JP2014017212A - Composite particle and anisotropic conductive adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite particle in which a satisfactory amount of a sub-particle is adhered to an outside of a mother particle, and that keeps high coverage even after ultrasonic dispersion; and further an anisotropic conductive adhesive that includes the composite particle, that can maintain a satisfactory insulation characteristic and a conduction characteristic even in connection of a fine circuit, and that is excellent in hygroscopic resistance.SOLUTION: A composite particle includes: a mother particle; and two or more sub-particles adhered to an outside of the mother particle, wherein the mother particle is a spherical particle in which an average particle diameter is 1-10 μm, the sub-particle has an average maximum grain size of at least 140 nm and at most 500 nm, and the composite particle is a semicircle type particle that has an average maximum thickness of 20-80% of an average maximum grain size.

Description

  The present invention relates to composite particles and an anisotropic conductive adhesive using the same.

  Composite particles in which a plurality of spherical child particles are attached to the outside of a mother particle are known in various technical fields. Examples of such composite particles include insulating coated conductive particles composed of mother particles that are conductive particles and child particles that are insulating particles.

  Conventionally, when electrically connecting circuit boards or IC chips or electronic components and a circuit board, an insulating adhesive, an anisotropic conductive adhesive in which conductive particles are dispersed, or the like is used. Such a connection form is remarkable in the liquid crystal field. The method of mounting the liquid crystal driving IC on the glass panel for liquid crystal display can be broadly classified into two types: COG (Chip-on-Glass) mounting and COF (Chip-on-Flex) mounting. In COG mounting, an IC for liquid crystal is directly bonded onto a glass panel using an anisotropic conductive adhesive containing conductive particles. On the other hand, in COF mounting, a liquid crystal driving IC is bonded to a flexible tape having metal wiring, and these are bonded to a glass panel using an anisotropic conductive adhesive containing conductive particles. The anisotropy referred to here means conduction in the pressing direction and insulation in the non-pressing direction. As the conductive particles, particles obtained by performing nickel plating on the outside of plastic particles, particles obtained by plating nickel and gold or palladium in this order, or the like is used.

By the way, with recent high definition of liquid crystal display, metal bumps, which are circuit electrodes of liquid crystal driving ICs, are narrowed in pitch and area, so that the circuit where adjacent conductive particles of anisotropic conductive adhesive are adjacent. There is a risk of causing a short circuit by flowing out between the electrodes. This tendency is particularly remarkable in COG mounting. When conductive particles flow out between adjacent circuit electrodes, the number of conductive particles in the anisotropic conductive adhesive captured between the metal bumps and the glass panel decreases, and the connection resistance between the opposing circuit electrodes increases. There is a risk of poor connection. Such a tendency becomes more remarkable when 20,000 particles / mm ² or more of conductive particles are introduced per unit area.

  Therefore, as a method for solving these problems, a method has been proposed in which a plurality of insulating particles (child particles) are attached to the surface of conductive particles (mother particles) to form composite particles. For example, Patent Document 1 and Patent Document 2 propose a method of attaching spherical resin particles to the surface of conductive particles. In Patent Document 3 and Patent Document 4, composite particles in which core-shell type resin particles are attached to the surface of the conductive particles, and in Patent Document 5, composite particles in which hollow resin fine particles are attached to the surface of the conductive particles, Each has been proposed. Patent Document 6 proposes a method of connecting conductive particles and insulating particles with a polymer electrolyte in order to prevent peeling of the conductive particles and insulating particles.

Japanese Patent No. 4777385 Japanese Patent No. 3869785 Japanese Patent No. 4686120 Japanese Patent No. 4904353 Japanese Patent No. 4391836 JP 2008-120990 A

  Regarding the conventional composite particles described in Patent Documents 1 to 6, when applying a technique such as ultrasonic dispersion in order to prevent aggregation of the insulating coated conductive particles, the conductive particles and the insulating particles are peeled off. There is still room for improvement.

  The present invention has been made in view of the above-mentioned problems of the prior art, and provides composite particles in which a sufficient amount of child particles are attached to the outside of the mother particles and maintain a high coverage even after ultrasonic dispersion. With the goal. Furthermore, an object of the present invention is to provide an anisotropic conductive adhesive containing the composite particles, capable of maintaining sufficient insulation and conduction characteristics even in connection of a minute circuit, and having excellent moisture absorption resistance. To do.

  The present invention is a composite particle comprising a mother particle and a plurality of child particles attached to the outside of the mother particle, wherein the mother particle is a spherical particle having an average particle diameter of 1 to 10 μm, The particles relate to composite particles which are semicircular particles having an average maximum particle size of 140 nm to 500 nm and an average maximum thickness of 20 to 80% of the average maximum particle size.

  When the composite particle of the present invention has the above-described configuration, a connection area between the child particle and the mother particle is increased, and a composite particle having excellent adhesion strength between the child particle and the mother particle can be obtained.

  The child particles of the present invention preferably have a flat shape or a red blood cell shape from the viewpoint of increasing the connection area between the child particles and the mother particles and further improving the adhesion strength.

  The mother particle of the present invention can have a plastic core and a conductive film covering the plastic core. By having such mother particles, the composite particles of the present invention can be used for anisotropic conductive adhesives.

  Furthermore, from the viewpoint of achieving both flexibility and solvent resistance, the child particles are preferably organic-inorganic hybrid particles.

  The child particles are preferably attached to the outside of the conductive particles via a polymer electrolyte. By using the polymer electrolyte, sufficient insulating properties and good electrical connection can be obtained. Further, from the viewpoint of adhesion strength with the polymer electrolyte, the mother particles and the child particles preferably each have a functional group that reacts with the polymer electrolyte on the surface.

  From the viewpoint of controlling the shape of the child particle, the child particle is a copolymer obtained by polymerizing a monomer composition containing at least an organic monomer having a carbon-carbon double bond and an alkoxysilane having a carbon-carbon double bond. It is preferable to contain.

  The present invention further relates to an anisotropic conductive adhesive containing the composite particle. By using the composite particles of the present invention, it is possible to provide an anisotropic conductive adhesive that is excellent in both insulating properties, conduction properties and moisture absorption resistance.

  According to the present invention, it is possible to provide a composite particle in which a sufficient amount of child particles are attached to the outside of the mother particle and maintain a high coverage even after ultrasonic dispersion. Furthermore, by using the composite particles, it is possible to provide an anisotropic conductive adhesive that can maintain sufficient insulation characteristics and conduction characteristics even in connection of a minute circuit and is excellent in moisture absorption resistance. .

It is a schematic cross section which shows one Embodiment of composite particle. A plurality of semicircular child particles are attached to the outside of the mother particle. It is sectional drawing which shows one Embodiment of the circuit connection method by anisotropically conductive adhesive. It is sectional drawing which shows one Embodiment of a circuit connection structure. It is a SEM photograph of the child particle obtained in Example 1, and magnification is 15,000 times. It is the schematic diagram (a) and sectional drawing (b) of one Embodiment of a child particle. It is a SEM photograph of the insulation coating electroconductive particle obtained in Example 1, and magnification is 25,000 times (a) and 7,000 times (b).

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  FIG. 1 is a schematic cross-sectional view showing one embodiment of a composite particle. The composite particle 14 according to the present embodiment includes a mother particle 12 and a plurality of child particles 13 attached to the outside of the mother particle. The mother particle 12 has a plastic core 10 and a metal coating 11 that covers the plastic core. Further, the child particle 13 covers a part of the surface of the mother particle 12.

  The average particle diameter of the mother particles 12 used in the present embodiment is 1 to 10 μm, preferably 2 to 5 μm, and more preferably 2 to 3 μm. When the mother particles 12 are used as conductive particles in the insulating coated conductive particles (hereinafter also referred to as “conductive particles”), if the average particle diameter of the mother particles 12 is 1 μm or more, variations in electrode height can be absorbed. It is possible to improve the conduction characteristics. Moreover, it is excellent in an insulation characteristic as an average particle diameter is 10 micrometers or less.

  The average particle diameter of the mother particles 12 described here is obtained by photographing about 100 conductive particles at a magnification of several thousand to several tens of thousands of times with an electron microscope (SEM), and then measuring the particle diameter by image analysis. Assume that you have asked. The particle diameter in this example was measured by HITACHI S-4800 (manufactured by Hitachi High-Tech Co., Ltd., trade name). The average particle diameter of the mother particles 12 can also be obtained by measuring the average particle diameter of the plastic core 10 by the same method as described above, then measuring the thickness of the metal coating 11 and adding them up. The thickness of the metal coating 11 can be measured by a general method such as an atomic absorption photometer or SEM cross-sectional observation.

  The method for coating the plastic core 10 with the metal coating 11 is not particularly limited, and examples thereof include a sputtering method and a plating method. Among these, the plating method is preferable from the viewpoint of simplicity.

  Although it does not specifically limit as a metal coat | covered by plating etc., For example, metals, such as gold | metal | money, silver, copper, platinum, zinc, iron, palladium, nickel, tin, chromium, titanium, aluminum, cobalt, germanium, cadmium, ITO, Examples thereof include metal compounds such as solder. From the viewpoint of corrosion resistance, the metal to be coated is preferably one or more metals selected from the group consisting of nickel, palladium and gold. In addition, carbon compounds such as carbon nanotubes and carbon black can be mixed with the above metal in order to improve conduction characteristics and hardness.

  The metal coating 11 may have a single layer structure or a laminated structure composed of a plurality of layers. In the case of a single layer structure, the plating layer is preferably nickel from the viewpoints of cost, conduction characteristics, and corrosion resistance. Furthermore, considering the recent flattening of the glass electrode, nickel plating having protrusions on the surface is preferable in order to improve conduction characteristics. Moreover, when it is a multilayer structure, what has a noble metal like gold | metal | money or palladium on the outer side of nickel from viewpoints, such as an electroconductive property, is preferable.

  Examples of the method for forming protrusions on the metal coating 11 include a method using abnormal deposition of plating and a method using a core material. However, in consideration of making the protrusion shape uniform, a method using a core material is preferable. Examples of the core material include conductive materials such as nickel, carbon, palladium, and gold, and non-conductive materials such as plastic, silica, and titanium oxide. When a ferromagnetic material is used for the core material, magnetic aggregation increases at the stage of covering the insulating particles, and it becomes difficult to attach the child particles 13. For example, when nickel, which is a ferromagnetic material, is used as the core material, The core material preferably further contains a nonmagnetic material such as phosphorus.

  The size of the protrusion is preferably 30 to 300 nm, and more preferably 50 to 200 nm. If the size of the protrusion is 300 nm or less, the short-circuit probability is reduced, and if the size is 30 nm or more, more excellent conduction characteristics can be obtained. The coverage of the protrusions is preferably 5 to 60% with respect to the total surface area of the base particles 12. Further, it is assumed that the size of the protrusion is not included in the average particle diameter of the mother particle 12. In addition, the coverage of protrusions can be obtained by image analysis of SEM photographs.

  Although the thickness of the metal film 11 is not specifically limited, It is preferable that it is 0.001-1 micrometer, and it is more preferable that it is 0.005-0.3 micrometer.

  If the thickness of the metal coating 11 is 0.001 μm or more, conduction failure can be prevented to a higher degree, and if it is 1 μm or less, the conduction characteristics are more excellent.

  The material of the plastic core 10 is not particularly limited, and examples thereof include acrylic resins such as polymethyl methacrylate and polymethyl acrylate, polyolefin resins such as polyethylene, polypropylene, polyisobutylene, and polybutadiene, and copolymers of olefin and acrylic acid. . From the viewpoint of easy adjustment of the glass transition temperature (Tg) and the hardness of the plastic core 10, the plastic core 10 is preferably a copolymer of olefin and acrylic acid, and divinylbenzene, acrylic acid, More preferably, it is a copolymer of

  The child particles 13 used in the present invention are semicircular particles. By using semicircular particles, the contact area between the child particles 13 and the mother particles 12 is wider than that of spherical particles, and the adhesion strength is excellent.

  In this specification, “semicircular particles” are defined as particles that have a circular portion in two dimensions and are not spherical. The semicircular particles are preferably flat and red blood cells. In the present specification, the erythrocyte-shaped particles may have dents on both sides, or may have dents only on one side (hereinafter also referred to as bowl-shaped particles).

  The average maximum particle size of the child particles 13 may be 140 to 500 nm, but is preferably 200 to 450 nm, and more preferably 250 to 400 nm. When the average maximum particle size is 500 nm or less, the adhesion strength between the child particles 13 and the mother particles 12 can be improved. When the average maximum particle size is 140 nm or more, the insulating properties are excellent when the composite particles 14 are used as insulating particles in the insulating coated conductive particles.

  The average maximum thickness of the child particles 13 is 20 to 80% of the average maximum particle size. Preferably, the average maximum thickness is 20 to 70% of the average maximum particle size, more preferably 30 to 60%. When the average maximum thickness is 80% or less of the average maximum particle diameter, the adhesion strength between the child particles 13 and the mother particles 12 is excellent. Further, when the average maximum thickness is 20% or more of the average maximum particle diameter, aggregation of the mother particles can be prevented, and the insulation resistance can be improved when the composite particles 14 of the present invention are used as the insulating coated conductive particles. Can do.

  The average maximum thickness of the child particles 13 is further preferably 100 nm or more, more preferably 120 nm or more, and further preferably 150 nm or more. When the average maximum thickness is 100 nm or more, aggregation of the mother particles can be further prevented.

  The ratio between the average maximum particle size and the average maximum thickness of the child particles 13 is preferably 1.25 to 5, and more preferably 1.3 to 5. When the ratio of the average maximum particle size to the average maximum thickness is 1.25 or more, the adhesive strength with the mother particles is excellent, and when it is 5 or less, the conductive particles 14 are aggregated when the composite particles 14 are used as the conductive particles. Can be prevented, and a decrease in insulation resistance can be prevented.

  In this specification, “average maximum particle size” is the average value of the diameter of the two-dimensional circle portion, and “average maximum thickness” is the average value of the maximum height when the circle is placed on a plane. Means.

  The “diameter of the two-dimensional circle portion” and “the maximum height when the circle is placed on a plane” will be described with reference to FIG. FIG. 5A is a perspective view of a red blood cell-shaped particle (a bowl-shaped particle), and FIG. 5B is a cross-sectional view taken along the line AA in the particle of FIG. In the particles shown in FIG. 5, X corresponds to “the diameter of a two-dimensional circle portion”, and Y corresponds to “the maximum height when the circle is placed on a plane”.

  When the mother particles 12 have protrusions, the average maximum particle size of the child particles 13 is desirably larger than the protrusions from the viewpoint of easily attaching the child particles 13 to the mother particles 12.

  The variation (hereinafter also referred to as CV) of the average maximum particle size of the child particles 13 is preferably 10% or less, and more preferably 3% or less. When the CV is 10% or less, the insulation characteristics and the conduction characteristics can be improved.

  Examples of the child particle 13 that covers the mother particle 12 include organic fine particles, inorganic oxide fine particles, and organic-inorganic hybrid particles.

  Examples of the organic fine particles include particles containing a polyolefin resin such as polyethylene, polypropylene, and polybutadiene, an acrylic resin such as polymethyl methacrylate, an epoxy resin, a polystyrene resin, and a polyimide resin.

  Among these, from the viewpoint of improving solvent resistance, heat resistance and Tg, crosslinked plastic fine particles obtained by copolymerizing methyl methacrylate and styrene with a crosslinking component are preferable.

The inorganic oxide fine particles preferably contain oxides of silicon, aluminum, zirconium, titanium, niobium, zinc, tin, cerium and magnesium. Further, when the child particles 13 are used as insulating particles (hereinafter also referred to as insulating particles) in the insulating coated conductive particles, water-dispersed colloidal silica (SiO ₂ ) particles having a controlled particle diameter are more preferable from the viewpoint of insulating characteristics.

  Further, from the viewpoint of achieving both flexibility and solvent resistance, organic-inorganic hybrid particles in which an organic substance and an inorganic substance are mixed are preferable. Examples of the organic / inorganic hybrid type particles include copolymer particles of a monomer containing silicon and a hydrocarbon. Among these, from the viewpoint of ease of synthesis, it is preferable to include a silicon compound having a double bond.

  As a manufacturing method of the child particles 13, soap-free emulsion polymerization is preferable. In order to obtain semicircular particles, it is preferable to control the shape using a monomer composition containing at least an organic monomer having a carbon-carbon double bond and an alkoxysilane having a carbon-carbon double bond. .

  Examples of the organic monomer having a carbon-carbon double bond include acrylic resins such as styrene and methyl acrylate, methacrylic resins such as methyl methacrylate, and vinyl resins.

  The content of the monomer having a carbon-carbon double bond is preferably 50 mol% or more based on the total amount of the monomer composition.

  Examples of the alkoxysilane having a carbon-carbon double bond include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, Examples include 3-acryloxypropyltrimethoxysilane.

  The content of the alkoxysilane having a carbon-carbon double bond is preferably 1 to 5 mol% with respect to the total amount of the monomer composition.

  Examples of the radical polymerization initiator include benzoyl peroxide, t-butylbenzoate, potassium peroxodisulfate, 1,1-azobis (cyclohexane-1-carbonitrile), 2,2-azobisisobutyronitrile and the like. However, it is not limited to these.

  When soap-free emulsion polymerization is performed, by adding a hydrophilic monomer, the particles can be synthesized more stably and the control of the particle size becomes easier. Specific examples of the hydrophilic monomer include styrene sulfonic acid, sodium styrene sulfonate, methacrylic acid, and sodium methacrylate.

  It is preferable that content of a hydrophilic monomer is 0.1-10 mol% with respect to the monomer composition whole quantity.

  In order to improve the solvent resistance, heat resistance and glass transition temperature of the child particles 13, it is desirable to add a crosslinking agent. Specifically, divinylbenzene, diacrylate and the like are preferable as the crosslinking agent. In addition, the content of the crosslinking agent is preferably 0 to 10 mol% with respect to the total monomers of the child particles 13 from the viewpoint of ease of synthesis. Further, in view of characteristics, the content of the crosslinking agent is More preferably, it is 1-5 mol%.

Soap-free emulsion polymerization methods are well known to those skilled in the art. Preferably, for example, a monomer for synthesis, water, and a polymerization initiator are placed in a flask, and stirring is performed at a stirring speed of 100 to 500 min ⁻¹ (rpm) in a nitrogen atmosphere. The total monomer content is desirably 1 to 20% by mass with respect to the solvent water.

  The polymerization temperature of soap-free emulsion polymerization is preferably 40 to 90 ° C., and the polymerization time is preferably in the range of 2 hours to 15 hours. Appropriate polymerization temperature and time can be appropriately selected by those skilled in the art.

  The method of attaching the child particles 13 to the mother particles 12 is not particularly limited, and examples thereof include a method of attaching the child particles 13 having functional groups to the mother particles 12 having functional groups. Therefore, it is desirable that the child particles have a functional group with good reactivity such as a hydroxyl group, a silanol group, or a carboxyl group on the outside.

  It is preferable that a functional group such as a hydroxyl group, a carboxyl group, an alkoxy group, or an alkoxycarbonyl group is formed on the surface of the mother particle 12. When the mother particle 13 has these functional groups on the surface, a strong bond such as a covalent bond or a hydrogen bond by dehydration condensation can be formed with the functional group on the surface of the child particle 12.

  When the mother particle 12 has a gold or palladium surface, a hydroxyl group, a carboxyl group on the surface of the metal layer using a compound having any of a mercapto group, a sulfide group, and a disulfide group that forms a coordinate bond with gold or palladium, One or more functional groups selected from the group consisting of an alkoxyl group and an alkoxycarbonyl group may be introduced. Specifically, mercaptoacetic acid, 2-mercaptoethanol, methyl mercaptoacetate, mercaptosuccinic acid, thioglycerin, cysteine and the like are used.

  When the mother particle 12 has a nickel surface, a compound having a silanol group or a hydroxyl group that forms a strong bond with nickel, or a nitrogen compound is selected from the group consisting of a hydroxyl group, a carboxyl group, an alkoxyl group, and an alkoxycarbonyl group on the nickel surface. One or more functional groups selected may be introduced. Specifically, carboxybenzotriazole or the like is used.

  The method for treating the surface of the metal layer with the above compound is not particularly limited, but a compound such as mercaptoacetic acid or carboxybenzotriazole is dispersed at a concentration of 10 to 100 mmol / L in an organic solvent such as methanol or ethanol, There is a method of dispersing conductive particles having a metal surface.

  However, the surface potential (zeta potential) of the mother particle 12 having a functional group such as a hydroxyl group, a carboxyl group, an alkoxyl group, or an alkoxycarbonyl group is usually negative when the pH is in a neutral region. On the other hand, the surface potential of the child particle 13 having a hydroxyl group is usually negative. In many cases, it is difficult to sufficiently cover the surface of particles having a negative surface potential with particles having a negative surface potential. However, by providing a polymer electrolyte layer between them, the child particles 13 can be efficiently attached to the mother particles 13. It can be attached to the particles 12.

  Furthermore, by providing the polymer electrolyte layer, the child particles 13 can be uniformly coated on the surface of the mother particles 12 without any defects. Thereby, when the composite particles are used as the insulating coated conductive particles, the insulation characteristics are ensured even when the circuit electrode interval is narrow, while the connection resistance is low between the electrically connected electrodes and the conduction characteristics are good.

The method of attaching the child particles 13 having a functional group to the outside of the mother particles 12 having a functional group via a polymer electrolyte is not particularly limited, but a method of alternately laminating the polymer electrolyte and the child particles 13 is preferable. . As a more specific manufacturing method,
(1) dispersing the mother particles 12 having a functional group in a solution containing a polymer electrolyte, adsorbing the polymer electrolyte on at least a part of the surface of the mother particles 12 having a functional group, and rinsing;
(2) The mother particles 12 on which the polymer electrolyte is adsorbed are dispersed in a dispersion containing the child particles 13, and the polymer electrolyte is adsorbed on at least part of the surface of the mother particles 12 having functional groups. Adsorbing and rinsing the child particles 13;
including. By the above method, composite particles 14 having a polymer electrolyte and child particles 13 laminated on the surface can be produced.

  Such a method is called an alternating lamination method (Layer-by-Layer assembly). The alternate lamination method is described in G.H. This is a method for forming an organic thin film published in 1992 by Decher et al. (Thin Solid Films, 210/211, p831 (1992)). In this method, the substrate is alternately immersed in an aqueous solution containing a polymer electrolyte having a positive charge (polycation) and a polymer electrolyte having a negative charge (polyanion). As a result, a combination of polycation and polyanion adsorbed by electrostatic attraction on the substrate is laminated to obtain a composite film (alternate laminated film).

  In the alternate lamination method, a film grows by attracting a charge of a material formed on a substrate and a material having an opposite charge in a solution by electrostatic attraction. When the adsorption proceeds and the charge is neutralized, no further adsorption occurs. Accordingly, when reaching a certain saturation point, the film thickness does not increase any more. Lvov et al. Applied an alternate lamination method to fine particles, and reported a method of laminating a polymer electrolyte having a charge opposite to the surface charge of the fine particles by using the fine particle dispersions of silica, titania and ceria. (Langmuir, Vol. 13, p6195-6203 (1997)). When this method is used, insulating particles having negative surface charges and polydiallyldimethylammonium chloride (PDDA) or polyethyleneimine (PEI), which are polycations having opposite charges, are alternately laminated to form insulating particles. It is possible to form a fine-particle laminated thin film in which and a polymer electrolyte are alternately laminated.

  After immersing the mother particle 12 having a functional group in a solution containing the polymer electrolyte and before immersing in the dispersion containing the child particles 13, the solution containing the excess polymer electrolyte may be washed away by rinsing with only the solvent. preferable. Moreover, it is preferable to wash away the dispersion liquid containing the surplus child particles 13 by rinsing with only the solvent even after the mother particles 12 having a functional group adsorbing the polymer electrolyte are immersed in the dispersion liquid containing the child particles 13. . Similarly, after the mother particle 12 having a functional group is immersed in the dispersion of inorganic oxide fine particles and before being immersed in the polymer electrolyte solution, the dispersion containing excess inorganic oxide fine particles is washed away by rinsing with only the solvent. It is preferable.

  Examples of the solvent used for such rinsing include, but are not limited to, water, alcohol, acetone, and a mixed solvent thereof.

  The polymer electrolyte is capable of adsorbing with the functional group introduced on the surface of the mother particle 12. This polymer electrolyte is, for example, electrostatically adsorbed to the functional group. As such a polymer electrolyte, a polymer (polyanion or polycation) ionized in an aqueous solution and having a charged functional group in the main chain or side chain can be used. Examples of polyanions generally include those having a negatively charged functional group such as sulfonic acid, sulfuric acid, and carboxylic acid. When the surface potential of the mother particle 12 and / or the child particle 13 is negative, A polycation may be used. The polycation generally has a positively charged functional group such as polyamines such as polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polydiallyldimethylammonium chloride (PDDA). , Polyvinyl pyridine (PVP), polylysine, polyacrylamide, and a copolymer containing at least one of them can be used. Among these, PEI is preferably used because of its high electrification density and strong bonding strength.

  Among these polymer electrolytes, alkali metal (Li, Na, K, Rb, Cs) ions, alkaline earth metal (Ca, Sr, Ba, Ra) ions and halide ions are used to avoid electromigration and corrosion. What does not substantially contain (fluorine ion, chloride ion, bromine ion, iodine ion) is preferable.

  Any of these polymer electrolytes is water-soluble or soluble in an organic solvent such as alcohol. The weight average molecular weight of the polymer electrolyte cannot be generally determined depending on the type of the polymer electrolyte to be used, but generally 1,000 to 200,000 is preferable, and 2,000 to 150,000 is preferable. More preferred is 5,000 to 100,000. When the weight average molecular weight of the polymer electrolyte is 1,000 to 200,000, sufficient dispersibility of the mother particles can be obtained, and even if the average particle diameter of the mother particles 12 is 3 μm or less, the mother particles 12 Aggregation can be prevented.

  The polymer electrolyte solution is dissolved in water or a mixed solvent of an organic solvent. Examples of water-soluble organic solvents that can be used include methanol, ethanol, propanol, acetone, dimethylformamide, acetonitrile, and the like.

  In general, the concentration of the polymer electrolyte in the solution is preferably 0.01 to 10% by mass, more preferably 0.05 to 2% by mass, and 0.1 to 1% by mass. More preferably. Adhesiveness and dispersibility can be improved as the concentration of the polymer electrolyte is 0.01 to 10% by mass or more. Further, the pH of the polymer electrolyte solution is not particularly limited.

  Further, the coverage of the mother particles 12 by the child particles 13 can be controlled by adjusting the type, molecular weight or concentration of the polymer electrolyte.

  Specifically, when a polymer electrolyte with a high charge density such as PEI is used, the coverage by the child particles 13 tends to be high, and when a polymer electrolyte with a low charge density such as PDDA is used, it depends on the child particles 13. The coverage tends to be low. Further, when the weight average molecular weight of the polymer electrolyte is large, the coverage by the child particles tends to be high, and when the weight average molecular weight of the polymer electrolyte is small, the coverage by the child particles 13 tends to be low. Furthermore, when the polymer electrolyte is used at a high concentration, the coverage by the child particles 13 tends to be high, and when the polymer electrolyte is used at a low concentration, the coverage by the child particles 13 tends to be low. The type, molecular weight and concentration of such a polymer electrolyte can be appropriately selected by those skilled in the art.

  When the base particle 12 is a particle having the plastic core 10 and the metal coating 11 covering the plastic core, the magnetic aggregation increases as the particle size decreases, making it difficult to attach the child particles 13. In that case, when the surface of the mother particle 12 preferably has a polymer having a weight average molecular weight of 1,000 or more, dispersion of the mother particle 12 is promoted and adhesion becomes easy.

  Further, it is desirable that the child particles 13 have a polymer or oligomer having a weight average molecular weight of 500 to 10,000, more preferably 1,000 to 4,000, on the surface. Such a polymer or oligomer is preferably a silicone oligomer having a functional group having a weight average molecular weight of 1,000 to 4,000. The functional group is preferably one that reacts with the polymer electrolyte, more preferably a glycidyl group, a carboxyl group or an isocyanate group, and particularly preferably a glycidyl group. Thereby, while making the dispersibility of the child particle 13 favorable, stronger bond can be expected by reacting the functional group on the polymer or oligomer with the functional group on the mother particle 12.

  Thus, by combining particles having a chemically reactive polymer, a strong bond that has never been obtained can be obtained. In particular, when the composite particles 14 are used as the insulating coated conductive particles, it is possible to cope with the reduction in the diameter of the conductive particles and the increase in the diameter of the insulating particles.

  The coverage of the child particles 13 is preferably 10 to 70%, and more preferably 20 to 60%. When the coverage is 10% or more, better insulating characteristics can be obtained when the composite particles 14 are used as the insulating coated conductive particles, and excellent conduction characteristics are maintained when the coverage is 70% or less. Further, the coating variation (CV) is preferably in the range of 0.3 or less, more preferably 0.25 or less, and further preferably 0.2 or less. When CV is 0.3 or less, more insulating characteristics and conductive characteristics can be obtained. The coverage is calculated by analyzing the center part of the mother particle 12 in the SEM photograph of the composite particle (a circle having a length half the diameter of the outer circle of the mother particle 12 and concentric with the outer circle). What you can do. Specifically, the total surface area of the center part of the mother particle 12 in the SEM photograph is W (area calculated from the particle diameter of the mother particle), and the child particle 13 covers the center part of the mother particle 12 in the SEM photograph. The coverage is expressed as P / W × 100 (%), where P is the surface area of the portion analyzed as being. CV is expressed as standard deviation / average coverage x 100 (%). In addition, the surface area P of the portion analyzed to be covered in the present embodiment is an average value of the surface areas obtained from 200 SEM photographs of the composite particles.

  In general, the insulating coated conductive particles tend to have high insulation characteristics and poor conduction characteristics when the insulation particle coverage is high, and the conduction characteristics and insulation characteristics are poor when the insulation particle coverage is low. Tend to be. However, when the flat or erythrocyte-shaped semicircular child particles of the present embodiment are used, good conduction characteristics are maintained even at a high coverage of 70%, and both the insulation characteristics and the conduction characteristics are excellent. Conductive particles can be obtained.

  Further, from the viewpoint of easily controlling the amount of lamination, it is preferable that only one layer of the child particles 13 is coated.

  The composite particles 14 can further strengthen the bond between the child particles 13 and the mother particles 12 by heating and drying. The reason why the binding force increases is, for example, the strengthening of chemical bonds between a functional group such as a carboxyl group introduced on the surface of the mother particle 12 and a functional group such as a hydroxyl group introduced on the surface of the child particle 13. The heat drying temperature is preferably 60 to 100 ° C., and the time is preferably 10 to 180 minutes. If the temperature is 60 ° C. or higher, the child particles 13 are difficult to peel off from the mother particles 12, and if the temperature is 100 ° C. or lower, the mother particles 12 are difficult to deform. Similarly, if the heat drying time is 10 minutes or more, the child particles 13 are difficult to peel off, and if it is 180 minutes or less, the mother particles 12 are difficult to deform.

  The composite particles 14 having functional groups on the surface can be further surface treated with a silicone oligomer, octadecylamine or the like. Thereby, when the composite particles 14 are used as the insulating coated conductive particles, the insulating characteristics can be improved, and the insulating coated conductive particles having excellent insulating characteristics can be obtained. Furthermore, if necessary, the insulating properties can be further improved by using a condensing agent.

  Said composite particle 14 can be used as an insulation coating electroconductive particle provided with the mother particle 12 which is an electroconductive particle, and the child particle 13 which is an insulating particle. Further, the insulating coated conductive particles can be dispersed in the adhesive 5 to be used as an anisotropic conductive adhesive.

  As the adhesive of the anisotropic conductive adhesive of the present embodiment, a mixture of a thermosetting resin and a curing agent is used. Examples of the thermosetting resin include radical reactive resins, and examples of the curing agent include organic peroxides. Further, energy ray curable resins such as ultraviolet rays are also used. Such a resin, curing agent, organic peroxide, and energy beam can be selected by those skilled in the art as needed.

  In the present embodiment, from the viewpoint of adhesiveness, the thermosetting resin constituting the adhesive is preferably an epoxy resin. Epoxy resins used include bisphenol-type epoxy resins derived from epichlorohydrin and bisphenol A, bisphenol F, bisphenol AD, etc., epoxy novolac resins derived from epichlorohydrin, phenol novolac, cresol novolac, etc., and a skeleton containing a naphthalene ring. Examples thereof include a compound having two or more glycidyl groups in one molecule such as naphthalene-based epoxy resin, glycidylamine, glycidyl ether, biphenyl, and alicyclic. These epoxy resins may be used alone or in combination of two or more.

For these epoxy resins, it is preferable to use a high-purity product in which impurity ions (Na ⁺ , Cl ^{− and the} like), hydrolyzable chlorine and the like are reduced to 300 ppm or less, in order to prevent electromigration.

  Examples of the curing agent include latent curing agents such as imidazole, hydrazide, boron trifluoride-amine complex, sulfonium salt, amine imide, polyamine salt, and dicyandiamide.

  In order to reduce the stress after adhesion or to improve the adhesion, the adhesive may further contain a rubber such as butadiene rubber, acrylic rubber, styrene-butadiene rubber, silicone rubber or the like.

  The anisotropic conductive adhesive can be used as a film or a paste. In order to make the anisotropic conductive adhesive into a film, it is effective to blend a thermoplastic resin such as phenoxy resin, polyester resin, polyamide resin or the like into the adhesive as a film-forming polymer. These thermoplastic resins also have a stress relieving effect when the thermosetting resin is cured. In addition, it is more preferable that the film-forming polymer has a functional group such as a hydroxyl group because the adhesiveness is improved.

  The anisotropic conductive adhesive film includes, for example, a step of dissolving or dispersing an adhesive composed of an epoxy resin, acrylic rubber, a latent curing agent, and composite particles 4 in an organic solvent to make it liquefied; Can be obtained by a method comprising a step of applying a liquid composition containing selenium onto a peelable substrate and a step of removing the organic solvent from the applied liquid composition at a temperature lower than the activation temperature of the curing agent. The organic solvent used at this time is preferably a mixed solvent of an aromatic hydrocarbon type and an oxygen-containing type from the viewpoint of improving the solubility of the material.

  In the anisotropic conductive adhesive film, the adhesive layer is preferably multilayered. For example, a two-layer anisotropic conductive adhesive film formed by laminating a conductive adhesive layer for imparting anisotropic conductivity and an insulating adhesive layer, and a conductive adhesive layer, and insulating on both sides Examples thereof include an anisotropic conductive adhesive film having a three-layer structure in which an adhesive layer is laminated. In addition, a conductive contact bonding layer contains the above-mentioned insulation coating electroconductive particle. By disposing the insulating adhesive layer on the metal bump side and the conductive adhesive layer on the glass side, the insulating coated conductive particles can be efficiently captured on the metal bump side, which is advantageous for narrow pitch connection. .

  The conductive adhesive layer is preferably as thin as possible from the viewpoint of connectivity. On the other hand, the insulating adhesive layer is preferably thicker and more fluid than the conductive adhesive layer. Specifically, the thickness of the conductive adhesive layer is 3 to 15 μm, and the thickness of the insulating adhesive layer is 7 to 20 μm. When the thickness of the conductive adhesive layer is 3 μm or more and 15 μm or less, better connectivity can be obtained. When the thickness of the insulating adhesive layer is 7 μm or more and 20 μm or less, the fluidity is excellent.

  Moreover, it is preferable that content of an electroconductive contact bonding layer is 50 mass% or less of the total mass of an anisotropic conductive adhesive film.

  Furthermore, the anisotropic conductive adhesive film preferably has a three-layer structure in which an insulating adhesive layer is disposed on both surfaces of the conductive adhesive layer in order to enhance the adhesiveness with the glass substrate or ITO. The thickness of the two insulating adhesive layers in the anisotropic conductive adhesive film having such a three-layer structure may be the same or different. For example, one is preferably 2 to 15 μm and the other is preferably 7 to 20 μm. .

  As described above, the case where the mother particle has the plastic core and the metal film covering the plastic core has been described. However, the mother particle may be other conductive particles or non-conductive particles. . Examples of the conductive particles include particles made of only metal, and those obtained by coating an organic core or an inorganic core with a metal conductive film. Among these, those in which a plastic core is coated with a metal film are preferable because the distribution of particle diameters can be narrowed. Moreover, as a nonelectroconductive particle, a resin particle and a silica particle are mentioned, for example.

  One embodiment of a method for producing a connection structure using the anisotropic conductive adhesive will be described with reference to FIG.

  FIG. 2 is a cross-sectional view showing an embodiment of a circuit connection method using an anisotropic conductive adhesive using the composite particles of the present invention as insulating coated conductive particles. A first circuit member 20 having an IC chip 1 and metal bumps 2 provided on the IC chip, and a second circuit member 30 having a glass substrate 8 and an electrode 7 provided on the glass substrate, The metal bumps 2 and the electrodes 7 are arranged so as to face each other. An anisotropic conductive adhesive 9 is disposed between the first circuit member 20 and the second circuit member 30. The electrode 7 is an ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide) electrode. The anisotropic conductive adhesive 9 is insulated from the insulating adhesive layer 3 disposed on the first circuit member 20 side, the insulating adhesive layer 6 disposed on the second circuit member 30 side, and the insulating adhesive layer 3. This is a three-layer configuration of a conductive adhesive layer 40 disposed between the conductive adhesive layer 6 and the conductive adhesive layer 6. The conductive adhesive layer 40 is composed of the adhesive 5 and the insulating coated conductive particles 4 dispersed in the adhesive.

  By heating and pressurizing the whole in such a state, a connection structure 100 in which the first circuit member 20 and the second circuit member 30 are connected as shown in the cross-sectional view of FIG. 3 is obtained. It is done. The heating and pressurizing conditions are appropriately adjusted according to the curability of the adhesive 5 in the anisotropic conductive adhesive 9 so that the anisotropic conductive film is cured and sufficient adhesive strength is obtained. can do. In the connection structure manufactured in this way, the conductive particles are easily captured on the metal bumps 2, so that higher conduction characteristics can be obtained between the metal bumps 2 and the glass substrate. In addition, the improvement in the supplement rate reduces the proportion of conductive particles flowing between adjacent circuit electrodes, thereby improving the insulation characteristics.

[Preparation of Conductive Particle 1]
10 g of a plastic core composed of a copolymer of divinylbenzene and acrylic acid having an adjusted degree of crosslinking and having a carboxyl group on the surface was prepared. The average particle size of the plastic core was 2.6 μm.

The hardness of the plastic core was 2746 MPa (280 kgf / mm ² ). The hardness was measured as a compression elastic modulus and 20% K value when the particle diameter was displaced by 20% at 200 ° C.

  Next, electroless nickel plating and electroless palladium plating were performed in this order on the plastic core to produce conductive particles. The thickness of the obtained nickel layer was 100 nm, and the thickness of the palladium layer was 16 nm.

(Preparation of insulating particles 1)
In 400 g of pure water contained in a 500 ml flask, 600 mmol of styrene, 6 mmol of potassium peroxodisulfate and 30 mmol of 3-methacryloxypropyltrimethoxysilane were added as initiators, and a small amount of styrene sulfonic acid was added as a particle size control agent. The mixture was heated for 6 hours with stirring. The stirring speed was 200 min ⁻¹ (rpm).

  As a result of measuring the particle size of the synthesized fine particles by image analysis of HITACHI S-4800 (trade name, manufactured by Hitachi High-Tech Co., Ltd.), the obtained particles had an average maximum particle size of 480 nm and an average maximum thickness of 180 nm. It was. As shown in the SEM photograph (magnification 15,000 times) in FIG. 4, the obtained particles were the bowl-shaped particles shown in the schematic diagram in FIG.

(Preparation of insulating particles 2)
Insulating particles 2 were produced in the same manner as insulating particles 1 except that the amount of 3-methacryloxypropyltrimethoxysilane was 20 mmol.

(Preparation of insulating particles 3)
Insulating particles 3 were produced in the same manner as the insulating particles 1 except that the amount of 3-methacryloxypropyltrimethoxysilane was changed to 10 mmol.

(Preparation of insulating particles 4)
Insulating particles 4 were produced in the same manner as insulating particles 1 except that the amount of 3-methacryloxypropyltrimethoxysilane was changed to 5 mmol.

(Preparation of insulating particles 5)
The insulating particles 5 were produced in the same manner as the insulating particles 1 except that the amount of 3-methacryloxypropyltrimethoxysilane was changed to 0 mmol.

(Preparation of insulating particles 6)
Insulating particles 6 were produced in the same manner as insulating particles 1 except that the amount of 3-methacryloxypropyltrimethoxysilane was 40 mmol.

(Preparation of insulating particles 7)
Insulating particles 7 were produced in the same manner as the insulating particles 1 except that the amount of 3-methacryloxypropyltrimethoxysilane was 50 mmol.

(Preparation of silicone oligomer 1)
A solution containing 118 g of 3-glycidoxypropyltrimethoxysilane and 5.9 g of methanol was added to a glass flask equipped with a stirrer, a condenser and a thermometer. Further, 5 g of activated clay and 4.8 g of distilled water were added, and the mixture was stirred at 75 ° C. for a certain time, and then a silicone oligomer having a weight average molecular weight of 1,300 was obtained. The obtained silicone oligomer has a methoxy group or a silanol group as a terminal functional group that reacts with a hydroxyl group. Methanol was added to the obtained silicone oligomer solution to prepare a treatment liquid having a solid content of 20% by weight.

In addition, the weight average molecular weight of the silicone oligomer was measured by a gel permeation chromatography method (GPC) method, and was calculated by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
GPC conditions Pump: Hitachi L-6000 type (trade name, manufactured by Hitachi, Ltd.)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above, Hitachi Chemical Co., Ltd., trade name)
Eluent: Tetrahydrofuran (THF)
Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (trade name, manufactured by Hitachi, Ltd.)

[Preparation of insulating coated conductive particles]
(Insulation coated conductive particles 1)
A reaction solution was prepared by dissolving 8 mmol of mercaptoacetic acid in 200 ml of methanol. Next, 10 g of the conductive particles 1 was added to the reaction solution, and the mixture was stirred at room temperature for 2 hours with a three-one motor and a stirring blade having a diameter of 45 mm. After washing with methanol, the mixture was filtered using a membrane filter (manufactured by Millipore) having a pore size of 3 μm to obtain 10 g of conductive particles 1 having a carboxyl group on the surface.

  Next, a 30% polyethyleneimine aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) having a weight average molecular weight of 70,000 was diluted with ultrapure water to obtain a 0.3 wt% polyethyleneimine aqueous solution. 10 g of the conductive particles having a carboxyl group were added to a 0.3% by weight polyethyleneimine aqueous solution and stirred at room temperature for 15 minutes. Thereafter, the conductive particles were filtered using a membrane filter (manufactured by Millipore) having a pore size of 3 μm, and the filtered conductive particles were put into 200 g of ultrapure water and stirred at room temperature for 5 minutes. Furthermore, the conductive particles were filtered using a membrane filter (manufactured by Millipore) having a pore diameter of 3 μm, and washed twice with 200 g of ultrapure water on the membrane filter. By performing these operations, unimsorbed polyethyleneimine was removed, and conductive particles coated on the surface with an amino group-containing polymer were obtained.

  Next, the insulating particles 1 were treated with the silicone oligomer 1 to prepare a methanol dispersion medium for the insulating particles 1 having a glycidyl group-containing oligomer on the surface.

  By immersing the conductive particles whose surfaces are coated with amino group-containing polymer in isopropyl alcohol and dropping the methanol dispersion medium of insulating particles 1 having glycidyl group-containing oligomers on the surface, the insulating particle coverage becomes 40%. Insulating coated conductive particles were prepared as described above. The coverage was adjusted by the dropping amount.

  The obtained insulating coated conductive particles were treated with a condensing agent (4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (DMTMM)) and octadecylamine. The surface was hydrophobized by washing. Then, the insulating coated conductive particles 1 were produced by heating and drying at 80 ° C. for 30 minutes and further heating and drying at 80 ° C. for 1 hour. In addition, the SEM photograph of the obtained insulating coating conductive particles is shown in FIG. 6A (magnification: 25,000 times) and FIG. 6B (magnification: 7,000 times).

(Insulation coated conductive particles 2)
The insulating coated conductive particles 2 were produced in the same manner as the insulating coated conductive particles 1 except that the insulating particles 2 were used instead of the insulating particles 1.

(Insulation coated conductive particles 3)
The insulating coated conductive particles 3 were produced in the same manner as the insulating coated conductive particles 1 except that the insulating particles 3 were used instead of the insulating particles 1.

(Insulation coated conductive particles 4)
The insulating coated conductive particles 4 were produced in the same manner as the insulating coated conductive particles 1 except that the insulating particles 4 were used instead of the insulating particles 1.

(Insulation coating conductive particles 5)
The insulating coated conductive particles 5 were produced in the same manner as the insulating coated conductive particles 1 except that the insulating particles 5 were used instead of the insulating particles 1.

(Insulation coated conductive particles 6)
The insulating coated conductive particles 6 were produced in the same manner as the insulating coated conductive particles 1 except that the insulating particles 6 were used instead of the insulating particles 1.

(Insulation coating conductive particles 7)
The insulating coated conductive particles 7 were produced in the same manner as the insulating coated conductive particles 1 except that the insulating particles 7 were used instead of the insulating particles 1.

Example 1
300 g of a solvent in which ethyl acetate and toluene are mixed at a weight ratio of 1: 1, 100 g of phenoxy resin (trade name: PKHC, manufactured by Union Carbide), acrylic rubber (40 parts by weight of butyl acrylate, 30 parts by weight of ethyl acrylate, 30 parts of acrylonitrile) By weight, a copolymer of 3 parts by weight of glycidyl methacrylate and 75 g of a weight average molecular weight: 850,000) were dissolved to obtain a solution. Liquid epoxy (Eboxy equivalent 185, manufactured by Asahi Kasei Epoxy Co., Ltd., trade name: NovaCure HX-3941) containing a microcapsule type latent curing agent in this solution, and liquid epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., commercial product) Name: YL980) 400 g was added and stirred. A silica slurry (manufactured by Nippon Aerosil Co., Ltd., trade name: R202) in which silica having an average particle diameter of 14 nm was dispersed in a solvent was added to the obtained mixed solution to prepare an adhesive solution 1. The silica slurry was added so that the content of the silica solid content was 5% by weight with respect to the total solid content of the mixed solution.

  In a beaker, 10 g of a dispersion medium in which ethyl acetate and toluene were mixed at a weight ratio of 1: 1 and the insulating coated conductive particles 1 were placed and ultrasonically dispersed. The ultrasonic dispersion was performed by immersing the above beaker in an ultrasonic bath (Fujimoto Kagaku, trade name: US107) having a frequency of 38 kHz, energy of 400 W, and volume of 20 L, and stirring for 1 minute. A part of the insulating coated conductive particles was taken out from the dispersion medium of ethyl acetate and toluene, and observed by SEM.

The obtained dispersion liquid of insulating coated conductive particles 1 was dispersed in the adhesive solution 1. The obtained dispersion was applied to a separator (silicone-treated polyethylene terephthalate film, thickness 40 μm) with a roll coater and dried at 90 ° C. for 10 minutes to prepare an adhesive film A having a thickness of 10 μm. This adhesive film has 100,000 insulating particles / mm ² of insulating coated conductive particles per unit area.

  Further, the adhesive solution 1 was applied to a separator (silicone-treated polyethylene terephthalate film, thickness 40 μm) with a roll coater, and dried at 90 ° C. for 10 minutes to prepare an adhesive film B having a thickness of 3 μm.

  Further, the adhesive solution 1 was applied to a separator (silicone-treated polyethylene terephthalate film, thickness 40 μm) with a roll coater and dried at 90 ° C. for 10 minutes to prepare an adhesive film C having a thickness of 10 μm.

  Next, each adhesive film was laminated in the order of adhesive film B, adhesive film A, and adhesive film C, and anisotropic conductive adhesive film D consisting of three layers was produced.

(Example 2)
An anisotropic conductive adhesive film D was prepared in the same manner as in Example 1 except that the insulating coated conductive particles 2 were used instead of the insulating coated conductive particles 1.

(Example 3)
An anisotropic conductive adhesive film D was produced in the same manner as in Example 1 except that the insulating coated conductive particles 3 were used instead of the insulating coated conductive particles 1.

Example 4
An anisotropic conductive adhesive film D was produced in the same manner as in Example 1 except that the insulating coated conductive particles 4 were used instead of the insulating coated conductive particles 1.

(Example 5)
An anisotropic conductive adhesive film D was produced in the same manner as in Example 1 except that the insulating coated conductive particles 6 were used instead of the insulating coated conductive particles 1.

(Comparative Example 1)
An anisotropic conductive adhesive film D was produced in the same manner as in Example 1 except that the insulating coated conductive particles 5 were used instead of the insulating coated conductive particles 1.

(Comparative Example 2)
An anisotropic conductive adhesive film D was produced in the same manner as in Example 1 except that the insulating coated conductive particles 7 were used instead of the insulating coated conductive particles 1.

Using the produced anisotropic conductive adhesive film D, a chip (area 1.7 × 1.7 mm ² ) provided with metal bumps (area 30 × 90 μm ² , space 8 μm, height 15 μm, number of bumps 362). , A thickness of 0.5 μm) and a glass substrate (thickness 0.7 mm) provided with electrodes were connected as shown below.

After the anisotropic conductive adhesive film D was attached to a glass substrate equipped with electrodes under conditions of a temperature of 80 ° C. and a pressure of 0.98 MPa (10 kgf / cm ² ), the separator was peeled off to prepare for the chip. The glass substrate provided with the bumps and the electrodes are aligned. Next, heating and pressurization were performed for 10 seconds from above the chip under the conditions of a temperature of 190 ° C. and a pressure of 0.39 N / bump (40 gf / bump) to perform the main connection. The anisotropic conductive adhesive film D was disposed such that the adhesive film B was on the glass substrate side and the adhesive film C was on the metal bump side.

[Insulation resistance test and conduction resistance test]
An insulation resistance test and a conduction resistance test were performed on the anisotropic conductive adhesive films prepared in Examples and Comparative Examples. It is important that the anisotropic conductive adhesive film has high insulation resistance between metal bumps and low conduction resistance between metal bumps / glass side electrodes. Regarding the insulation resistance between the metal bumps, an initial value was measured, and the value of the insulation resistance was calculated from an average value of 20 samples. Further, the yield was calculated when the insulation resistance> 10 ⁹ (Ω) was regarded as a good product. The distance between the bumps was 10 μm. Moreover, regarding the conduction resistance between the metal bump / glass side electrode, the initial value and the value after the moisture absorption heat test were measured, and the value of the conduction resistance was calculated from the average value of 14 samples. In addition, the moisture absorption heat test was performed by leaving it to stand for 500 hours under conditions of an air temperature of 85 ° C. and a humidity of 85%.

[Insulator particle coverage]
The coverage of the insulating particles and the coating variation were calculated by the method described above by taking SEM photographs immediately after the production of the insulating coated conductive particles and after dispersing the solvent, analyzing the images, and analyzing the images.

  The measurement results are shown in Tables 2 and 3. According to the sample of each Example, it is possible to provide insulating coated conductive particles having a good coverage after ultrasonic dispersion and excellent in insulation resistance, conduction resistance and moisture absorption resistance.

  As described above, according to the present invention, it is possible to provide conductive particles excellent in insulation and conduction characteristics by suppressing the drop-off of child particles, which has been a conventional problem.

  DESCRIPTION OF SYMBOLS 1 ... IC chip, 2 ... Metal bump, 3 ... Insulating adhesive layer, 4 ... Insulation coating conductive particle, 5 ... Adhesive, 5a ... An anisotropic conductive adhesive layer after hardening, 6 ... Insulating adhesive layer, 7 DESCRIPTION OF SYMBOLS ... Glass side electrode, 8 ... Glass substrate, 9 ... Anisotropic conductive adhesive, 10 ... Plastic core, 11 ... Metal coating, 12 ... Mother particle, 13 ... Child particle, 14 ... Composite particle, 20 ... First Circuit member, 30 ... second circuit member, 40 ... conductive adhesive layer, 100 ... connection structure.

Claims (8)

A composite particle comprising a mother particle and a plurality of child particles attached to the outside of the mother particle,
The mother particles are spherical particles having an average particle diameter of 1 to 10 μm,
The child particle is a composite particle having an average maximum particle diameter of 140 nm or more and 500 nm or less and a semicircular particle having an average maximum thickness in a range of 20 to 80% of the average maximum particle diameter.   The composite particle according to claim 1, wherein the child particle has a flat shape or a red blood cell shape.   The composite particle according to claim 1, wherein the base particle has a plastic core and a conductive coating that covers the plastic core.   The composite particle according to any one of claims 1 to 3, wherein the child particle is an organic-inorganic hybrid type particle.   The composite particle according to any one of claims 1 to 4, wherein the child particle is attached to the outside of the base particle via a polymer electrolyte.   The composite particle according to claim 5, wherein the child particle and the mother particle each have a functional group that reacts with the polymer electrolyte on the surface.   The said child particle contains the copolymer which polymerized the monomer composition containing the organic monomer which has a double bond between carbons, and the alkoxysilane which has a double bond between carbons at least. The composite particle according to any one of the above. An anisotropic conductive adhesive comprising the composite particles according to any one of claims 3 to 7.