepared. 100 parts by weight of the organic core particles and 40 parts by weight of a surfactant hexadecyltrimethylammonium bromide are dispersed in a mixed solvent of 1800 parts by weight of isopropyl alcohol (SP value 11.4) and 200 parts by weight of water. 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 300 parts by weight of tetraethoxysilane in 1200 parts by weight of isopropyl alcohol was added, and the mixture was stirred at 25 ° C. for 24 hours while applying ultrasonic waves. The reaction solution is taken out, filtered with suction through a membrane filter made of PTFE (polytetrafluoroethylene), washed twice with isopropyl alcohol, then dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles A4 was obtained.

  100 parts by weight of the organic-inorganic hybrid particles A4 obtained above and 1000 parts by weight of hydrochloric acid were put into a beaker and stirred at 60 ° C. for 9 hours using a stirring and heating type hot stirrer. The reaction solution is taken out, filtered with suction through a membrane filter made of PTFE (polytetrafluoroethylene), washed twice with isopropyl alcohol, then dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles E was obtained.

(Example 8)
As the organic core particles, “Micropearl ELP-00375” (styrene / acrylic copolymer, average particle diameter of 3.75 μm) manufactured by Sekisui Chemical Co., Ltd. was prepared. 100 parts by weight of the organic core particles and 40 parts by weight of a surfactant hexadecyltrimethylammonium bromide are dispersed in a mixed solvent of 1800 parts by weight of isopropyl alcohol (SP value 11.4) and 200 parts by weight of water. 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 900 parts by weight of tetraethoxysilane in 1200 parts by weight of isopropyl alcohol was added, and the mixture was stirred at 25 ° C. for 24 hours while applying ultrasonic waves. The reaction solution is taken out, filtered with suction through a membrane filter made of PTFE (polytetrafluoroethylene), washed twice with isopropyl alcohol, then dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles A5 was obtained.

  100 parts by weight of the organic-inorganic hybrid particles A5 obtained above and 1000 parts by weight of hydrochloric acid were put into a beaker and stirred for 9 hours at 60 ° C. using a stirring and heating type hot stirrer. The reaction solution is taken out, filtered with suction through a membrane filter made of PTFE (polytetrafluoroethylene), washed twice with isopropyl alcohol, then dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles F was obtained.

(Comparative Example 1)
“Micropearl ELP-00375” (styrene / acrylic copolymer, average particle size of 3.75 μm) manufactured by Sekisui Chemical Co., Ltd. was used as the particles of Comparative Example 1 (organic core particles).

(Comparative Example 2)
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 a filter paper, taken out from water, and dried for 24 hours with a vacuum dryer at 50 ° C. to obtain polyurethane fine particles 1 bound with a silane coupling agent.

  100 parts by weight of the obtained polyurethane fine particles 1 are placed in a 1 L flask, 75 parts by weight of methanol (SP value 14.5), 25 parts by weight of water, 2 parts by weight of tetraethoxysilane, and 25% by weight aqueous ammonia solution. A tetraethoxysilane liquid containing 10 parts by weight 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 through a PTFE membrane filter, and washed twice using ethanol, and then dried in a vacuum dryer at 50 ° C. for 24 hours to obtain organic-inorganic hybrid particles 1.

(Comparative Example 3)
Organic-inorganic hybrid particles 2 were obtained in the same manner as in Comparative Example 2 except that the amount of tetraethoxysilane added was changed to 600 parts by weight.

(Comparative Example 4)
Organic-inorganic hybrid particles 3 were obtained in the same manner as in Comparative Example 2 except that the amount of tetraethoxysilane added was changed to 900 parts by weight.

(Comparative Example 5)
Organic-inorganic hybrid particles 4 were obtained in the same manner as in Comparative Example 2 except that the amount of tetraethoxysilane added was changed to 1800 parts by weight.

(Preparation of conductive particles)
A nickel layer was formed on the surface of the obtained organic-inorganic hybrid particles and other particles from the organic-inorganic hybrid particles and other particles obtained in the examples and comparative examples by electroless plating to produce conductive particles. . The nickel layer had a thickness of 0.1 μm.

(Evaluation)
(1) Inorganic shell specific gravity of organic-inorganic hybrid particles and organic core particles Using the obtained organic-inorganic hybrid particles and organic core particles, using a density bottle method density measuring device such as “Acpyc 1330” manufactured by Shimadzu Corporation, The true specific gravity of the organic-inorganic hybrid particles was measured under conditions of 15 to 25 ° C. and He gas as a carrier gas. Next, the value obtained by subtracting the specific gravity of the organic core particles was used as the specific gravity of the inorganic shell layer.

(2) Ratio of organic / inorganic hybrid particle and organic core particle diameter and inorganic shell thickness to radius of organic core particle The obtained organic / inorganic hybrid particle and organic core particle were analyzed using a scanning electron microscope (Hitachi High Technology Corporation). (“S-3500N”)), and a particle image of a magnification of 3000 is taken. The particle size of 50 particles in the obtained image is measured with a caliper, and the number average is obtained to determine the organic-inorganic hybrid particles and the organic core particles. The particle size was determined.

  The particle diameter of the organic core particles used when producing 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 particle.

(3) Pore volume and pore diameter Using the "BELSORP-mini" manufactured by Nippon Bell Co., Ltd., the pretreatment conditions were vacuum degassing at 80 ° C, and the gas type was nitrogen. As a method, the BET multipoint method (total pore volume P / P0 = 0.98) was used for measurement. The pore volume and pore diameter at that time were determined.

(4) Compression elastic modulus (10% K value and 30% K value) of organic-inorganic hybrid particles and organic core particles
The compression elastic modulus (10% K value and 30% K value) of the obtained organic-inorganic hybrid particles and organic core particles was measured by the above-described method using a micro compression tester (Fischer Scope H-100 manufactured by Fischer). It measured using.

(5) Load calculation method when 65% of organic / inorganic hybrid particles and organic core particles are distorted By the above-described method, the obtained organic / inorganic hybrid particles are micro-compressed tester (“Fischerscope H-100” manufactured by Fischer). , And the compressive load at 65% strain with respect to the particle diameter was read.

(6) Conductive material 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 microcapsule type curing 50 parts by weight of the agent (“HX3941HP” manufactured by Asahi Kasei Chemicals Co., Ltd.) and 2 parts by weight of the silane coupling agent (“SH6040” manufactured by Toray Dow Corning Silicone Co., Ltd.), and the content of the resulting conductive particles is 3%. % Was added and dispersed to obtain a conductive material (resin composition).

(7) Connection resistance Fabrication of connection structure:
A resin composition (conductive material) (before standing) obtained by the above evaluation was prepared. This conductive material was left at 25 ° C. for 1 hour.

The conductive material after being left standing was applied to a PET (polyethylene terephthalate) film having a thickness of 50 μm on which one side was released, 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. PET substrate (width 3 cm, length 3 cm) provided with ITO (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 Affixed to the center of the ITO electrode. 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. A 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. 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 was measured by the 4-terminal method. Connection resistance was determined according to the following criteria.

[Criteria for connection resistance]
○○○: Organic core particles are not destroyed, connection resistance is 2.0Ω or less ○○: Organic core particles are not destroyed, connection resistance exceeds 2.0Ω, 3.0Ω or less ○: Organic Core particle is not destroyed, connection resistance exceeds 3.0Ω, and 4.0Ω or less Δ: A part of organic core particle is destroyed, connection resistance exceeds 4.0Ω, and 5.0Ω or less × : Part of the organic core particle is destroyed, the connection resistance exceeds 5.0Ω, 6.0Ω or less XX: The organic core particle is destroyed, the connection resistance exceeds 7.0Ω

(8) Connection reliability Connection reliability was determined according to the following criteria. The connection structure obtained by the above (5) evaluation of connection resistance was left in an atmosphere of 85 ° C. and 85% for 100 hours. Thereafter, it was measured at 25 locations whether the adjacent electrodes were insulative or conductive. Connection reliability was determined according to the following criteria.

[Connection reliability criteria]
○○○: 30 or more between conductive electrodes ○○: 25 or more and less than 30 between conductive electrodes ○: 20 or more and less than 25 conductive electrodes : 15 or more and less than 20 between conductive electrodes ×: Less than 15 between conductive electrodes

(9) Display quality (spacer characteristics) of liquid crystal display devices (examples of use as spacers for liquid crystal display elements)
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, Examples 1 to 8 (organic-inorganic hybrid particles) and Comparative Examples 1 to 5 (organic core particles, SC) in 100% by weight of the obtained spacer dispersion liquid. The spacer for liquid crystal display element of the organic / inorganic hybrid particles using the agent was added so that the solid content concentration was 2% by weight and stirred to obtain a spacer dispersion liquid crystal display element. 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. A predetermined voltage was applied to the liquid crystal display device, and the presence or absence of display defects such as light leakage caused by the spacer particles was observed with an electron microscope, and the display quality was evaluated according to the following criteria.

[Judgment criteria for display quality]
○: Almost no spacer particles are present in the region corresponding to the pixel region (display portion), and display defects such as uneven spacing (gap) between the substrates due to the spacer particles and light leakage due to scratches on the substrate are not recognized at all. △: Excellent display quality △: Spacer particles are slightly present in the region corresponding to the pixel region (display portion), and light is lost due to unevenness (gap) of the substrate due to the spacer particles or damage to the substrate ×: Light caused by unevenness in the gap (gap) of the substrate or damage to the substrate caused by the spacer particles, in which there are many spacer particles in the region corresponding to the pixel region (display portion). Significant display defects such as missing

  The results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... Conductive particle 2 ... Conductive layer 11 ... Organic-inorganic hybrid particle 12 ... Organic core particle 13 ... Inorganic shell 21 ... Conductive particle 22 ... Conductive layer 22A ... 1st conductive layer 22B ... 2nd conductive layer 31 ... Conductive Conductive Particles 31a ... Protrusions 32 ... Conductive Layer 32a ... Protrusions 33 ... Core Material 34 ... Insulating Material 51 ... Connection Structure 52 ... First Connection Target Member 52a ... First Electrode 53 ... Second Connection Target Member 53a ... 2nd electrode 54 ... Connection part 81 ... Liquid crystal display element 82 ... Transparent glass substrate 83 ... Transparent electrode 84 ... Orientation film 85 ... Liquid crystal 86 ... Sealing agent

Claims (6)

An organic-inorganic hybrid particle, and a conductive layer disposed on the surface of the organic-inorganic hybrid particle,
The organic-inorganic hybrid particle includes an organic core particle and an inorganic shell disposed on the surface of the organic core particle,
In the organic-inorganic hybrid particle, the specific gravity of the inorganic shell is 1.8 g / cm ³ or more and 2.3 g / cm ³ or less, and the ratio of the thickness of the inorganic shell to the radius of the organic core particle is 0.00. The electroconductive particle which is 05 or more and 0.70 or less. The organic-inorganic hybrid particle comprises or contains no pores, and the pore volume of the organic-inorganic hybrid particles is 0.01 cm 3 / ^g or less, the conductive particles of claim 1. The electroconductive particle according to claim 1 or 2, wherein the organic-inorganic hybrid particle does not contain or contains pores, and the pore size of the organic-inorganic hybrid particle is 10 nm or less. The compressive elastic modulus at 10% compression of the organic-inorganic hybrid particles is 2000 mN / mm ² or more and 15000 mN / mm ² or less,
The ratio of the compressive elastic modulus when compressed by 10% of the organic-inorganic hybrid particles to the compressive elastic modulus when compressed by 30% of the organic-inorganic hybrid particles is 1.0 or more,
The organic-inorganic hybrid particles is load required when distorted 65% is not less than 2.5 mN, the conductive particles according to any one of claims 1 to 3. Including a conductive material and conductive particles, wherein the binder resin in any one of claims 1-4. A first connection object member having a first electrode on its surface;
A second connection target member having a second electrode on its surface;
It has a connection part which has connected the 1st above-mentioned connection object member and the above-mentioned 2nd connection object member, The above-mentioned connection part is formed with conductive particles given in any 1 paragraph of Claims 1-4. Is formed of a conductive material containing the conductive particles and a binder resin ,
Before Symbol a first electrode and the second electrode are electrically connected by the conductive particles, the connection structure.

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