TWI288419B - Coated particle - Google Patents

Abstract

This invention aims to provide coated particles having excellent connection reliability. The coated particles each comprises a care particle having a surface layer made of a metal, wherein the core surface has been partly modified with an organic compound through a functional group (A) having bondability to the metal.

Description

1288419 A7 ______B7___ _ V. INSTRUCTION DESCRIPTION (\) [Technical Field to Which the Invention Is Ascribed] The present invention relates to coated particles. ------------钃装—(Please read the precautions on the back and fill out this page) [Background] The isotropic conductive particles for electrical connection are used for electrode conduction of liquid crystal display panels. An anisotropic conductive film for assembling a material or an LSI wafer. The above-mentioned anisotropic conductive film ’ is used by, for example, dispersing metal plating particles on an insulating material, forming a film or the like. When the anisotropic conductive film is sandwiched between the electrodes and pressurized and heated, the insulating material is melted, and the metal plating particles act as conductive particles to electrically connect the electrodes. Printed by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives. However, with the fine pitch of the electrodes in recent years, in order to ensure high connection reliability, it is necessary to increase the amount of conductive particles in the anisotropic conductive film. Therefore, conduction or the like in the lateral direction is caused by the adjacent particles, and as a result, a problem such as a short circuit between adjacent electrodes occurs. In order to improve the above-mentioned problem, for example, it is disclosed in Japanese Patent Laid-Open Publication No. Sho. No. 62-4 183 that the periphery of the metal plating particles is coated with a resin which is incompatible with the resin of the film layer, and then pulverized to reach the particles. A method of coating metal plating particles with microcapsules is described in Japanese Laid-Open Patent Publication No. Hei 8-335407. However, in the above method, since the resin used for coating is physically adsorbed on the metal plating particles, the bonding force with the metal is weak, and after the coating treatment, the aggregated particles are singulated into a single particle. During the pulverization process, the coated particles will peel off, and the thickness of the coated resin will decrease or the surface of the metal plating particles will be exposed, not only the conduction of the electrode direction, or even X 297 mm. 1288419 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 5. Inventive Note (/) It also causes conduction in the lateral direction, and sometimes the short circuit in the lateral direction becomes large. Further, in the above method, since the resin is deposited on the surface area of the metal particles, when the coated particles are kneaded to the binder resin or the adhesive, there is also a problem that the laminated resin is peeled off. Further, when the anisotropic conductive film containing the coated particles is thermocompression bonded at a high temperature, the resin may be peeled off from the surface of the coated particles. [Brief Description of the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide a coated particle excellent in connection reliability. The coated particles of the present invention have a core having a surface composed of a metal as a core, and a functional group (A) having a bonding property to the surface of the metal is partially modified by an organic compound. In the coated particles of the present invention, the surface of the particles having the surface composed of the metal is grafted with the organic compound, or the particles having the surface composed of the metal are used as the core, and the surface is coated with the organic particles (including the pair of metal It is desirable to make a partial modification of the bonding functional group (A). In the coated particles of the present invention, when the organic compound is grafted on the surface of the particles having the surface composed of the metal, the coated particles of the present invention are introduced into the surface by using particles having a surface composed of a metal as a core. a compound containing a polymerizable or chain-transferring functional group or a catalyst (C), graft polymerization starting from the above-mentioned polymerization or chain transfer functional group or catalyst (C), to borrow from the surface of the particle It is desirable to make partial modifications of organic compounds. The above graft polymerization is preferably carried out by metathesis polymerization. In particular, the use of ring-shaped monomer 4 This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) - (Please read the note on the back and fill in this page) -=0 · 丨 line Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed 1288419 A7 ____B7______ V. Invention Description (Qiao) The open-loop metathesis polymerization is desirable because of the ease of reaction. The above organic compound preferably has a positive or negative charge. The above organic compound is preferably an insulating compound. [Detailed Disclosure of the Invention] The present invention will be described in detail below. Further, in the present specification, "the surface is partially modified by an organic compound" means that the entire surface is not completely covered by the organic compound. The coated particles of the present invention have particles (hereinafter also referred to as metal surface particles) having a surface composed of a metal as a core. The metal is not particularly limited as long as it has conductivity, and examples thereof include metals such as gold, platinum, silver, copper, iron, nickel, aluminum, and chromium; and metal compounds such as ITO and solder. Among them, the use of gold is preferred from the viewpoint that the resistance is low. The metal surface particles are not particularly limited as long as the outermost layer is made of a metal, and may be a particle composed only of the above metal or may be vapor deposited on the surface of a core particle composed of an organic or inorganic compound. The particles obtained by forming the above metal layer by plating, coating, or the like. In the coated particles of the present invention, the surface of the metal surface is used as a core, and the surface is transmitted through a functional group (A) having a bonding property to a metal and partially modified by an organic compound. : For the above-mentioned metal bonding functional group (A), as long as it can be associated with genus ion bonding, covalent bonding, or coordination bonding, the base is not limited by the stomach. For example, decyl, stanol, carboxyl, amine, ammonium 5 paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the back note and fill out this page) Packed: «· 1288419 A7 ____B7____ V. Invention Description (V) ------------ Pack--- (Please read the notes on the back and fill out this page) Base, Nitro, Meridian , carbonyl, thio, carboxylic acid, sulfhydryl, boronic acid, oxopipelinyl, anthracene (trolidone, phosphate, nitroxide, etc.. Coordination bonding to metal bonds is preferred) Therefore, it is preferred to use a group having 8, N, and p atoms. For example, when the metal is gold, it is preferably a sulfur group which can form a coordination bond with gold. The organic compound is not particularly limited as described above. For example, (un)saturated hydrocarbons, aromatic hydrocarbons, (un)saturated fatty acids, aromatic decanoic acids, (un)saturated ketones, aromatic ketones, (not a saturated alcohol, an aromatic alcohol, a (un)saturated gas, an aromatic ammonia, a (un)saturated thiol, an aromatic thiol, an organic sand compound, a derivative thereof, or a compound of at least one of these A condensate, a polymer composed of at least one of these compounds, etc. Further, the above-mentioned (not) saturated means both saturated and unsaturated.

The condensate or polymer produced by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs may, for example, be a polyolefin such as polyethylene or polybutadiene; a polyether such as polyethylene glycol or polypropylene glycol; or polystyrene; , poly(meth)acrylic acid, poly(meth)acrylate, polyvinyl alcohol, polyvinyl ester, phenolic resin, melamine resin, allyl resin, furan resin, polyester, epoxy resin, enamel resin, polyfluorene Imine resin, polyurethane, Teflon, acrylonitrile/styrene resin, styrene/butadiene resin, vinyl resin, polyamide resin, polycarbonate, polyacetal, polyether sulfonate, polyphenylene ether, Sugar, house powder, cellulose, peptides, etc. These organic compounds may be used singly or in combination of at least two. When the coated particles of the present invention are used as the anisotropic conductive particles, it is preferred to select the insulating compound as the organic compound. As a method of partial modification with the above organic compound, as long as it is 6 paper scales, it applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1288419 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative prints A7 B7 V. Invention Description (<) The method of imparting a functional group (A) having a bonding property to a metal is not particularly limited, and examples thereof include a method of grafting an organic compound on a metal surface, and a functional group containing a bonding property to a metal. A method in which the organic particles of (A) are bonded to a metal surface, a method in which fine pores are formed by coating an organic compound with a metal surface, and the like. Among them, a method of grafting an organic compound on a metal surface, and a method of bonding an organic particle containing a functional group (A) having a bonding property to a metal to a metal surface are suitable. The coated particles of the present invention can be obtained by grafting an organic compound onto the surface of the metal particles. The method of grafting the organic compound to the surface of the metal particles is not particularly limited, and examples thereof include: 1) a method in which the organic compound contains a functional group (A) having a bonding property to a metal and then introduced into a metal surface 2) allowing a functional group (A) having a bonding property to a metal and a hydroxyl group, a carboxyl group, an amine group, an epoxy group, an allyl group, a decyl alcohol group, an isocyanate group or the like to form a covalent bond by a chemical reaction The compound of the reactive functional group (B) is reacted on the surface of the metal, and then the reactive functional group (B) is substituted into the above organic compound by one or more stages; 3) the surface of the metal particle is permeable to the metal. The functional group (A) is introduced to introduce a compound containing a polymerizable or chain-transferring functional group or a catalyst (C), and graft polymerization is carried out starting from the above-mentioned polymerization or chain transfer functional group or catalyst (C). Method and so on. Among them, the method of graft polymerization of 3) can be suitably used. The coated particles of the present invention can be introduced into a metal-bonding functional group (A) onto a metal particle-containing functional group (A) to introduce a compound having a polymerizable or chain-transferring functional group or a catalyst (C) to the above-mentioned polymerization or chain. Transferring functional groups or 7 -----------·Installation --------, order---------- line, (please read the notes on the back first) Fill in this page again. This paper size applies to China National Standard (CNS) A4 specification (21〇X 297 public) 1288419 A7 B7 V. Inventive Note (L) Catalyst (c) is obtained by graft polymerization. Packing--- (Please read the note on the back and fill out this page.) The above-mentioned polymerized or chain-transferred functional group or catalyst (c) means a functional group or catalyst that can act as a starting point for graft polymerization. Examples thereof include a radical cleavable group such as an azo group or a perester group; a chain mobile group such as a thio group, a sulfide group, a dithiocarbamic acid group, a nitrate group or a halogen group; and a vinyl group; Unsaturated bond group such as a succinyl group or an ethyl group, a cyclic ether group, a cyclic methyl sulphonate group, a lactone group, an indolyl group, a cyclic imidate group, a cyclic olefin group, and a ring a cyclic group such as an oxalate group or a cyclic phosphazene group; an aldehyde group, a ketone group, an isocyanate group, a hydroxyl group, an amine group, or a carboxyl group; and has a choice of Li, Na, Mg, Ti, V, Cr, Fe, Co a halide of a central metal of one or at least two of Ni, Cu, Zr, Nb, Mo, Ru, Hf, Ta, W, Re, Os, Ir; hydroxyhalide, organic ammonium salt; organometallic compound The Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives, which printed the above-mentioned graft polymerization, as the case of open-loop metathesis, as The functional group or catalyst (C) for polymerization or chain transfer is a central metal having one selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, RU, Ta, W, Re, Os, and Ir. A metathesis-reactive catalyst such as a polyacetylene complex such as a chloride, an organometallic compound, an alkylidene complex or a vinylidene complex, or a hydrocarbon carbide complex. Examples of the metathesis-reactive catalyst include metal chlorides such as TiCl4, V0C13, MoC15, ReCl5, IrCl3, ZrCl4, NbCl5, WC16, RuC13, VC14, TaCl5, WOCl4, and 〇sci3; An organometallic compound such as a molybdenum molybdenum; an organometallic complex such as bis(tricyclohexylphosphine) benzyl guanidine (IV) or the like. Among these, the central metal is suitable for use as a crucible. 8 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1288419 A7 B7____ V. Inventive Note (' ) As the above graft polymerization, depending on the polymerization or chain transfer functional group or catalyst ( The type of C) is generally a radical polymerization, an ionic polymerization, a coordination polymerization, a metathesis polymerization, a polycondensation reaction, a polyaddition reaction, and the like. Among them, living radical polymerization, cationic polymerization, anionic polymerization, metathesis polymerization, etc., which can control the length of the polymerization chain, are preferred. Among them, it is preferred to carry out ring-opening metathesis polymerization with easy reaction. The ring-opening metathesis polymerization is easier to control the length of the polymer chain, and the catalyst metal can be easily removed. There is no case where the active control group such as halogen such as living polymerization remains at the end of the molecule. The monomer to be subjected to the above graft polymerization has radical polymerizability, ionic polymerizability, ring-opening polymerizability, isomerization polymerizability, cyclization polymerizability, depolymerization property, polycondensation property, polyaddition property, and the like. The polymerization reactivity is not particularly limited, and examples thereof include ethylene, butadiene, and styrene derivatives; (meth)acrylic acid and ester derivatives thereof; decylamine derivatives; vinyl ester derivatives, vinyl ether derivatives, and the like. a vinyl-containing compound; a cyclic olefin compound such as a cyclooctadiene or a norbornene derivative; a cyclic ether such as an ethylene oxide derivative, a tetrahydrofuran derivative or a trioxane derivative; 1, 3 a cyclic acetal such as a dioxaheptacyclic derivative, a 4H, 7H-1,3-dioxaheptacyclic derivative; a cyclic ester of ε-caprolactone, glycolide, trimethyl carbonate or the like; nitrogen An aliphatic cyclic amine such as a heterocyclopropane or a monomethylpropionimide; a cyclic sulfide such as propylene sulfide; an oxazoline derivative, an acetonitrile imine, a pyrrolidone, or an ε-caprolactam; a cyclic oxime such as hexamethylcyclotrioxane; hexachlorophosphazen E-cyclic phosphazene; formic acid, ethyl acetonide and other acids; phenolic derivatives; aniline derivatives; hexamethylene isocyanate, etc. The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ------------Installation - (Please read the notes on the back and fill out this page) ^Book · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1288419 A7 B7 V. Invention Description (Name) a compound containing a cyanate group; a compound containing a hydroxy group, such as ethylene glycol or tetramethyl diol; an amine group-containing compound such as hexamethylenediamine; a carboxyl group-containing compound such as adipic acid or an acid; a base acid derivative; a urea derivative or the like. These monomers may be used singly or in combination of at least two. Wherein, in the case where the graft polymerization is a ring-opening metathesis polymerization, as the monomer for performing the above graft polymerization, it is preferred to have a metathesis polymerization property, for example, cyclobutene, cyclopentene or cyclooctane. a monocyclic olefin such as a olefin or a cyclooctadiene or a derivative thereof; a polycyclic olefin such as norbornene, norbornadiene, dicyclopentadiene or tricyclopentadiene; and a derivative thereof; 3-dihydrofuran, ex〇-3,6-epoxy-1,2,3,6-tetrahydroanhydropeptidic acid, 9-oxadicyclo[6.1.0]9-tetraene, exo-N —Methyl-7—oxocyclo[2.2.1]septa-5-ene-2,3-dicarboxyarsenine, I,4-dihydro-M-epoxynaphthalene, etc. Olefins, etc. These monomers may be used singly or in combination of at least two. In the case of the above graft polymerization, it is preferred that the organic compound on the surface of the metal surface particles is modified to have a positive or negative charge. If the organic metal compound has a positive or negative charge in the molecule, the grafting density can be easily controlled when the surface of the metal particle is grafted due to mutual repulsion between the organic compound and the molecule. Further, the prevention of the aggregation of the conductive particles and the dispersibility in the binder resin can be improved. In order to have a positive or negative charge in the molecule of the above organic compound, it is desirable to have a functional group at the side chain of the molecule and/or at the end of the molecule. Examples of the functional group include a surface group, a mercapto group, a sulfonic acid group, a carboxyl group, a phosphoric acid group, a boric acid group, a nitro group, and the like. 10 ------------装--- (Please read the notes on the back and fill out this page) Order. -Line - Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1288419 A7 ___B7 _ V. Description of Invention (1) There is no particular limitation on the method of introducing the above functional group. A method of copolymerizing a monomer having the above functional group during polymerization, a method of introducing a side chain by a chemical reaction after polymerization, and the like. When the above graft polymerization is carried out, a chain transfer agent, a catalyst, a catalyst, or the like may be used if necessary. When the polymerizable or chain-transferring functional group or the catalyst (C) is a metal chloride or an organic metal, as the above-mentioned promoter, an alkyl aluminum such as triethylaluminum or the like may be used. An organotin compound such as dimethyltin, phenyldiazomethane or methyl diazoacetate. The compound containing the above-mentioned polymerization or chain transfer functional group or the catalyst (C) may be an organic compound or an inorganic compound. The method of introducing a compound containing a polymerizable or chain-transporting functional group or a catalyst (C) onto the surface of the metal surface particle is not particularly limited, and examples thereof include: 3-1) allowing polymerization or The chain transfer functional group or the compound formed by the catalyst (C) contains a functional group (A) which is bonded to the metal and then introduced into the metal surface; 3-2) the bonding property of the metal is contained a compound formed by a functional group (A) and a reactive functional group (B), which reacts with a metal surface particle, and then, by one or more stages, a reactive functional group (B) is substituted into a polymerized or chain-transferred functional group. a method of reacting with a catalyst (C); 3-3) reacting a compound containing a functional group (A) having a metal bond with a metal surface particle, and then modifying the surface into a reaction by plasma treatment or the like The functional group (B) is a method in which the above reactive functional group (B) is further substituted into a polymerizable or chain-transferring functional group or a catalyst (C) by a one-stage or multi-stage reaction. The above 3-1) will contain a polymerized or chain-transferred functional group or a catalyst 11 (please read the back of the back sheet and fill out this page). Loading: · -% This paper size applies to the Chinese National Standard (CNS) A4. Specifications (210 X 297 mm) 1288419 A7 B7___ V. Description of invention (1) ------------ Pack--- (Please read the notes on the back and fill out this page) (C) A compound used in a method of introducing a compound into a surface of a metal surface particle, as long as it has a functional group (A) having a bonding property to a metal surface particle, and a functional group which is polymerized or chain-transferred in the same molecule The catalyst (C) is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azodimercaptopropane dihydrochloride, nonylphenol, and hydrazine. P-hexanol, terminal thiopolyvinyl alcohol, 4-hydroxyphenyl dimethyl hydrazine methyl sulfate, mercaptopropionic acid, 2,2'-dipyridyl-4,4'-dicarboxylic acid, lipoic acid 4—imidazoleacetic acid, histidine, cysteine, methionine, p-nonylstyrene, sodium p-styrenesulfonate, p-dimethylsulfonyl phenyl methacrylate, Salts of sulfuric acid group, acrylonitrile, bis (tricyclohexylphosphine) dichloride, a ruthenium dodecyloxy a benzyl River (W) and the like.

The method of introducing the polymerizable or chain-transferring functional group or the catalyst (C) into the metal surface particles is not particularly limited, and for example, the above-mentioned 3-2) a reactive functional group (B) having a hydroxyl group, a carboxyl group, an amine group, an epoxy group, an allyl group, a decyl alcohol group, an isocyanate group or the like, and a compound having a metal functional group (A) bonded thereto Introducing a metal surface, and then having a compound having a functional group covalently bonded to the above reactive functional group (B) and a polymerizable or chain-transferring functional group or a catalyst (C) The functional group (B) is reacted to introduce a polymerization or chain transfer functional group or a catalyst (C). Specifically, a hydroxyl group is introduced into the metal surface particles by a nonylphenol, and then a decane coupling using 2-(4-chlorosulfonyl)ethyltrichloromethane is carried out to convert the functional group into a chain mobility property ( C) The method of chlorosulfonyl group; introduction of hydroxyl groups to metal surface particles by 4-hydroxyphenyl dimethyl sulfhydryl sulfate, 12 paper scales applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1288419 A7 B7 Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, Printing 5, Inventions (u) Next, the method of converting the esterification to a polymerizable functional group (c) with a methacrylic acid chloride; Method for introducing an amine group into a metal surface particle by an acid followed by a method of converting to a chlorine group of a chain transfer functional group (C) by an addition reaction of 4-mono(chloromethyl)phenylisocyanate; The introduction of a hydroxyl group into the metal surface particle by the alcohol is followed by a decane coupling using 2-norbornyl-6-methyldichlorodecane to convert to a norbornene group to further carry out bis(tricyclohexylphosphine) dichloride. Coordination of sodium sulfonate-benzyl hydrazine (!V) , a method of converting to a base of a chain transferable catalyst (C), and the like. The method of introducing the polymerizable or chain-transferring functional group or the catalyst (C) into the surface of the metal surface particle is not particularly limited, and for example, it may have a bonding property to the metal. The compound formed by the functional group (A) is introduced into the metal surface particles, and then converted into a reactive functional group (7) by plasma treatment, oxidation treatment, or the like, and then converted into a polymerization or chain transfer property by the method shown in the above 3-2). The functional group or the method of the catalyst (C). The coated particles of the present invention can also be obtained by a method in which organic particles (containing a metal-bonding functional group (A)) are bonded to a metal surface. The above-mentioned organic particles mean that the particles constituting the above-mentioned organic compound are partially modified by the above-mentioned organic particles, and since the modified conductive particles have low aggregability with each other, the pulverization process for single-particle granulation is The load of the particles is small, and peeling of the coated organic compound is less likely to occur. It is preferable that the above organic compound has a positive or negative electric charge on the surface or the inside, and thus, the mutually exclusive action can be utilized to prevent the organic particles from condensing with each other. 13 ------------ Read the notes on the back and fill out this page. l·Order: 丨 Line paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1288419 A7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print __B7_______ V. Invention Description (〆) Set. The method of introducing a positive or negative charge is not particularly limited, and examples thereof include a method of mixing an organic or inorganic ionic compound in the production of the organic particles, a method of introducing a surface of the organic particles by a chemical bond, and a physical adsorption. A method of introducing a surface of an organic particle, a method of chemically treating the surface of the organic particle to improve the surface of the organic particle, a method of improving the surface of the organic particle by ionization or the like, or the like. The method of allowing the organic particles to contain the above-mentioned metal-bonding functional group (A) is not particularly limited, and examples thereof include a method of mixing in the production of organic particles, a method of introducing a surface of an organic particle by a chemical bond, and a method of borrowing a method of physically adsorbing a surface of an organic particle, a method of chemically treating the surface of the organic particle to improve the surface to a bond with the metal, and improving the surface of the organic particle to bond with the metal by plasma or the like The method of sex and so on. The particle diameter of the organic particles is not particularly limited. However, when the coated particles of the present invention are used as the anisotropic conductive particles, it is preferably 1 to 200 Å. When it is within this range, the insulating property between adjacent conductive particles can be ensured, and the conductive property can be obtained when the coated particles of the present invention are pressure-bonded between the electrodes. The method for producing the organic particles is not particularly limited, and a conventionally known method such as an emulsion polymerization method, a soap free precipitation polymerization method, a dispersion polymerization method, a suspension polymerization method, or a hardened resin may be used. Method, etc. The coated particles of the present invention are partially modified by the above organic compound 14 (please read the back of the note first and then fill out this page) 装 l·订: 丨% This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1288419 A7 B7 V. Inventive Note (A) The thickness of the organic layer formed varies depending on the area to be modified, etc., and is not particularly limited, but the coated particles of the present invention are used as anisotropic conductivity. When the particles are used, it is preferably 1 to 2000 nm. If it is within this range, "insulation between adjacent conductive particles can be ensured" and conductivity can be obtained when the coated particles of the present invention are pressure-bonded between the electrodes. The area of the coated particles of the present invention modified by the above organic compound varies depending on the molecular weight of the modifying organic compound, the structure, the thickness of the organic layer, and the like, and is not particularly limited, but generally 10 of the surface area of the metal plating particles. ~90% is better. When the coated particles of the present invention are used as the anisotropic conductive particles, the insulation between the adjacent conductive particles can be ensured, and the coated particles of the present invention can be crimped between the electrodes. Continuity is obtained. More preferably 20 to 90%. Since the coated particles of the present invention are nucleated by particles having a surface composed of a metal, and the surface thereof is partially modified by the functional group (A) having a bonding property to the metal, the organic layer and the metal bond are coated. The strength is strong, and there are few cases where the organic layer peels off. Therefore, when the coated particles of the present invention are used as the anisotropic conductive particles, it is possible to maintain high connection reliability while ensuring insulation between adjacent particles. Further, when a method of modifying an organic compound on the surface of a metal surface particle by grafting is used, since the control of the area and thickness of the modification is easy, modification suitable for the use condition of the coated particle can be carried out. Further, if a method of modifying an organic compound on the surface of a metal surface particle by grafting is used, the type of the monomer to be used can be selected, the layer structure can be easily controlled, and adhesion, anti-aggregation, and hydrophobicity can be imparted. The 15 paper grades for the performance and hydrophilicity are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm).--- (Please read the note on the back and fill out this page). Employee Consumer Cooperatives Printed 1288419 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed 5, Invention Description () Effect, can play excellent performance. [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the embodiments. (Example 1) In a separable flask equipped with four separable caps, a stirring blade, a three-way valve, a cooling tube, and a temperature detector of 10 mL, 'the commercially available terminal has a sulfur group. 5 g of polyglycol (average molecular weight 20,000) was dissolved in 500 g of distilled water under an argon atmosphere. The solution was dispersed in a particle size of about 100 g of gold-plated particles under an argon atmosphere, and stirred at 40 ° C for 12 hours. The unreacted polyvinyl alcohol was removed by filtration, washed with hot water, and dried to obtain coated particles whose surface was partially modified by an insulating organic compound. (Example 2) A commercially available terminal having a sulfur-based polymethyl group in a separable flask equipped with four separable caps, a stirring blade, a three-way valve, a cooling tube, and a temperature detector of a volume of 1000 mL 5 g of methyl acrylate (average molecular weight 12,000) was dissolved in 500 g of tetrahydrofuran obtained by distillation purification under an argon atmosphere. The solution was dispersed in an argon atmosphere at a particle size of about 5 // m, and the surface-plated particles were 10 g, and stirred at 40 ° C for 12 hours. Unfiltered poly 16 by filtering (please read the note on the back and fill out this page) Binding·

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 1288419 A7 B7 V. Invention description (V<) Methyl methacrylate removal, washing with tetrahydrofuran and drying, the surface is made of insulating The organic compound is a partially modified coated particle. (Example 3) 99 g of methyl methacrylate and lg methacrylate were placed in a separable flask having a capacity of 500 mL of a separable lid, a stirring blade, a three-way valve, a cooling tube, and a temperature detector. 1.5 g of thioacetic acid was stirred at 85 ° C, followed by addition of 2,2, azobisisobutyronitrile 〇.lg, and polymerization was carried out for 1.5 hours. After purification, it was dried to obtain a polymethyl methacrylate/methacrylic acid copolymer having an alkyl group at the terminal (having an average molecular weight of 20,000). 5 g of the above polymethyl methacrylate/methacrylic acid copolymer was dissolved in 500 g of tetrahydrofuran obtained by distillation under an argon atmosphere. This solution was dispersed in an argon atmosphere at a particle size of about 5 / / m and 10 g of gold-plated particles on the surface, and stirred at 40 ° C for 12 hours. The unreacted polymethyl methacrylate/methacrylic acid copolymer was removed by filtration, washed with tetrahydrofuran, and dried to obtain coated particles whose surface was partially modified with an insulating organic compound. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing ------------ Pack--- (Please read the back note first and then fill out this page) «% (Example 4) In the installation 4 A separable separable lid, a stirrer, a three-way valve, a cooling tube, and a temperature detector having a capacity of 500 mL in a separable flask were dissolved in 5 mL of tetrahydrofuran obtained by distillation.

The solution was dispersed in an argon atmosphere at a particle size of about 100 g of gold-plated particles, and was disturbed at 40 ° C for 12 hours. By the furnace, the unreacted L 17 paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1288419 A7 ____B7 __ V. Description of the invention (VIII) Removal of the base propionic acid, after washing with tetrahydrofuran Dry and re-disperse in 500 mL of tetrahydrofuran. Packing--- (Please read the precautions on the back and fill out this page) Add 5g of polymethyl methacrylate (molecular weight 15,000) with an epoxy group at the end of the dispersion under an argon atmosphere. Stir at 40 ° C for 1 hour. The unreacted polymethyl methacrylate was removed by filtration, washed with tetrahydrofuran, and dried to obtain coated particles whose surface was partially modified with an insulating organic compound. (Example 5) In a separable flask equipped with four separable caps, a stirring blade, a three-way valve, a cooling tube, and a temperature detector of a volume of 100 mL, decyl undecyl alcohol 5 mm 〇l was dissolved in The obtained tetrahydrofuran (500 mL) was purified by distillation. This solution was dispersed in an argon atmosphere at a particle size of about 5/zm, and 10 g of gold-plated particles were surface-ground at 40 ° C for 12 hours. Unreacted 锍% decyl undecyl alcohol was removed by filtration, washed with tetrahydrofuran, dried, and dispersed again in 200 mL of distilled water. The Ministry of Economic Affairs, Intellectual Property Office, and the Consumer Cooperatives Co., Ltd. printed 5 mol of hydroxymethyl methacrylate to the dispersion. After thorough stirring, an O.lmol/L ammonium cerium nitrate solution prepared by adding 1 N aqueous nitric acid solution was added. Stir for 10 hours. Filtered, washed with methanol and dried to obtain a coated particle partially modified with an insulating organic compound (Example 6). Four detachable lids, a stirring plate, a three-way valve, and a cooling tube 18 were installed. The scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1288419 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (\'), temperature detector capacity lOOOOl separable flask In the above, 5 mmol of nonylphenol was dissolved in 200 mL of tetrahydrofuran obtained by distillation. The solution was dispersed in a argon atmosphere at a particle size of about 5 # m and surface-plated particles of l〇g, and stirred at 40 ° C for 12 hours. The unreacted nonylphenol was removed by filtration, washed with tetrahydrofuran, and then re-dispersed in purified toluene 500 mL. To the dispersion, 5 mmol of 2-(4-chlorosulfonium)ethyltrichloromethane was added, and the mixture was stirred at 40 ° C for 6 hours. Unreacted 2-(4-chlorosulfonyl)ethyltrichloromethane was removed by filtration and washed with toluene, and then dispersed in purified toluene under an argon gas stream. To the dispersion, copper bromide 10 mmol, 4,4'-di-n-heptyl- 2,2'-dibipyridinyl 20 mmol, methyl methacrylate 5 mol, and p-toluenesulfonate were added under a hydrogen atmosphere. The base chloride was 2.5 mmol and stirred at 90 ° C for 12 hours. After cooling to room temperature, 100 g of n-hexane was added, and after filtration, it was further washed with n-hexane and dried to obtain coated particles whose surface was partially modified with an insulating organic compound. (Example 7) 5 mM of nonylphenol was dissolved in a separable flask having a capacity of 100 mL of a detachable lid, a stirring blade, a three-way valve, a cooling tube, and a temperature detector. Tetrahydrofuran 500 mL. The solution was dispersed in an argon atmosphere at a particle size of about 5 // m, and the surface mineral particles were 10 g, and stirred at 40 ° C for 12 hours. The unreacted nonylphenol is removed by filtration, washed with tetrahydrofuran, and then dispersed in refined tetrahydrofuran. The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public) ----- ------ φ 装-------- order--------- line (please read the back of the note before you fill out this page) 1288419 A7 B7 V, invention description (4) In the 500mL. To the dispersion, 5 mmol of (p-chloromethyl)phenyltrichloromethane was added, and the mixture was shaken at 40 C for 6 hours. Unreacted (p-chloromethyl)phenyltrichloromethane was removed by filtration, washed with toluene, and then dispersed again in purified tetrahydrofuran. To the dispersion was added 100 mmol of sodium N,N-diethyldithiocarbamate, and the mixture was stirred at room temperature for 18 hours. The unreacted sodium N,N-diethyldithiocarbamate was removed by filtration, washed with toluene, and then dispersed in purified toluene under an argon gas stream. To the dispersion, 2 mmol of methyl methacrylate and 0.02 mmol of methyl acrylate were added under an argon atmosphere, and a high-pressure mercury lamp (manufactured by SEN Light Co., Ltd., HLR100T-1) was used as a light source, and light irradiation was performed at 4 Torr. Stir at °C for 3 hours. After cooling to room temperature, washing with n-hexane, filtering and drying to obtain coated particles whose surface is partially modified by an insulating organic compound ------------ armored - (please read the back first) Note on this page)

Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative (Example 8) In a separable flask equipped with 4 separable caps, stirrer blades, three-way valves, cooling tubes, and temperature detectors in a volume of 1000 mL 5 mmol of thioldecylundecyl alcohol was dissolved in 500 mL of tetrahydrofuran obtained by distillation purification. The solution was dispersed in an argon atmosphere at a particle size of about 1 g of gold-plated particles, and stirred at 40 ° C for 12 hours. The unreacted succinyl alcohol was removed by filtration, washed with tetrahydrofuran, dried, and dispersed in 20 refined scales. The national standard (CNS) A4 specification (210 x 297 mm ^ 1288419 A7 B7 Ministry of Economy) Intellectual Property Bureau employee consumption cooperative printing 5, invention description (j) toluene 500mL. Add 2 - norbornene- 6-methyl dichlorodecane 5mmol ' to the dispersion, stir at 40 ° C for 6 hours to carry out the reaction Converting the hydroxyl group into the base of the norbornene. By dissolving it in toluene according to the [unreacted 2 - norbornene-based 6-methyl-*chlorodecane removal], it is again dispersed in an argon atmosphere. Adding 500 mL of purified toluene. Add bis(tricyclohexylphosphine) benzyl guanidine (IV) 5 mm 二 as a metathesis polymerization catalyst to the dispersion, and react at room temperature for 30 minutes to form norbornene. The base is converted to a decyl alkynyl group. The unreacted bis(tricyclohexylphosphine) benzyl hydrazine (IV) is removed by filtration, washed with toluene, and then dispersed in a purified toluene 400 mL under an argon gas stream. Adding the dispersion as a graft polymerization under an argon atmosphere 2 mmol of norbornene dissolved in 100 mL of purified toluene was graft-polymerized at room temperature for 30 minutes, washed with methanol, and dried to obtain coated particles partially modified with insulating organic particles. 9) In a separable flask equipped with 4 separable caps, stirring plates, three-way valves, cooling tubes, and temperature detectors in a volume of 1000 mL, 500 mmol of styrene and phenyl dimethyl methacrylate were added to the stomach. Methylsulfate 5 mmol, 2,2'-azobis(2-mercaptopropane) dihydrochloride 5 mm Ql, = and 25 mL of distilled water, stirred at 2 rpm, at 60 ° C under a nitrogen atmosphere Polymerization was carried out for 7 hours to obtain an 18% dispersion of latex particles with an average of 220 nm on the surface. 21 (Please read the notes on the back and fill out this page) Loading. - Line paper size applies to China National Standard (CNS) A4 specifications. (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1288419 A7 ___B7___ V. Inventive Note (/) 5 〇〇mL of the above latex particle dispersion diluted to 1% with distilled water, in an argon atmosphere Lower dispersion 5/zm, gold-plated particles l〇g, stirred at 40 ° C for 12 hours. Filtered by a filter of 3 / / m sieves. After further washing with methanol, drying, the surface is obtained by insulating organic particles. Partially modified coated particles. (Example 1〇) In a separable flask equipped with four separable lids, a stirrer, a three-way valve, a cooling tube, and a temperature detector, l〇〇mL, 500 mmol of styrene, 1.92 mmol of sodium benzoate, 0.94 mm of barium persulfate, and 475 mL of distilled water were placed, stirred at 200 rpm, and polymerized under a nitrogen atmosphere at 60 ° C for 12 hours to obtain a surface. A 10% dispersion of latex particles having an average particle diameter of sulfonic acid groups of 〇5 nm. 500 mL of the above-mentioned latex particle dispersion diluted with distilled water to 1% was dispersed in a argon atmosphere at a particle size of 100 μg of gold-plated particles, and stirred at 40 ° C for 12 hours. The mixture was filtered through a filter of a 3# m sieve, and further washed with methanol and dried to obtain coated particles whose surface was partially modified by insulating organic particles. (Example 11) In a separable flask equipped with four separable lids, a stirring blade, a three-way valve, a cooling tube, and a temperature detector of 10 mL, a styrene 250 mmol, A was placed. 250 mmol of glycidyl acrylate, 5 mmol of 2,2'-azobis(2-propenylpropane) dihydrochloride, and distilled water 22 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) Pack--- (Please read the note on the back and fill out this page) Order: Line 1284849 A7 B7 V. Invention Description (4) Pack--- (Please read the note on the back and fill out this page) 549mL, After stirring at 200 rpm, 7 (TC was carried out for 2 hours under a nitrogen atmosphere, followed by addition of 40 mmol of glycidyl methacrylate, and further polymerization was carried out for 12 hours to obtain latex particles having an average particle diameter of 120 nm on the surface thereof. 10% dispersion liquid. 250 mmol of 3-mercaptopropionic acid was added to the above latex particle dispersion, and reacted under reflux for 5 hours, washed by centrifugation, and diluted with distilled water to obtain latex particles having an average particle diameter of 120 nm on the surface. 10% dispersion. The latex particle dispersion l〇〇mL was dispersed in an argon atmosphere at a particle size of about 5 #m and 5 g of gold-plated particles on the surface, and stirred at 40 ° C for 12 hours. Filtered by a filter of 3/m sieve. After that, it was further washed with methanol and dried to obtain coated particles whose surface was partially modified with an insulating organic compound. (Comparative Example 1) The Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative printed on the installation of four detachable covers, 5 g of polyvinyl alcohol (average molecular weight 10,000) was dissolved in 500 g of distilled water in a separable flask of a stirring piece, a three-way valve, a cooling tube, and a temperature detector of 1000 mL in a nitrogen atmosphere. 10 g of gold-plated particles having a particle size of about 5 #m' dispersed in a gas atmosphere, and stirred at 40 ° C for 12 hours. The unreacted polyvinyl alcohol was removed by filtration, further washed with hot water, and dried to obtain a surface. Insulating organic compounds are fully modified coated particles. 23 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) A7 1288419 ______B7__ V. Invention description (W) (Comparative Example 2) 10 g of gold-plated particles of 5//m and 5 g of fluorinated vinylidene resin were introduced into a hybridization apparatus, and treated at 90 ° C for 3 minutes to obtain coated particles partially modified with an insulating organic compound (evaluation). The thickness of the coated organic layer of the coated particles obtained in Examples 1 to 11 and Comparative Examples 1 and 2, and the ratio of the area covered by the organic compound among the surfaces of the metal surface particles (coating density). Next, each of the coated particles was singulated by a jet mill (manufactured by Nippon Engineering Co., Ltd.: current jet CT-2.5) by a force of lN/cm2 and 5 N/cm2, and the coating density of the single particles was measured. Further, the presence or absence of the aggregate after the jet mill treatment was judged by visual observation. The results are shown in Table 1. --- (Please read the notes on the back and fill out this page) I* ί 丨 经济 经济 经济 经济 经济 经济 经济 员工 员工 员工 员工 24 24 24 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本1288419 A7 B7 Table 1 Covered organic compound species Single-particleized before Jetmill treatment Aggregate presence and/or coverage Density coating Organic layer Thickness coating density 1 N/cm2 5 N/cm2 Aggregate-coated density Aggregate coating density Example 1 polyvinyl alcohol 15nm 65% 65% ΊΗ γ 65% Example 2 Polymethyl methacrylate 10nm 65% 65% iltr 65% Example 3 Methyl methacrylate / decenoic acid copolymer 15nm 60% There are 60 % ^frrr No 60% Example 4 Polymethyl methacrylate 12 nm 67% 67% Μ 67% Example 5 Polyhydroxymethyl methacrylate 20 nm 72% 72% 4\rr No 72% Example ό Polymethyl methacrylate 22 nm 80% 80% Utr j\\\ 79% Example 7 Polymethyl methacrylate 25 nm 82% 82% / rtf No 81% Example 8 Poly(norbornene) 30 nm 77 % 77% Mil J\\\ 77% Example 9 Surface sulfhydryl-polystyrene particles 43% / rrr heat 41% I m? 12% Example 10 Surface sulfonic acid-polystyrene particles - 58% Μ y 1 \\ 57% M j\\\ 25% Example 11 Surface thio-polymethyl Methyl acrylate particles 69% /fnT mi-y» 69% ΙΙΙΓ jw\ 32% Comparative Example 1 Polyvinyl alcohol 15 nm -100% 65% No 18% Comparative Example 2 Polyvinyl fluoride fork 15 nm 65% 58% Λττ IIIΓ J\s\ 20% • --- (Please read the notes on the back and fill out this page) 1Τ: -丨线· Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed by Table 1, we can see that Comparative Examples 1 and 2 When the obtained coated particles were single-particleized, the coating density was remarkably lowered. On the other hand, the coated particles obtained in Examples 1 to 11 had a small decrease in the coating density, and in particular, the coatings obtained in Examples 1 to 8. There was almost no decrease in the coating density of the particles. Further, in the coated particles obtained in Examples 9 to 11, no aggregates were observed even if the jet milling treatment was carried out with a slight force. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1288419 A7 ___B7_ V. Description of the invention (fire) [Industrial Applicability] The present invention provides a Coated particles excellent in connection reliability. ------------•装—— (Please read the note on the back and fill out this page) Line. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print 26 This paper scale applies to Chinese national standards ( CNS) A4 size (210 X 297 mm)

Claims (1)

1288419 > No. 90112987 Double Xiali application "Replacement of patent application scope (replacement in March 1996) | '...~ ...... , ........ | | I '一^^ ,广, ΛI 卟年;月如修 (more) is replacing page 1·—the kind of cover is sold for it, is to see the ear tag: prayer rain ^ the surface of the particles as the core, the surface through the metal key Constitutive functional group (a) (selected from decyl, stanol, carboxyl, amine, ammonium, nitro, hydroxy, carbonyl, thio, sulfonate, sulfhydryl, boronic acid, acetophenone a group, a ketone group, a phosphate group, a nitroxide group, a partial modification by an organic compound grafting 'and' by using an organic particle (having a functional group (A) having a bonding property to a metal) and the metal Surface bonding is partially modified. 2. The coated particles according to the first aspect of the patent application, wherein a particle having a surface composed of a metal is used as a core, and a compound containing a polymerizable or chain-transferring functional group or a catalyst (C) is introduced into the surface. Graft polymerization is carried out starting from the above-mentioned polymerization or chain transfer functional group or catalyst (C) to partially modify the surface of the particles by an organic compound. 3. The coated particle of claim 2, wherein the graft polymerization is open-loop metathesis polymerization. 4. The coated particle of claim 1, wherein the organic compound has a positive or negative charge. 5. The coated particle of claim 2, wherein the organic compound has a positive or negative charge. 6. The coated particle of claim 3, wherein the organic compound has a positive or negative charge. 7. The coated particle of claim 1, wherein the organic compound has a positive or negative charge. 8. The coated particle of claim 1, wherein the organic compound is an insulating compound. 27 1288419 9. The coated particle of claim 2, wherein the organic compound is an insulating compound. 10. The coated particle of claim 3, wherein the organic compound is an insulating compound. 11. The coated particle of claim 1, wherein the organic compound is an insulating compound. 12. The coated particles of claim 4, wherein the organic compound is a conjugate. 13. The coated particle of claim 5, wherein the organic compound is an insulating compound. 14. The coated particle of claim 6, wherein the organic compound is an insulating compound. 15. The coated particle of claim 7, wherein the organic compound is an insulating compound. 28