JP2014208788A - Method for producing organic-inorganic hybrid particle, electroconductive particle, electroconductive material, and connection structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an organic-inorganic hybrid particle, in which the compression modulus of the organic-inorganic hybrid particle is made higher when the organic-inorganic hybrid particle to be obtained is compressed by 10% to suppress agglomeration thereof.SOLUTION: The method for producing the organic-inorganic hybrid particle 11 comprises the steps of: using a dispersion liquid containing an organic core 11, an inorganic monomer and a solvent; and disposing an inorganic shell 13 on the surface of the organic core 11 by a sol-gel reaction. When the sol-gel reaction is performed, both of the dispersion liquid and a filling liquid of an ultrasonic tank are irradiated with an ultrasonic wave or only the dispersion liquid is irradiated with the ultrasonic wave so that an irradiation amount of the ultrasonic wave per 1 L of the total amount of the dispersion liquid and the filling liquid or the irradiation amount of the ultrasonic wave per 1 L of the dispersion liquid is 4-30 W inclusive to obtain the organic-inorganic hybrid particle 11 having 0.05-0.70 inclusive of a ratio of the thickness of the inorganic shell 13 to the radius of the organic core 12.

Description

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

  Anisotropic conductive materials such as anisotropic conductive pastes and anisotropic conductive films are widely known. In the anisotropic conductive material, conductive particles are dispersed in a binder resin. The anisotropic conductive material is used to electrically connect electrodes of various connection target members such as a flexible printed circuit (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure. ing. In addition, conductive particles having resin particles and a conductive layer disposed on the surface of the resin particles may be used as the conductive particles.

  As an example of the resin particles used for the conductive particles, the following Patent Document 1 discloses organic-inorganic hybrid particles having an inorganic compound (A) as a shell and an organic polymer (b) as a core. . After producing the organic polymer fine particles (B0) formed of the organic polymer (b), the surface of the organic polymer fine particles (B0) is coated with the inorganic compound (A), whereby the organic-inorganic hybrid particles are obtained. Moreover, in patent document 1, as a method of disperse | distributing the organic polymer (b) in the water containing a dispersing agent, a high-speed shearing type, a friction type, a high-pressure jet type, an ultrasonic type etc. can be used preferably, and in these It is described that the high-speed shearing type is more preferable.

  In the following Patent Document 2, the step (I) of obtaining a polymerizable organopolysiloxane particle (S1) by hydrolyzing and condensing a silicon compound group containing a hydrolyzable silicon compound having a polymerizable organic group as an essential component, A step (II) of obtaining the organic-inorganic composite particles (P1) by polymerizing the polymerizable organopolysiloxane particles (S1), and adding a polymerizable monomer (M1) to the organic-inorganic composite particles (P1) An organic-inorganic hybrid comprising a step (III) of obtaining inorganic composite particles (P2) and a step (IV) of polymerizing the organic-inorganic composite particles (P2) to obtain core-shell type organic-inorganic composite particles (P3) A method for producing particles is disclosed.

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

  As an example of a method for producing resin particles used for the conductive particles or the spacers for liquid crystal display elements, the following Patent Document 3 includes a polyfunctional silane compound having a polymerizable unsaturated group and the presence of a surfactant. A method for producing organic-inorganic hybrid particles which are hydrolyzed and polycondensed under the conditions is disclosed. In Patent Document 3, the polyfunctional silane compound is at least one radical polymerizable group-containing first silicon compound selected from a compound represented by the following formula (X) and a derivative thereof.

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

JP 2006-156068 A JP 2010-229303 A JP 2000-204119 A

  In the conventional method for producing organic-inorganic hybrid particles as described in Patent Documents 1 to 3, the compression modulus (10% K value) when the obtained organic-inorganic hybrid particles are compressed by 10% may be relatively low. In addition, it is difficult to obtain organic-inorganic hybrid particles having a sufficiently high 10% K value. Furthermore, the obtained organic-inorganic hybrid particles may easily aggregate.

  For this reason, when the organic-inorganic hybrid particles are used as spacers for liquid crystal display elements and placed between substrates, or a conductive layer is formed on the surface and used as conductive particles to electrically connect electrodes. The spacer for liquid crystal display element or the conductive particles may not contact the substrate or the electrode sufficiently. The spacing between the substrates cannot be controlled with high accuracy, or the conduction reliability between the electrodes is lowered.

  An object of the present invention is to provide a method for producing organic-inorganic hybrid particles capable of increasing the compression elastic modulus at 10% compression of the obtained organic-inorganic hybrid particles and suppressing aggregation, and the organic-inorganic hybrid particles. It is providing the electroconductive particle, the electrically-conductive material, and connection structure using this.

  According to a broad aspect of the present invention, there is provided a method for producing organic-inorganic hybrid particles comprising an organic core and an inorganic shell disposed on the surface of the organic core, comprising the organic core, an inorganic monomer, and a solvent. A step of disposing the inorganic shell on the surface of the organic core by a sol-gel reaction using a dispersion liquid, and superposing both the dispersion liquid and the filling liquid in the ultrasonic tank in an ultrasonic tank. In the case of irradiating a sonic wave, when performing the sol-gel reaction, the dispersion liquid and the dispersion liquid and the filling liquid are adjusted so that the ultrasonic irradiation amount per liter of the total liquid volume of the dispersion liquid and the filling liquid is 4 W or more and 30 W or less. When irradiating the filling liquid with ultrasonic waves and irradiating only the dispersion liquid with ultrasonic waves, the amount of ultrasonic irradiation per liter of the dispersion liquid is 4 W or more and 30 W or less when performing the sol-gel reaction. So that the dispersion Is provided with a method for producing organic-inorganic hybrid particles, in which organic-inorganic hybrid particles having a ratio of the thickness of the inorganic shell to the radius of the organic core of 0.05 to 0.70 are obtained. The

  In a specific aspect of the method for producing organic-inorganic hybrid particles according to the present invention, ultrasonic waves are used until 60% by weight or more of the inorganic monomer reacts with respect to 100% by weight of the inorganic monomer in the dispersion before the reaction. Irradiate.

  On the specific situation with the manufacturing method of the organic inorganic hybrid particle which concerns on this invention, when performing the said sol-gel reaction, the temperature of the said dispersion liquid shall be 10 degreeC or more and 50 degrees C or less.

  In a specific aspect of the method for producing organic-inorganic hybrid particles according to the present invention, the number of the organic-inorganic hybrid particles aggregated is 50 or less per 100 organic-inorganic hybrid particles obtained. Get.

  The organic-inorganic hybrid particle manufacturing method according to the present invention is an organic-inorganic hybrid used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer, or used as a spacer for a liquid crystal display element. A method for producing particles is preferred. In addition, the method for producing organic-inorganic hybrid particles according to the present invention is preferably a method for producing organic-inorganic hybrid particles used for obtaining conductive particles having a conductive layer formed on the surface and having the conductive layer. .

  According to a wide aspect of the present invention, there is provided conductive particles comprising organic-inorganic hybrid particles obtained by the above-described method for producing organic-inorganic hybrid particles, and a conductive layer disposed on the surface of the organic-inorganic hybrid particles. The

  According to a wide aspect of the present invention, an organic-inorganic hybrid particle comprising conductive particles and a binder resin, wherein the conductive particles are obtained by the method for producing organic-inorganic hybrid particles described above, and the organic-inorganic hybrid particles A conductive material is provided comprising a conductive layer disposed on the surface.

  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 comprise organic-inorganic hybrid particles obtained by the above-described method for producing organic-inorganic hybrid particles, and a conductive layer disposed on the surface of the organic-inorganic hybrid particles, the first electrode and the A connection structure is provided in which a second electrode is electrically connected by the conductive particles.

  The method for producing organic-inorganic hybrid particles according to the present invention includes a step of disposing an inorganic shell on the surface of the organic core by a sol-gel reaction using a dispersion containing an organic core, an inorganic monomer, and a solvent. Furthermore, in the method for producing organic-inorganic hybrid particles according to the present invention, when irradiating both the dispersion liquid and the filling liquid in the ultrasonic tank with ultrasonic waves in the ultrasonic tank, the sol-gel reaction is performed. When performing, the dispersion liquid and the filling liquid are irradiated with ultrasonic waves so that the ultrasonic irradiation amount per liter of the total liquid volume of the dispersion liquid and the filling liquid is 4 W or more and 30 W or less, and the dispersion is performed. When irradiating only the liquid with ultrasonic waves, when performing the sol-gel reaction, the dispersion liquid is irradiated with ultrasonic waves so that the amount of ultrasonic irradiation per liter of the dispersion liquid is 4 W or more and 30 W or less. , The above inorganic In order to obtain organic-inorganic hybrid particles in which the ratio of the thickness of the shell to the radius of the organic core is 0.05 or more and 0.70 or less, the compression elastic modulus at 10% compression of the obtained organic-inorganic hybrid particles is increased. And aggregation can be suppressed.

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.

  Hereinafter, the present invention will be described in detail.

(Organic / inorganic hybrid particles and organic / inorganic hybrid particle production method)
The method for producing organic-inorganic hybrid particles according to the present invention is a method for producing organic-inorganic hybrid particles comprising an organic core and an inorganic shell disposed on the surface of the organic core. The method for producing organic-inorganic hybrid particles according to the present invention includes a step of disposing the inorganic shell on the surface of the organic core by a sol-gel reaction using a dispersion liquid containing the organic core, an inorganic monomer, and a solvent. . 1) In the method for producing organic-inorganic hybrid particles according to the present invention, when irradiating both the dispersion liquid and the filling liquid in the ultrasonic tank with ultrasonic waves in the ultrasonic tank, the sol-gel reaction is performed. When performing, the dispersion liquid and the filling liquid are irradiated with ultrasonic waves so that the ultrasonic irradiation amount per liter of the total liquid volume of the dispersion liquid and the filling liquid is 4 W or more and 30 W or less. On the other hand, 2) In the method for producing organic-inorganic hybrid particles according to the present invention, when only the dispersion liquid is irradiated with ultrasonic waves, the amount of ultrasonic irradiation per liter of the dispersion liquid when performing the sol-gel reaction. The dispersion is irradiated with ultrasonic waves so that is 4 W or more and 30 W or less. Furthermore, in the method for producing organic-inorganic hybrid particles according to the present invention, the ratio of the thickness of the inorganic shell to the radius of the organic core (inorganic shell thickness / organic core radius) is 0.05 or more and 0.70 or less. Organic-inorganic hybrid particles are obtained.

  In the method for producing organic-inorganic hybrid particles according to the present invention, since the above-described configuration is provided, the obtained organic-inorganic hybrid particles have a high compressive elastic modulus (10% K value) at 10% compression and can be obtained. Aggregation of the resulting organic-inorganic hybrid particles can be suppressed. In particular, the inventors found for the first time that the 10% K value is increased by irradiating ultrasonic waves with a specific ultrasonic irradiation dose. It is considered that the 10% K value is increased because the degree of condensation of siloxane bonds is improved by the ultrasonic irradiation conditions.

  As a result of being able to increase the 10% K value, the organic-inorganic hybrid particles are used as spacers for liquid crystal display elements and disposed between the substrates, or a conductive layer is formed on the surface and used as conductive particles between the electrodes. Are electrically connected to each other, the spacer for the liquid crystal display element or the conductive particles sufficiently contacts the substrate or the electrode. For this reason, the space | interval between board | substrates can be controlled with high precision, and the conduction | electrical_connection reliability between electrodes can fully be improved.

  Moreover, as a result of suppressing aggregation of the organic-inorganic hybrid particles, the spacer for liquid crystal display element or the conductive particles can be efficiently arranged between the substrates or between the electrodes. For this reason, the display quality is unlikely to deteriorate in the liquid crystal display device, and the connection resistance is reduced in the connection structure in which the electrodes are electrically connected. Furthermore, insulation reliability can be improved in the connection structure in which the electrodes are electrically connected.

  In addition, when using organic-inorganic hybrid particle | grains as a spacer for liquid crystal display elements, the spacer for liquid crystal display elements is added in binder resin, for example in order to wet-spread. The conductive particles are often added to a binder resin and used in the form of a conductive paste or a conductive film.

  In the method for producing organic / inorganic hybrid particles according to the present invention, a dispersion containing the organic core, the inorganic monomer, and the solvent is used. The dispersion includes the organic core, the inorganic monomer, and the solvent. The inorganic shell is formed by polymerizing the inorganic monomer.

  Examples of the solvent include water, alcohol, ether solvent, acetonitrile and the like.

  The content of the organic core in 100% by weight of the dispersion before the reaction is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 30% by weight or less, more preferably 10% by weight or less. It is.

  The content of the inorganic monomer in 100% by weight of the dispersion before the reaction is preferably 0.1% by weight or more, more preferably 1% by weight, preferably 50% by weight or less, more preferably 25% by weight or less. It is. The content of the inorganic monomer used in the total of 100% by weight of the component excluding the inorganic monomer and the inorganic monomer used in the dispersion before the reaction is preferably 0.1% by weight or more, more preferably 1% by weight. In addition, it is preferably 50% by weight or less, more preferably 25% by weight or less.

  When ultrasonic waves are applied to both the dispersion liquid and the filling liquid in the ultrasonic tank in an ultrasonic tank, the total liquid of the dispersion liquid and the filling liquid is used when performing the sol-gel reaction. The dispersion liquid and the filling liquid are irradiated with ultrasonic waves so that the ultrasonic irradiation amount per 1 L is 4 W or more and 30 W or less. For example, when the ultrasonic wave of 100 W is applied to the total liquid volume 10 L of the dispersion liquid and the filling liquid, the ultrasonic wave irradiation amount per 1 L of the total liquid volume of the dispersion liquid and the filling liquid is 10 W. . From another viewpoint, when the ultrasonic density is (ultrasonic irradiation amount (W)) / (total liquid amount of dispersion and filling liquid (L)), the sol-gel reaction is performed. The dispersion liquid and the filling liquid are irradiated with ultrasonic waves so that the ultrasonic density is 4 W / L or more and 30 W / L or less.

  When only the dispersion liquid is irradiated with ultrasonic waves, the ultrasonic wave is applied to the dispersion liquid so that the amount of ultrasonic irradiation per liter of the dispersion liquid is 4 W or more and 30 W or less when performing the sol-gel reaction. Irradiate. For example, when 100 W of ultrasonic waves is applied to the dispersion 10 L, the amount of ultrasonic irradiation per 1 L of the dispersion is 10 W. From another viewpoint, when the ultrasonic density is (ultrasonic irradiation amount (W)) / (dispersion liquid amount (L)), the ultrasonic density is 4 W when the sol-gel reaction is performed. The dispersion is irradiated with ultrasonic waves so as to be not less than / L and not more than 30 W / L.

  It is preferable to irradiate both the dispersion liquid and the filling liquid in the ultrasonic tank with ultrasonic waves in the ultrasonic tank. However, you may irradiate only the said dispersion liquid with an ultrasonic wave.

  When the ultrasonic irradiation amount is less than 4 W (the ultrasonic density is less than 4 W / L), the 10% K value of the obtained organic-inorganic hybrid particles is not sufficiently high, and aggregation of the organic-inorganic hybrid particles occurs. It becomes easy. If the amount of ultrasonic irradiation is greater than 30 W (the ultrasonic density is greater than 30 W / L), the formed inorganic shell may be destroyed because the ultrasonic waves are too strong. From the viewpoint of further increasing the 10% K value and further suppressing the aggregation of the organic-inorganic hybrid particles, the ultrasonic irradiation amount is preferably 6 W or more, and preferably 20 W or less.

  When performing the sol-gel reaction, the ultrasonic wave may be irradiated from the start of the sol-gel reaction to the end of the sol-gel reaction, or may be irradiated from the start of the sol-gel reaction to the middle stage of the sol-gel reaction. To the end of the sol-gel reaction. Moreover, an ultrasonic wave may be irradiated continuously and may be irradiated intermittently.

  In carrying out the sol-gel reaction, the temperature of the dispersion is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, preferably 50 ° C. or lower, more preferably 40 ° C. or lower. When the temperature of the dispersion is equal to or higher than the lower limit, the production efficiency of the organic-inorganic hybrid particles is further increased. Aggregation of organic-inorganic hybrid particles is further suppressed when the temperature of the dispersion is equal to or lower than the upper limit.

  From the viewpoint of effectively increasing the dispersibility of the obtained organic-inorganic hybrid particles and further reducing the connection resistance between the electrodes, the inorganic compound is added to 100% by weight of the inorganic monomer in the dispersion before the reaction. It is preferable to irradiate ultrasonic waves until 50% by weight or more of the monomers have reacted. It is more preferable to irradiate ultrasonic waves until 55% by weight or more of the inorganic monomer reacts with respect to 100% by weight of the inorganic monomer in the dispersion before the reaction. It is more preferable to irradiate ultrasonic waves until 60% by weight or more of the inorganic monomer reacts with respect to 100% by weight of the inorganic monomer in the dispersion before the reaction. It is particularly preferable to irradiate the ultrasonic wave until 65% by weight or more of the inorganic monomer reacts with respect to 100% by weight of the inorganic monomer in the dispersion before the reaction. It is preferable to start ultrasonic irradiation until 5% by weight of the inorganic monomer reacts with respect to 100% by weight of the inorganic monomer in the dispersion before the reaction.

  The frequency at the time of irradiating the ultrasonic waves is preferably 28 kHz or more, and preferably 100 kHz or less. When the frequency is in the range of 28 to 100 kHz, the 10% K value is sufficiently high and aggregation is sufficiently suppressed by irradiating the ultrasonic wave with the ultrasonic irradiation amount within the above-described range.

  The dispersion may contain a surfactant, a catalyst such as an aqueous ammonia solution, and the like in addition to the organic core, the inorganic monomer, and the solvent.

  As a specific method for performing the sol-gel reaction, a dispersion liquid in which an inorganic monomer such as tetraethoxysilane coexists in a liquid containing an organic core, a solvent such as water or alcohol, a surfactant, and a catalyst such as an aqueous ammonia solution. And a method of performing an interfacial sol reaction. In the sol-gel method, the inorganic monomer is preferably hydrolyzed and polycondensed. The inorganic monomer is preferably a metal alkoxide.

  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 hexadecyltrimethylammonium bromide.

  In the sol-gel reaction, it is desirable that the reaction vessel containing the solvent, the organic core, and the surfactant is irradiated with ultrasonic waves to disperse each component in the reaction vessel in advance before adding the inorganic monomer. The dispersion time is preferably 1 minute or more, more preferably 5 minutes or more.

  In the sol-gel reaction, it is possible to add the inorganic monomer and the catalyst separately after starting the reaction.

  The ratio of the thickness of the inorganic shell to the radius of the organic core (the thickness of the inorganic shell / the radius of the organic core) is 0.05 or more and 0.70 or less. When the ratio is not less than the above lower limit and not more than the above upper limit, the 10% K value of the organic-inorganic hybrid particles can be sufficiently increased, the connection resistance between the electrodes can be decreased, and the insulation reliability can be increased. be able to. The ratio (inorganic shell thickness / organic core radius) is preferably 0.1 or more, more preferably 0.15 or more, preferably 0.65 or less, more preferably 0.60 or less. When the above ratio is preferably not less than the above lower limit and not more than the above upper limit, the 10% K value of the organic-inorganic hybrid particles can be easily made not less than the above lower limit and not more than the above upper limit, and the connection resistance between the electrodes is further reduced. Insulation reliability can be further increased.

Compression modulus when the organic-inorganic hybrid particles 10% compressive deformation (10% K value) is preferably 2000N / mm ² or more, more preferably 3000N / mm ² or more, more preferably 3600N / mm ² or more, even more preferably 4000 N / mm ² or more, particularly preferably 5000N / mm ² or more, most preferably 6000 N / mm ² or more, preferably 15000 N / mm ² or less, more preferably 10000 N / mm ² or less, more preferably 8500N / mm ² or less. The organic-inorganic hybrid particles having the 10% K value of not less than the above lower limit and not more than the above upper limit have good compression deformation characteristics.

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

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

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

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

  In the organic-inorganic hybrid particles according to the present invention, the number of the organic-inorganic hybrid particles aggregated per 100 organic / inorganic hybrid particles obtained is preferably 50 or less, more preferably 30 or less, and still more preferably 10 Or less, particularly preferably 5 or less, and most preferably 0.5 or less. For example, in 100 organic-inorganic hybrid particles, when there are 20 aggregates of 2 and 60 organic-inorganic hybrid particles present alone, the aggregated per 100 organic-inorganic hybrid particles obtained. The number of the above organic-inorganic hybrid particles is 40. The smaller the number of the aggregated organic-inorganic hybrid particles, the more efficiently the spacers for liquid crystal display elements or the conductive particles can be arranged between the substrates or the electrodes. For this reason, the display quality in the liquid crystal display device is more difficult to deteriorate, and the connection resistance is further reduced in the connection structure in which the electrodes are electrically connected. Furthermore, in the connection structure in which the electrodes are electrically connected, the insulation reliability is further increased.

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

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

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

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

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

  From the viewpoint of effectively increasing the 10% K value and effectively suppressing aggregation, the organic core is preferably a polymer of a styrene monomer or a carboxyl group-containing monomer.

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

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

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

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

  From the viewpoint of effectively increasing the 10% K value, the inorganic shell preferably contains silica as a main component. When the main component of the inorganic shell is silica, 50% by weight or more in 100% by weight of the inorganic shell is silica. The content of silica in 100% by weight of the inorganic shell is more preferably 60% by weight or more, and still more preferably 80% by weight or more.

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

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

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

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

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

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

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

  When R1 is an alkyl group having 1 to 30 carbon atoms, specific examples of R1 include methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, n-hexyl group, cyclohexyl group, n-octyl group, And n-decyl group. This alkyl group preferably has 10 or less carbon atoms, more preferably 6 or less. The alkyl group includes a cycloalkyl group.

  Examples of the polymerizable double bond include a carbon-carbon double bond. When R1 is an organic group having 1 to 30 carbon atoms having a polymerizable double bond, specific examples of R1 include a vinyl group, an allyl group, an isopropenyl group, and a 3- (meth) acryloxyalkyl group. Etc. Examples of the (meth) acryloxyalkyl group include a (meth) acryloxymethyl group, a (meth) acryloxyethyl group, and a (meth) acryloxypropyl group. The carbon number of the organic group having 1 to 30 carbon atoms having a polymerizable double bond is preferably 2 or more, preferably 30 or less, more preferably 10 or less. The above “(meth) acryloxy” means methacryloxy or acryloxy.

  When R1 is an organic group having 1 to 30 carbon atoms having an epoxy group, specific examples of R1 include 1,2-epoxyethyl group, 1,2-epoxypropyl group, 2,3-epoxypropyl group, Examples include 3,4-epoxybutyl group, 3-glycidoxypropyl group, and 2- (3,4-epoxycyclohexyl) ethyl group. 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. In order to effectively increase the content of silicon atoms contained in the inorganic shell, R2 preferably represents a methyl group or an ethyl group.

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

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

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

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

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

M (OR2) ₄ Formula (1a)

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

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

Si (OR2) ₄ Formula (1Aa)

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

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

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

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

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

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

  The ratio of the number of silicon atoms in which four -O-Si groups are directly bonded and the four oxygen atoms in the four -O-Si groups are directly bonded (the ratio of the number of Q4 (%)). As a measuring method, for example, using an NMR spectrum analyzer, Q4 (four -O-Si groups are directly bonded and four oxygen atoms in the four -O-Si groups are directly bonded). The peak area of silicon atoms) and Q1 to Q3 (1 to 3 —O—Si groups are directly bonded, and 1 to 3 oxygen atoms in 1 to 3 —O—Si groups are directly bonded to each other. And a peak area of silicon atoms). By this method, in the total number of 100% of silicon atoms contained in the inorganic shell, four —O—Si groups are directly bonded, and four silicon atoms in the four —O—Si groups are directly bonded. The ratio of the number of bonded silicon atoms (the ratio of the number of Q4) can be obtained. In addition, in the NMR measurement result which calculated | required the ratio of the number of Q4 of the Example mentioned later, four -O-Si groups are couple | bonded directly and the four silicon atoms in four said -O-Si groups couple | bond together directly. The peak derived from the silicon atom is evaluated.

  The thickness of the inorganic shell is preferably 1 nm or more, more preferably 10 nm or more, still more preferably 50 nm or more, particularly preferably 100 nm or more, preferably 100,000 nm or less, more preferably 10,000 nm or less, still more preferably 2000 nm or less. When the thickness of the inorganic shell is not less than the above lower limit and not more than the above upper limit, the 10% K value shows a more suitable value, and the organic / inorganic hybrid particles are suitably used for the use of conductive particles and spacers for liquid crystal display elements. It becomes possible. The thickness of the inorganic shell is an average thickness per organic-inorganic hybrid particle. The thickness of the inorganic shell can be controlled by controlling the sol-gel method.

  In the present invention, the thickness of the inorganic shell is determined by observing the organic-inorganic hybrid particles using a scanning electron microscope, and measuring the average particle size of 50 arbitrarily selected organic-inorganic hybrid particles with calipers, and the organic core. It can obtain | require from the difference with the average value of the particle size of. The particle diameter of the organic-inorganic hybrid particles means a diameter when the organic-inorganic hybrid particles are true spherical, and means a maximum diameter when the organic-inorganic hybrid particles have a shape other than the true spherical shape. The radius of the organic-inorganic hybrid particle is ½ of the particle size.

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

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

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

  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. 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. The organic / inorganic hybrid particles are preferably used as spacers for liquid crystal display elements. Since the organic-inorganic hybrid particles have a low 10% K value and aggregation is suppressed in the organic-inorganic hybrid particles, the organic-inorganic hybrid particles are used as spacers for liquid crystal display elements, and are arranged between substrates, By arranging conductive particles using the above organic-inorganic hybrid particles in between, the spacing between the substrates can be controlled with high accuracy, the connection resistance between the electrodes can be lowered, and the conduction reliability between the electrodes can be increased. Can do.

  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.

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

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

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

  The organic / inorganic hybrid particle 11 includes an organic core 12 and an inorganic shell 13 disposed on the surface of the organic core 12. The inorganic shell 13 covers the surface of the organic core 12. The conductive layer 2 is disposed on the surface of the inorganic shell 13. The conductive layer 2 covers the surface of the inorganic shell 13.

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

  The conductive particles 21 shown in FIG. 2 have organic / inorganic hybrid particles 11 and a conductive layer 22 disposed on the surface of the organic / inorganic hybrid particles 11. The conductive layer 22 includes a first conductive layer 22A that is an inner layer and a second conductive layer 22B that is an outer layer. On the surface of the organic / inorganic hybrid particle 11, the first conductive layer 22 </ b> A is disposed. On the surface of the inorganic shell 13, the first conductive layer 22A is disposed. A second conductive layer 22B is disposed on the surface of the first conductive layer 22A.

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

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

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

  The conductive particles 31 have a plurality of protrusions 31a on the conductive surface. The conductive layer 32 has a plurality of protrusions 32a on the outer surface. Thus, the conductive particles may have protrusions on the conductive surface or may have protrusions on the outer surface of the conductive layer. A plurality of core materials 33 are disposed on the surface of the organic-inorganic hybrid particles 11. A plurality of core materials 33 are arranged on the surface of the inorganic shell 13. The plurality of core materials 33 are embedded in the conductive layer 32. The core substance 33 is disposed inside the protrusions 31a and 32a. The conductive layer 32 covers a plurality of core materials 33. The outer surface of the conductive layer 32 is raised by the plurality of core materials 33, and protrusions 31a and 32a are formed.

  The conductive particles 31 have an insulating material 34 disposed on the outer surface of the conductive layer 32. At least a part of the outer surface of the conductive layer 32 is covered with an insulating material 34. The insulating substance 34 is made of an insulating material and is an insulating particle. Thus, the said electroconductive particle may have the insulating substance arrange | positioned on the outer surface of a conductive layer.

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

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

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

  The particle diameter of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 520 μm or less, more preferably 500 μm or less, still more preferably 100 μm or less, still more preferably 50 μm or less, and particularly preferably 20 μm. It is as follows. When the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrode becomes sufficiently large when the electrodes are connected using the conductive particles, and the conductive layer When forming the conductive particles, it becomes difficult to form aggregated conductive particles. Moreover, the space | interval between the electrodes connected via the electroconductive particle does not become large too much, and it becomes difficult for a conductive layer to peel from the surface of an organic inorganic hybrid particle. Further, when the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be suitably used for the use of the conductive material.

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

  The thickness of the conductive layer is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 10 μm or less, more preferably 1 μm or less, still more preferably 0.5 μm or less, and particularly preferably 0.3 μm or less. . The thickness of the conductive layer is the thickness of the entire conductive layer when the conductive layer is a multilayer. When the thickness of the conductive layer is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed when connecting the electrodes. .

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Example 1
(1) Preparation of organic-inorganic hybrid particles “Micropearl EYP-0025” (acrylic polymer, average particle size 2.5 μm) manufactured by Sekisui Chemical Co., Ltd. was prepared as an organic core. 1 part by weight of this organic core, 0.4 part by weight of hexadecyltrimethylammonium bromide as a surfactant, 0.8 part by weight of 25% aqueous ammonia solution, 18 parts by weight of 2-propanol and 2 parts by weight of water The mixture was dispersed in a mixed solvent and placed in a separable flask. Into a separable flask, 4.6 parts by weight of tetraethyl orthosilicate was added to prepare a dispersion.

  In Example 1, ultrasonic waves were applied to both the dispersion liquid and the filling liquid in the ultrasonic tank in an ultrasonic tank.

  The dispersion liquid and the filling liquid have a frequency of 45 kHz so that the ultrasonic irradiation amount per liter of the total liquid volume of the dispersion liquid and the filling liquid is 7.5 W (ultrasonic irradiation density 7.5 W / L). The mixture was stirred at 25 ° C. for 24 hours while irradiating with ultrasonic waves. When performing this sol-gel reaction, ultrasonic waves were irradiated until 88% by weight of the inorganic monomer reacted with respect to 100% by weight of the inorganic monomer in the dispersion before the reaction. The reaction was terminated when 88% by weight of the inorganic monomer reacted with 100% by weight of the inorganic monomer in the dispersion before the reaction. The reaction solution is taken out, suction filtered through a membrane filter made of PTFE (polytetrafluoroethylene), washed with ethanol twice, dried in a vacuum dryer at 50 ° C. for 24 hours, and organic-inorganic hybrid particles are removed. Obtained.

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

(Example 2)
Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that when performing the sol-gel reaction, ultrasonic waves were irradiated so that the ultrasonic irradiation amount was 15 W.

Example 3
The organic core was changed to “Micropearl EYP-00225” (acrylic polymer, average particle size 2.25 μm) manufactured by Sekisui Chemical Co., Ltd., the amount of tetraethyl orthosilicate was changed to 10.3 parts by weight, and When performing the sol-gel reaction, ultrasonic waves are irradiated until 100% by weight of the inorganic monomer in the dispersion before the reaction reacts with 77% by weight of the inorganic monomer in the dispersion before the reaction. Organic inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the reaction was terminated when 77% by weight of the inorganic monomer reacted with respect to 100% by weight of the inorganic monomer. .

Example 4
Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 3 except that when performing the sol-gel reaction, ultrasonic waves were irradiated so that the ultrasonic irradiation amount was 15 W.

(Example 5)
When performing the sol-gel reaction, ultrasonic waves are irradiated until 60% by weight of the inorganic monomer reacts with respect to 100% by weight of the inorganic monomer in the dispersion before the reaction, and in the dispersion before the reaction. Organic inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the reaction was terminated when 60% by weight of the inorganic monomer reacted with respect to 100% by weight of the inorganic monomer. .

(Example 6)
In performing the sol-gel reaction, ultrasonic waves are irradiated until 50% by weight of the inorganic monomer reacts with respect to 100% by weight of the inorganic monomer in the dispersion before the reaction, and in the dispersion before the reaction. Organic inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the reaction was terminated when 50% by weight of the inorganic monomer reacted with respect to 100% by weight of the inorganic monomer. .

(Example 7)
Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the frequency when irradiating ultrasonic waves was changed from 45 kHz to 28 kHz.

(Example 8)
Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the frequency when irradiating ultrasonic waves was changed from 45 kHz to 100 kHz.

Example 9
When performing the sol-gel reaction, ultrasonic waves are applied to 100% by weight of the inorganic monomer in the dispersion before the reaction until 55% by weight of the inorganic monomer reacts, and the dispersion in the dispersion before the reaction Organic inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the reaction was terminated when 55% by weight of the inorganic monomer reacted with respect to 100% by weight of the inorganic monomer. .

(Example 10)
Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the addition amount of tetraethyl orthosilicate was changed to 2.2 parts by weight.

(Example 11)
Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the addition amount of tetraethyl orthosilicate was changed to 14 parts by weight.

(Example 12)
Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the addition amount of tetraethyl orthosilicate was changed to 12 parts by weight.

(Comparative Example 1)
When performing the sol-gel reaction, the dispersion is stirred without irradiating ultrasonic waves in an ultrasonic bath, and the inorganic monomer is 88 wt% with respect to 100 wt% of the inorganic monomer in the dispersion before the reaction. Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the reaction was terminated when the reaction was completed.

(Comparative Example 2)
When the sol-gel reaction is performed, the dispersion is stirred without irradiating ultrasonic waves in an ultrasonic bath, and the inorganic monomer is 77% by weight with respect to 100% by weight of the inorganic monomer in the dispersion before the reaction. Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 3 except that the reaction was terminated when the reaction was completed.

(Comparative Example 3)
When performing the sol-gel reaction, ultrasonic waves were irradiated so that the ultrasonic irradiation amount was 3 W, and the inorganic monomers were 88 wt% with respect to 100 wt% of the inorganic monomers in the dispersion before the reaction. Organic-inorganic hybrid particles and conductive particles were obtained in the same manner as in Example 1 except that the reaction was terminated when the reaction was performed.

(Evaluation)
(1) Particle size of organic / inorganic hybrid particle, particle size of organic core and thickness of inorganic shell The obtained organic / inorganic hybrid particle was 3000 times with a scanning electron microscope (“S-3500N” manufactured by Hitachi High-Technology Corporation). The particle size of the organic-inorganic hybrid particles was determined by measuring the particle size of 50 particles in the obtained image with a caliper and determining the number average.

  The particle size of the organic core used for preparing the organic / inorganic hybrid particles was also measured by the same method as described above. The thickness of the inorganic shell was determined from the difference between the particle size of the organic-inorganic hybrid particle and the particle size of the organic core.

(2) The above-mentioned compression elastic modulus (10% K value) of organic-inorganic hybrid particles
The compression elastic modulus (10% K value) of the obtained organic-inorganic hybrid particles was measured by the above-described method using a micro compression tester (“Fischerscope H-100” manufactured by Fischer).

(3) Aggregation rate 200 organic-inorganic hybrid particles obtained were observed using a scanning electron microscope (SEM). The number of the organic-inorganic hybrid particles aggregated per 100 organic-inorganic hybrid particles obtained was determined.

(4) Reaction rate The reaction rate of tetraethyl orthosilicate was determined by comparing the ratio of the organic core in the dispersion before the sol-gel reaction with the ratio of the organic-inorganic hybrid particles in the dispersion during the sol-gel reaction. The ratio of the organic / inorganic hybrid particles is determined by taking out a part of the dispersion, suction filtering with a membrane filter made of PTFE (polytetrafluoroethylene), and repeating washing with ethanol twice, followed by vacuum at 50 ° C. It dried for 24 hours with the dryer and calculated | required from the weight of the obtained organic inorganic hybrid particle. The reaction rate of tetraethyl orthosilicate was calculated from the weight of the inorganic shell obtained by subtracting the weight of the organic core from the weight of the organic-inorganic hybrid particle, assuming that the ethoxy group of tetraethyl orthosilicate was completely condensed. And asked. The reaction rate may be used as a correlation diagram with the sol-gel reaction time to stop the reaction at a desired reaction rate.

(5) Dispersibility 1
The obtained organic-inorganic hybrid particles were used as spacers for liquid crystal display elements. To a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, a spacer for a liquid crystal display element is added so as to have a solid content concentration of 2% by weight in 100% by weight of the obtained spacer dispersion, and stirred. A spacer dispersion liquid for a liquid crystal display element was obtained.

  The obtained spacer dispersion liquid for a liquid crystal display element was wet-sprayed on a glass substrate, 5 cm square was observed with an optical microscope, and the dispersibility of the particles was observed. Dispersibility 1 was determined according to the following criteria.

[Criteria for dispersibility 1]
○: Less than 10 aggregated organic-inorganic hybrid particles per 100 organic-inorganic hybrid particles. Δ: 10 or more aggregated organic-inorganic hybrid particles per 100 organic-inorganic hybrid particles. Less than ×: The number of aggregated organic / inorganic hybrid particles is 60 or more per 100 organic / inorganic hybrid particles.

(6) Dispersibility 2
10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and a microcapsule type curing agent (Asahi Kasei Chemicals) 50 parts by weight of “HX3941HP” manufactured by “HX3941HP” and 2 parts by weight of a silane coupling agent (“SH6040” manufactured by Toray Dow Corning Silicone Co., Ltd.) are mixed so that the content of the obtained conductive particles is 3% by weight. The conductive material (resin composition) was obtained by adding and dispersing.

  The obtained conductive material was left at 25 ° C. for 10 minutes. It was observed whether or not the conductive particles were settled in the dispersion after being allowed to stand. Dispersibility 2 was determined according to the following criteria.

[Criteria for dispersibility 2]
○: Conductive particles do not settle and aggregate in the dispersion after standing ×: Conductive particles sediment or aggregate in the dispersion after standing

(7) Connection resistance Fabrication of connection structure:
The resin composition (conductive material) (before standing) obtained by the evaluation of (6) Dispersibility 2 was prepared. This conductive material was left at 25 ° C. for 10 minutes.

  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.

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

  The results are shown in Table 1 below. The aspect ratio of the organic-inorganic hybrid particles obtained in Examples 1 to 12 was 1.2 or less. Moreover, although the evaluation results of the connection resistances of Examples 5 and 9 to 11 were all “◯”, the connection resistances of Examples 10 and 11 were lower than the connection resistances of Examples 5 and 9. The evaluation results of the connection resistances of Examples 5 and 9 were all “◯”, but the connection resistance of Example 9 was lower than the connection resistance of Example 5.

(8) Usage example as spacer for liquid crystal display element Production of STN type liquid crystal display element:
In a dispersion medium containing 70 parts by weight of isopropyl alcohol and 30 parts by weight of water, the liquid crystal display element spacers (organic-inorganic hybrid particles) of Examples 1 to 12 in 100% by weight of the obtained spacer dispersion liquid have a solid content concentration of 2. It added so that it might become weight%, and stirred, and the spacer dispersion liquid for liquid crystal display elements was obtained.

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

  In the obtained liquid crystal display element, the space | interval between board | substrates was favorably controlled by the spacer for liquid crystal display elements of Examples 1-12. Moreover, the liquid crystal display element showed favorable display quality.

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

Claims (9)

A method for producing organic-inorganic hybrid particles comprising an organic core and an inorganic shell disposed on the surface of the organic core,
Using a dispersion containing the organic core, an inorganic monomer, and a solvent, and a step of disposing the inorganic shell on the surface of the organic core by a sol-gel reaction,
When ultrasonic waves are applied to both the dispersion liquid and the filling liquid in the ultrasonic tank in an ultrasonic tank, the total liquid of the dispersion liquid and the filling liquid is used when performing the sol-gel reaction. When irradiating the dispersion liquid and the filling liquid with ultrasonic waves and irradiating only the dispersion liquid with ultrasonic waves so that the ultrasonic irradiation amount per 1 L is 4 W or more and 30 W or less, the sol-gel reaction When performing the above, irradiating the dispersion with ultrasonic waves so that the amount of ultrasonic irradiation per liter of the dispersion is 4 W or more and 30 W or less,
A method for producing organic-inorganic hybrid particles, wherein organic-inorganic hybrid particles having a ratio of the thickness of the inorganic shell to the radius of the organic core of 0.05 to 0.70 are obtained.   The method for producing organic-inorganic hybrid particles according to claim 1, wherein ultrasonic waves are irradiated until 60% by weight or more of the inorganic monomer reacts with respect to 100% by weight of the inorganic monomer in the dispersion before the reaction.   The method for producing organic-inorganic hybrid particles according to claim 1 or 2, wherein the temperature of the dispersion is set to 10 ° C or higher and 50 ° C or lower when performing the sol-gel reaction.   The organic-inorganic hybrid according to any one of claims 1 to 3, wherein the organic-inorganic hybrid particles in which the number of aggregated organic-inorganic hybrid particles is 50 or less per 100 obtained organic-inorganic hybrid particles. A method for producing hybrid particles.   The method according to claim 1, wherein a conductive layer is formed on the surface and used for obtaining conductive particles having the conductive layer, or a method for producing organic-inorganic hybrid particles used as a spacer for a liquid crystal display element. The manufacturing method of the organic-inorganic hybrid particle | grains of any one.   The manufacturing method of the organic-inorganic hybrid particle | grains of Claim 5 which is a manufacturing method of the organic-inorganic hybrid particle | grains used in order to obtain the electroconductive particle which has a conductive layer formed on the surface and has the said conductive layer.   Electroconductive particle provided with the organic inorganic hybrid particle obtained by the manufacturing method of the organic inorganic hybrid particle of any one of Claims 1-6, and the conductive layer arrange | positioned on the surface of the said organic inorganic hybrid particle. Containing conductive particles and a binder resin,
An organic-inorganic hybrid particle obtained by the method for producing organic-inorganic hybrid particles according to any one of claims 1 to 6, and a conductive layer disposed on a surface of the organic-inorganic hybrid particle, A conductive material comprising. A first connection object member having a first electrode on its surface;
A second connection target member having a second electrode on its surface;
A connection portion connecting the first connection target member and the second connection target member;
The connecting portion is formed of conductive particles or formed of a conductive material containing the conductive particles and a binder resin;
An organic-inorganic hybrid particle obtained by the method for producing organic-inorganic hybrid particles according to any one of claims 1 to 6, and a conductive layer disposed on a surface of the organic-inorganic hybrid particle, With
A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles.

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