KR20220100632A - Electroconductive particle, its manufacturing method, and electroconductive material containing same - Google Patents

Abstract

The electroconductive particle by which the conductive layer is formed in the surface of the core material particle WHEREIN: The highest value of the compression hardness of the said electroconductive particle is 14700 N/mm< ² > or more, and compression hardness shows the highest value at less than 5% of compressibility, Compressibility 20 The average value of the compression hardness in % or more and 50% or less is 1300 N/mm ² or more and less than 5000 N/mm ² , and the ratio of the maximum value of the compression hardness to the average value of the compression hardness in the compressibility of 20% or more and 50% or less is 1.5 Electroconductive particles of 50 or more.

Description

Electroconductive particle, its manufacturing method, and electroconductive material containing same

This invention relates to electroconductive particle and the electroconductive material containing the same.

As conductive particles that can be used as conductive materials of anisotropic conductive materials such as anisotropic conductive films and anisotropic conductive pastes, those in which a conductive layer containing a metal is formed on the surface of a core material particle is generally known, and the conductive layer is used as an electrode or electrical connection between wirings.

When pressure-connecting between electrodes with such electroconductive particle, in order to aim at conduction, it is necessary to remove the oxide film currently formed in the electrode surface, and the hardness which can withstand initial pressurization is calculated|required by electroconductive particle. For example, in Patent Document 1, by including a crosslinkable monomer having a plurality of ethylenically unsaturated groups in the resin particles serving as a core material, the ratio of the compression hardness when compressed 10% to the compression hardness when compressed 50% is within a specific range. By doing it, the electroconductive particle which can make connection resistance low and can improve connection reliability is disclosed. However, in the initial stage at the time of the pressure connection between electrodes, in addition to the characteristic of a core material particle, the characteristic which a conductive layer has is also easy to influence.

From such a viewpoint, patent document 2 describes that the compression hardness at the time of being compressed 5% with the electroconductive particle containing the conductive layer containing the crystal layer which has a crystal structure of nickel and phosphorus is more than a specific value. Further, in Patent Document 3, the conductive portion has a plurality of projections on the outer surface, the ratio of the (111) plane in X-ray diffraction of the projections is 50% or more, and the average maximum diameter of the base is 1 nm or more and 500 nm or less. Electroconductive particles are described.

WO2014/007334 Japanese Patent Laid-Open No. 2013-214511 Japanese Patent Laid-Open No. 2016-119304

Both patent document 2 and patent document 3 can remove the oxide film currently formed in an electrode and a conductive layer by improving the characteristic of a conductive layer, By obtaining the electroconductive particle which the contact area of the electrode after connection and electroconductive particle becomes high, electrode Although it aims at making connection resistance low and improving connection reliability when electrically connecting between them, there exists room for further improvement.

Therefore, the objective of this invention is providing electroconductive particle with connection resistance low and connection reliability higher than conventionally.

As a result of earnestly examining this invention in order to solve the said subject, in the initial stage of pressurizing an electrode, the conductive layer which has the hardness of the grade which can remove the oxide film currently formed in the electrode, and electroconductive particle after being connected The electroconductive particle with which the ratio of hardness of which satisfy|fills the specific range can lower|hang connection resistance, and also discovered that it was excellent also in connection reliability, and completed this invention.

That is, this invention is electroconductive particle by which the conductive layer is formed in the surface of core material particle WHEREIN: The highest value of the compression hardness of the said electroconductive particle is 14700 N/mm< ² > or more, and compression hardness is the highest at less than 5% of compressibility. value, the average value of the compression hardness in the compressibility of 20% or more and 50% or less is 1300 N/mm ² or more and less than 5000 N/mm ² , and the compression hardness with respect to the average value of the compression hardness in the compressibility of 20% or more and 50% or less It is to provide the electroconductive particle whose ratio of the highest value is 1.5 or more and 50 or less.

Moreover, this invention is the manufacturing method of the electroconductive particle which forms a conductive layer on the surface of core material particle by the electroless-plating method, The electroconductive particle which has the process of adding a sulfur compound to the electroless-plating reaction liquid during formation of the said conductive layer. To provide a manufacturing method of

ADVANTAGE OF THE INVENTION According to this invention, connection resistance can provide low connection resistance, and electroconductive particle with high connection reliability.

BRIEF DESCRIPTION OF THE DRAWINGS It is an SEM image of the electroconductive particle obtained in Example 1.

The electroconductive particle of this invention is 14700 N/mm< ² > or more, Preferably it is 16000 N/mm< ² > or more, and the highest value of compression hardness (henceforth "K value") is less than 5% of compressibility, Preferably The compression hardness shows the highest value in any of 1%, 2%, 3%, or 4% of compressibility. It is preferable that the highest value of compressive hardness is 30000N/mm< ² > or less.

Compression hardness in this invention uses a micro compression tester (for example, Shimadzu Corporation MCTM-500), When a load is applied to electroconductive particle of radius R (mm) at a load speed of 2.23 mN/sec. It is a value calculated|required by the following formula by measuring the load value F(N).

Compressive hardness (N/mm ² )=(3/√2)×F×S ^-3/2 ×R ^-1/2

Here, the radius R (mm) of electroconductive particle is the value computed from the average particle diameter mentioned later, and a compressibility is the change rate of the length of the particle diameter direction, It is a ratio of compression displacement S (mm) with respect to an average particle diameter (mm).

Moreover, as for the electroconductive particle of this invention, the average value of the compression hardness in 20% or more of compressibility 50% or less is 1300 N/ ^mm2 or more and less than 5000 N/ ^mm2 , Preferably they are 2000-3500N/ ^mm2 , Compressibility 20% or more Ratio of the maximum value of compression hardness with respect to the average value of compression hardness in 50 % or less is 1.5 or more and 50 or less, Preferably they are 2 or more and 30 or less, Especially preferably, they are 3 or more and 15 or less.

Here, the average value of compression hardness in 20% or more of compressibility and 50% or less of compressibility is a K-value average value in the case of 20%, 30%, 40%, and 50% of compressibility.

In this invention, connection resistance is low that ratio of K value at the time of compression rate 3% with respect to K value at the time of 40% of compressibility is 1.5 or more and 70 or less, especially 3 or more and 50 or less, and connection resistance is high electroconductive particle It is preferable in that

Since the electroconductive particle of this invention is equipped with the characteristic that it is hard at the initial stage of compression and shows flexibility when it compresses as mentioned above, in the initial stage in the case of pressurizing an electrode, the oxide film formed in the electrode It becomes possible to fully remove, and connection resistance can be lowered|hung. Moreover, since flexibility is shown after pressure connection, the contact area with an electrode can be maintained and it is excellent also in connection reliability.

As for the electroconductive particle of this invention, the conductive layer is formed in the surface of core material particle|grains.

As said core material particle|grains, as long as it is a particulate form, even if it is an inorganic substance or an organic substance, it can use without restriction|limiting in particular. Examples of the inorganic core material particles include metal particles such as gold, silver, copper, nickel, palladium and solder, alloys, glass, ceramics, silica, metals or non-metal oxides (including water-containing substances), and metals containing aluminosilicates. silicates, metal carbides, metal nitrides, metal carbonates, metal sulfates, metal phosphates, metal sulfides, metal acid salts, metal halides and carbon. On the other hand, as the core material particles of the organic material, for example, natural fibers, natural resins, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polybutene, polyamide, polyacrylic acid ester, polyacrylnitrile, polyacetal, ionomer, poly and thermoplastic resins such as esters, alkyd resins, phenol resins, urea resins, benzoguanamine resins, melamine resins, xylene resins, silicone resins, epoxy resins, and diallyl phthalate resins. These may be used independently and may be used in combination of 2 or more type.

The core material particles may be composed of a material containing both an inorganic substance and an organic substance instead of the material containing any one of the inorganic substance and the organic substance described above. When the core material particles are composed of a material containing both an inorganic material and an organic material, the presence mode of the inorganic material and the organic material in the core material particles includes, for example, a core containing an inorganic material, and the surface of the core is coated. A core-shell type structure, such as an aspect provided with the shell containing an inorganic substance, or an aspect provided with the core containing an organic substance, and the shell containing the inorganic substance which coat|covers the surface of the said core, etc. are mentioned. In addition to these, a blend type configuration in which an inorganic substance and an organic substance are mixed or randomly fused in one core material particle, etc. are mentioned. As the core material particles composed of a material containing both an inorganic material and an organic material, the material constituting the above-described inorganic material core material particles or organic material core material particles can be used. These core material particle|grains may be used so that each material of an inorganic substance and an organic substance may be comprised independently, and may be used so that each of an inorganic substance and an organic substance may be combined and comprised by 2 or more types of materials.

It is preferable that the core material particle|grains are comprised from resin, and it is more preferable that this resin is a thermoplastic resin. By using the core material containing such a material, dispersion stability between particles can be improved, and appropriate elasticity can be expressed and conduction can be improved at the time of electrical connection of an electronic circuit.

In the case of using an organic material as the core material particles, those having no glass transition temperature or having a glass transition temperature of more than 100 ° C. are those in which the shape of the core material particles is easily maintained in the anisotropic conductive connection step, or the step of forming a metal film It is preferable from the point of being easy to maintain the shape of core material particle|grains in this. Moreover, when a core material particle has a glass transition temperature, it is preferable that a glass transition temperature is 200 degrees C or less at the point which becomes easy to take conduction|electrical_connection by becoming easy to soften electroconductive particle in anisotropic electrically conductive connection, and a contact area becomes large. From this viewpoint, when the core material particles have a glass transition temperature, the glass transition temperature is more preferably more than 100°C and 180°C or less, and particularly preferably more than 100°C and 160°C or less. A glass transition temperature can be calculated|required as the intersection of the tangent of the original baseline and an inflection point in the baseline shift part of a DSC curve obtained by differential scanning calorimetry (DSC), for example.

In the case of using an organic substance as the core material particles, when the organic substance is a highly crosslinked resin, the glass transition temperature is hardly observed even when measured up to 200°C by the above method. In this specification, such particle|grains are also called particle|grains which do not have a glass transition point, and in this invention, you may use such core material particle|grains. As a specific example of the core material particle material which does not have such a glass transition temperature mentioned above, it can obtain by copolymerizing using the crosslinkable monomer together with the monomer which comprises the organic substance illustrated above. Examples of the crosslinkable monomer include tetramethylene di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and ethylene oxide di(meth)acryl. rate, tetraethylene oxide (meth)acrylate, 1,6-hexanedi(meth)acrylate, neopentylglycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylol Propane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, tetramethylolpropane tetra (meth) acrylic Polyfunctional (meth)acrylates, such as late, dipentaerythritol penta(meth)acrylate, glycerol di(meth)acrylate, glycerol tridi(meth)acrylate, polyfunctional, such as divinylbenzene and divinyltoluene Silane-containing monomers such as vinyl monomers, vinyl trimethoxysilane, trimethoxysilyl styrene, and γ-(meth)acryloxypropyltrimethoxysilane, triallyl isocyanurate, diallyl phthalate, diallyl acrylamide and monomers such as diallyl ether. In particular, in the field of COG (Chip on Glass), core material particles made of such a hard organic material are often used.

The shape of the core material particles is not particularly limited. In general, the core material particles are spherical. However, the core material particles may have a shape other than a spherical shape, for example, a fibrous, hollow, plate-like, or needle-like shape, and may have a large number of protrusions on the surface thereof or may have an irregular shape. In this invention, the spherical core material particle|grains are preferable at the point which is excellent in fillability and it is easy to coat|cover a metal.

The conductive layer formed on the surface of core material particle|grains contains the metal which has electroconductivity. Examples of the metal constituting the conductive layer include gold, platinum, silver, copper, iron, zinc, nickel, tin, lead, antimony, bismuth, cobalt, indium, titanium, antimony, bismuth, germanium, aluminum, chromium, palladium, In addition to metals, such as tungsten and molybdenum, or these alloys, metal compounds, such as ITO and solder, etc. are mentioned. Among them, gold, silver, copper, nickel, palladium, or solder is preferable because of its low electrical resistance, and nickel, gold, nickel alloy or gold alloy is particularly preferably used. One type may be sufficient as a metal, and it can also use it in combination of 2 or more type.

A single layer structure may be sufficient as a conductive layer, or the laminated structure containing multiple layers may be sufficient as it. In the case of a multilayer structure including a plurality of layers, the outermost layer is preferably at least one selected from nickel, gold, silver, copper, palladium, nickel alloy, gold alloy, silver alloy, copper alloy, and palladium alloy.

In addition, the conductive layer does not need to coat|cover the whole surface of the core material particle|grains, and may coat|cover only the part. In the case where only a part of the surface of the core material particles is covered, the coating site may be continuous or may be discontinuously coated in an island shape, for example.

It is preferable that they are 0.1 nm or more and 2000 nm or less, and, as for the thickness of a conductive layer, it is more preferable that they are 1 nm or more and 1500 nm or less. When electroconductive particle has the processus|protrusion mentioned later, the height of a processus|protrusion shall not be included in the thickness of the conductive layer here. In addition, in this invention, the thickness of a conductive layer can cut|disconnect the particle|grains of a measurement object into two, and can measure the cross section of the cutout by SEM observation.

The average particle diameter of electroconductive particle becomes like this. Preferably they are 0.1 micrometer or more and 50 micrometers or less, More preferably, they are 1 micrometer or more and 30 micrometers or less. When the average particle diameter of metal-coated particle|grains is in the said range, it is easy to ensure conduction|electrical_connection between opposing electrodes, without generating the short circuit in a direction different from that between opposing electrodes. In addition, in this invention, the average particle diameter of electroconductive particle is the value measured using the scanning electron microscope (Scanning Electron Microscope:SEM). Specifically, the average particle diameter of electroconductive particle is measured by the method as described in an Example. In addition, a particle diameter is the diameter of circular electroconductive particle shape. When electroconductive particle is not spherical, a particle diameter says the largest length (maximum length) among the line segments which cross an electroconductive particle image.

When electroconductive particle has a processus|protrusion on the surface, the height of a processus|protrusion becomes like this. Preferably they are 20 nm or more and 1000 nm or less, More preferably, they are 50 nm or more and 800 nm or less. Although the number of protrusions changes with the particle diameter of electroconductive particle, per electroconductive particle, Preferably it is 1 or more 20,000 or less, More preferably, it is 5 or more and 5000 or less, it is advantageous at the point which improves the electroconductivity of electroconductive particle further. do. Further, the length of the base of the protrusion is preferably 5 nm or more and 1000 nm or less, more preferably 10 nm or more and 800 nm or less. The length of the base of a processus|protrusion means the length along the surface of the electroconductive particle in the site|part in which the processus|protrusion is formed, when measured using the electron microscope image in the cross section of a particle|grain, and the height of a processus|protrusion is a processus|protrusion from the base of a processus|protrusion It is the shortest distance to the vertex. In addition, when a single projection has a plurality of vertices, the highest vertex is the height of the projection. The length of the base of the projection and the height of the projection are the arithmetic mean values measured for 20 different particles observed with an electron microscope.

Although the shape of electroconductive particle changes with the shape of core material particle|grains, there is no restriction|limiting in particular. For example, fibrous, hollow, plate-like or needle-like may be sufficient, and the thing which has many processus|protrusions on the surface, or an amorphous thing may be sufficient. In this invention, it is preferable that it is a spherical shape or the shape which has many processus|protrusions on the outer surface at the point which is excellent in fillability and connectivity. In particular, it is easy to become electroconductive particle with a large compression hardness of a compression initial stage by a shape which has a large processus|protrusion on an outer surface.

Examples of a method for forming a conductive layer on the surface of the core material particles include a dry method using a vapor deposition method, a sputtering method, a mechanochemical method, a hybridization method, or the like, a wet method using an electrolytic plating method, an electroless plating method, or the like. Moreover, you may form a conductive layer on the surface of core material particle|grains combining these methods.

In this invention, since it is easy to obtain the electroconductive particle which has a desired compression hardness to form a conductive layer on the surface of core material particle|grains by the electroless-plating method, it is preferable.

Hereinafter, the case where a nickel-phosphorus plating layer is formed as a conductive layer is demonstrated.

When the conductive layer is formed on the surface of the core material particles by the electroless plating method, the surface of the core material particles is preferably surface-modified so that the surface has the ability to trap noble metal ions or to have the ability to trap noble metal ions. The noble metal ion is preferably an ion of palladium or silver. Having the ability to capture noble metal ions means that noble metal ions can be captured as chelates or salts. For example, when an amino group, an imino group, an amide group, an imide group, a cyano group, a hydroxyl group, a nitrile group, a carboxyl group, etc. exist on the surface of the core material particle, the surface of the core material particle has the ability to capture noble metal ions. have In the case of surface modification so as to have the ability to trap noble metal ions, for example, the method described in Japanese Patent Application Laid-Open No. 61-64882 can be used.

Using these core material particles, a noble metal is supported on the surface. Specifically, the core material particles are dispersed in an acidic aqueous solution in which a noble metal salt such as palladium chloride or silver nitrate is diluted. Thereby, noble metal ions are captured on the surface of the particles. The concentration of the noble metal salt is sufficient in the range of 1×10 ^-7 to 1×10 ^-2 moles per 1 m ² of the surface area of the particles. The core material particles in which noble metal ions are captured are separated from the system and washed with water. Then, the core material particle|grains are suspended in water, a reducing agent is added to this, and a noble metal ion reduction process is performed. Thereby, the noble metal is supported on the surface of the core material particle|grains. As the reducing agent, for example, sodium hypophosphite, sodium borohydride, potassium borohydride, dimethylamine borane, hydrazine, formalin, etc. are used, and among these, it is preferable to be selected based on the constituent material of the desired conductive layer.

Before trapping noble metal ions on the surface of the core material particles, a sensitization treatment for adsorbing tin ions on the surface of the particles may be performed. In order to adsorb the tin ions to the surface of the particles, for example, the surface-modified core material particles may be added to an aqueous solution of stannous chloride and stirred for a predetermined time.

A conductive layer formation process is performed on the core material particles subjected to the pretreatment in this way. There are two types of processing for forming the conductive layer: a treatment for forming a conductive layer having projections and a processing for forming a conductive layer with a smooth surface. First, the processing for forming a conductive layer having projections will be described.

In the process of forming the conductive layer which has a projection part, the following 1st process and 2nd process are performed.

The first step is an electroless nickel plating step of mixing an aqueous slurry of core material particles with an electroless nickel plating bath containing a dispersant, a nickel salt, a reducing agent, a complexing agent, and the like. In such a first step, the self-decomposition of the plating bath occurs simultaneously with the formation of the conductive layer on the core material particles. Since this self-decomposition occurs in the vicinity of the core material particles, the self-decomposed product is captured on the surface of the core material particles during the formation of the conductive layer, so that nuclei of minute projections are generated, and the conductive layer is formed at the same time. . With the nucleus of the generated microprotrusion as a starting point, the protrusion grows.

In the first step, the core material particles described above are preferably sufficiently dispersed in water in a range of 0.1 to 500 g/L, more preferably 1 to 300 g/L to prepare an aqueous slurry. The dispersing operation can be carried out using a shear dispersing device such as a normal stirring, high-speed stirring, or colloid mill or homogenizer. In addition, you may use an ultrasonic wave together for dispersion operation. If necessary, a dispersing agent such as a surfactant may be added in the dispersion operation. Next, an aqueous slurry of core material particles subjected to a dispersion operation is added to an electroless nickel plating bath containing a nickel salt, a reducing agent, a complexing agent, and various additives, and a first electroless plating step is performed.

Examples of the dispersant described above include nonionic surfactants, amphoteric ionic surfactants, and/or water-soluble polymers. Polyoxyalkylene ether type surfactant, such as polyethyleneglycol, polyoxyethylene alkyl ether, and polyoxyethylene alkylphenyl ether, can be used as a nonionic surfactant. As amphoteric surfactant, betaine-type surfactant, such as an alkyl dimethyl acetate betaine, an alkyl dimethyl carboxymethyl acetate betaine, and an alkyl dimethyl amino acetate betaine, can be used. As a water-soluble polymer, polyvinyl alcohol, polyvinylpyrrolidinone, hydroxyethyl cellulose, etc. can be used. These dispersants can be used 1 type or in combination of 2 or more types. The amount of the dispersant used varies depending on the type, but is generally 0.5 to 30 g/L with respect to the volume of the liquid (electroless nickel plating bath). In particular, it is preferable from a viewpoint that the adhesiveness of a conductive layer improves that the usage-amount of a dispersing agent is the range of 1-10 g/L with respect to the volume of a liquid (electroless nickel plating bath).

As the nickel salt, for example, nickel chloride, nickel sulfate or nickel acetate is used, and the concentration thereof is preferably in the range of 0.1 to 50 g/L. As a reducing agent, for example, the thing similar to that used for the reduction|restoration of the noble metal ion demonstrated previously can be used, and it is selected based on the constituent material of the target base film. When using a compound as a reducing agent, for example sodium hypophosphite, its concentration is preferably in the range of 0.1 to 50 g/L.

Examples of the complexing agent include carboxylic acids (salts) such as citric acid, hydroxyacetic acid, tartaric acid, malic acid, lactic acid, gluconic acid or alkali metal salts and ammonium salts thereof, amino acids such as glycine, and amine acids such as ethylenediamine and alkylamine. , other ammonium, EDTA or pyrophosphoric acid (salt), etc., a compound having a complexing action on nickel ions is used. These can be used individually by 1 type or in combination of 2 or more type. The concentration is preferably in the range of 1 to 100 g/L, more preferably 5 to 50 g/L. The pH of the preferable electroless nickel plating bath in this step is the range of 3-14. The electroless nickel plating reaction starts quickly when an aqueous slurry of core material particles is added, and is accompanied by generation of hydrogen gas. The first step is terminated when the generation of the hydrogen gas is not completely confirmed.

Next, in the second step, following the first step, (i) a first aqueous solution containing one of a nickel salt, a reducing agent and an alkali and a second aqueous solution containing the other two types are used, or ( ii) using a first aqueous solution containing a nickel salt, a second aqueous solution containing a reducing agent, and a third aqueous solution containing an alkali, and adding these aqueous solutions to the liquid in the first process simultaneously and over time, respectively Electroless nickel plating is performed. When these liquids are added, the plating reaction starts again, but by adjusting the amount added, the conductive layer to be formed can be controlled to a desired thickness. After the addition of the electroless nickel plating solution is completed, the generation of hydrogen gas is not completely confirmed, and then stirring is continued while maintaining the liquid temperature for a while to complete the reaction.

In the case of (i) above, it is preferable to use the first aqueous solution containing a nickel salt and the second aqueous solution containing a reducing agent and an alkali, but it is not limited to this combination. In this case, a reducing agent and an alkali are not contained in a 1st aqueous solution, and a nickel salt is not contained in a 2nd aqueous solution. As the nickel salt and the reducing agent, those described above can be used. As an alkali, the hydroxide of alkali metals, such as sodium hydroxide and potassium hydroxide, can be used, for example. The same applies to the case of (ii) above.

In the case of (ii) above, the first to third aqueous solutions each contain a nickel salt, a reducing agent, and an alkali, and each aqueous solution contains no other two components other than the component.

In any of the cases (i) and (ii), the concentration of the nickel salt in the aqueous solution is preferably 10 to 1000 g/L, particularly preferably 50 to 500 g/L. The concentration of the reducing agent is preferably 100 to 1000 g/L, particularly 100 to 800 g/L, when a phosphorus compound is used as the reducing agent. When a boron compound is used as the reducing agent, it is preferably 5 to 200 g/L, particularly 10 to 100 g/L. When hydrazine or a derivative thereof is used as the reducing agent, it is preferably 5 to 200 g/L, particularly 10 to 100 g/L. The concentration of the alkali is preferably 5 to 500 g/L, particularly preferably 10 to 200 g/L.

Although the 2nd process is performed continuously after completion|finish of a 1st process, instead of this, you may perform a 1st process and a 2nd process intermittently. In this case, after completion of the first step, the core material particles and the plating solution are separated by filtration or the like, and the core material particles are newly dispersed in water to prepare an aqueous slurry, and a complexing agent is added thereto, preferably 1 An aqueous solution dissolved in a concentration range of from 5 to 100 g/L, more preferably from 5 to 50 g/L is added, and the dispersant is preferably dissolved from 0.5 to 30 g/L, more preferably from 1 to 10 g/L. It may be a method of performing the second step of preparing an aqueous slurry by making the mixture, and adding each of the above-described aqueous solutions to the aqueous slurry. In this way, a conductive layer having projections can be formed.

Then, below, the process which forms the conductive layer with a smooth surface is demonstrated.

Formation of the conductive layer with a smooth surface can be performed by reducing the density|concentration of the nickel salt in the electroless nickel plating bath in the 1st process of the process of forming the said conductive layer which has a projection part. That is, as the nickel salt, for example, nickel chloride, nickel sulfate or nickel acetate is used, and the concentration thereof is preferably in the range of 0.01 to 0.5 g/L. The conductive layer with a smooth surface can be formed by the method of performing the said 1st process and 2nd process other than thinning the density|concentration of the nickel salt in an electroless nickel plating bath.

In this invention, since it is easy to become electroconductive particle with the large compression hardness of a compression initial stage to add a sulfur compound during formation of a conductive layer, it is preferable.

Examples of the sulfur compound include 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2-mercaptobenzimidazole, 2-mercapto-1-methylimidazole, thioglycolic acid, thiodiglycolic acid, and cysteine. , saccharin, thiamine nitrate, N,N-diethyl-dithiocarbamate sodium, 1,3-diethyl-2-thiourea, dipyridine, N-thiazole-2-sulfamylamide, 1,2,3 -benzotriazole-2-thiazoline-2-thiol, thiazole, thiourea, ethylenethiourea, thiosol, sodium thioindoxylate, o-sulfonamide benzoic acid, sulfanilic acid, acid orange, methyl orange, naphthionic acid, Naphthalene-α-sulfonic acid, 1-naphthol-4-sulfonic acid, Schaeferic acid, sulfadiazine, ammonium thiocyanate, potassium thiocyanate, sodium thiocyanate, rhodanine, ammonium sulfide, sodium sulfide, ammonium sulfate, etc. can These sulfur compounds can be used 1 type or in combination of 2 or more types. The amount of the sulfur compound used is preferably such that the total sulfur compound concentration in the electroless plating reaction solution is 0.01 mass ppm or more and 100 mass ppm or less, and more preferably 0.1 mass ppm or more and 50 mass ppm or less. When the amount of the sulfur compound used is too small, the effect of hardening the compression hardness at the initial stage of compression is hardly exhibited.

Although the time to add a sulfur compound should just be during formation of a conductive layer, it is preferable that it is in the middle of a 2nd process. In particular, since it becomes easy to harden the compression hardness of an initial stage of compression by starting addition 5-20 minutes after the start of a 2nd process, it is preferable. The sulfur compound may be added in the entire amount at once, may be added in a plurality of times, or may be added continuously. However, if the entire amount is added at once, it is preferable because it is easy to harden the compression hardness at the initial stage of compression.

In the case of the method of adding the entire amount of the sulfur compound at once, although it varies depending on the scale of the reaction system, for example, when a 1 L reactor is used, the addition time is preferably 30 seconds or less, and further 15 seconds or less. Although there is no lower limit for addition time, Usually, it is 0.1 second or more or 0.5 second or more. By adding a sulfur compound in this range, it becomes easy to harden the compression hardness of a compression initial stage.

In the present invention, in the process for forming the conductive layer having the above projections, by adding the sulfur compound in this way, the projections become large, so that the effect of further hardening the compression hardness at the initial stage of compression can be obtained. have.

In this way, the electroconductive particle of this invention is obtained.

When using the electroconductive particle of this invention as an electroconductive filler of a conductive adhesive as mentioned later, in order to prevent generation|occurrence|production of the short circuit between electroconductive particle, the surface can be coat|covered with insulating resin further. The coating of the insulating resin is destroyed by the heat and pressure applied when the surface of the conductive particles is not exposed as much as possible in the state where no pressure or the like is applied, and when the two electrodes are adhered using a conductive adhesive, and the conductive particles are damaged. At least protrusions on the surface are formed to be exposed. The thickness of the insulating resin can be about 0.1 to 0.5 µm. The insulating resin may cover the whole surface of electroconductive particle, and may only cover a part of the surface of electroconductive particle.

As an insulating resin, a thing well-known in the said technical field can be used widely. Examples thereof include phenol resins, urea resins, melamine resins, allyl resins, furan resins, polyester resins, epoxy resins, silicone resins, polyamide-imide resins, polyimide resins, polyurethane resins, fluororesins, polyolefin resins (Example: polyethylene, polypropylene, polybutylene), polyalkyl (meth) acrylate resin, poly (meth) acrylic acid resin, polystyrene resin, acrylonitrile-styrene-butadiene resin, vinyl resin, polyamide resin, polycarp Bonate resin, polyacetal resin, ionomer resin, polyethersulfone resin, polyphenyloxide resin, polysulfone resin, polyvinylidene fluoride resin, ethyl cellulose, and cellulose acetate are mentioned.

As a method for forming an insulating coating layer on the surface of the conductive particles, chemical methods such as coacervation method, interfacial polymerization method, in situ polymerization method and in-liquid curing coating method, spray drying method, suspension coating method in air, vacuum deposition coating method , physico-mechanical methods such as dry blending method, hybridization method, electrostatic coalescence method, fusion dispersion cooling method and inorganic encapsulation method, and physicochemical methods such as interfacial precipitation method.

The electroconductive particle of this invention obtained in this way is suitable as an electrically-conductive material etc. for connecting, for example, an anisotropic conductive film (ACF), a heat seal connector (HSC), and the electrode of a liquid crystal display panel to the circuit board of the LSI chip for a drive. is used sparingly In particular, the electroconductive particle of this invention is used suitably as an electroconductive filler of an electroconductive adhesive.

The above-described conductive adhesive is preferably used as an anisotropic conductive adhesive that is disposed between two substrates on which conductive substrates are formed, and which adheres the conductive substrate by heat and pressurization to conduct electricity. This anisotropically conductive adhesive contains the electroconductive particle of this invention, and adhesive resin. The adhesive resin can be used without particular limitation as long as it is insulating and is used as an adhesive resin. Any of a thermoplastic resin and thermosetting may be sufficient, and it is preferable that adhesive performance is expressed by heating. Such adhesive resins include, for example, a thermoplastic type, a thermosetting type, and an ultraviolet curing type. In addition, there are a so-called semi-thermosetting type, a composite type of a thermosetting type and an ultraviolet curing type, which exhibits intermediate properties between the thermoplastic type and the thermosetting type. These adhesive resins can be suitably selected according to the surface characteristics of the circuit board etc. which are adherend objects, and the use form. In particular, the adhesive resin comprised including a thermosetting resin is preferable at the point excellent in the material strength after adhesion|attachment.

Specific examples of the adhesive resin include ethylene-vinyl acetate copolymer, carboxyl-modified ethylene-vinyl acetate copolymer, ethylene-isobutyl acrylate copolymer, polyamide, polyimide, polyester, polyvinyl ether, polyvinyl butyral. , polyurethane, SBS block copolymer, carboxyl-modified SBS copolymer, SIS copolymer, SEBS copolymer, maleic acid-modified SEBS copolymer, polybutadiene rubber, chloroprene rubber, carboxyl-modified chloroprene rubber, styrene-butadiene rubber, iso 1 selected from butylene-isoprene copolymer, acrylonitrile-butadiene rubber (hereinafter referred to as NBR), carboxyl-modified NBR, amine-modified NBR, epoxy resin, epoxy ester resin, acrylic resin, phenol resin or silicone resin and those prepared with the main subject being obtained by a species or a combination of two or more species. Among these, as the thermoplastic resin, styrene-butadiene rubber, SEBS, and the like are preferable because of excellent reworkability. As a thermosetting resin, an epoxy resin is preferable. Among them, an epoxy resin is most preferable from the viewpoints of high adhesion, excellent heat resistance and electrical insulation, low melt viscosity, and enabling connection at low pressure.

As said epoxy resin, if it is a polyhydric epoxy resin which has two or more epoxy groups in 1 molecule, the epoxy resin generally used can be used. Specific examples include novolak resins such as phenol novolac and cresol novolac, polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, resorcin, and bishydroxydiphenyl ether, ethylene glycol, neopentyl glycol, glycerin, and trimethyl Polyhydric alcohols such as allpropane and polypropylene glycol, polyamino compounds such as ethylenediamine, triethylenetetramine, and aniline, polyvalent carboxy compounds such as adipic acid, phthalic acid, and isophthalic acid, etc. The glycidyl-type epoxy resin obtained by making chlorohydrin react is illustrated. Moreover, aliphatic and alicyclic epoxy resins, such as dicyclopentadiene epoxy and a butadiene dimer diepoxide, etc. are mentioned. These can be used individually by 1 type or in mixture of 2 or more types.

Moreover, it is preferable from a viewpoint of prevention of ion migration to use the high purity product in which impurity ions (Na, Cl, etc.), hydrolysable chlorine, etc. were reduced as various adhesive resin mentioned above.

The usage-amount of the electroconductive particle of this invention in an anisotropically conductive adhesive is 0.1-30 mass parts normally with respect to 100 mass parts of adhesive resin components, Preferably it is 0.5-25 mass parts, More preferably, it is 1-20 mass parts. When the usage-amount of electroconductive particle exists in this range, it is suppressed that connection resistance and melt viscosity become high, connection reliability is improved, and the anisotropy of connection can fully be ensured.

The anisotropically conductive adhesive may contain additives known in the art in addition to the conductive particles and adhesive resin described above. The compounding quantity can also be made into the range well-known in the said technical field. Other additives include, for example, tackifiers, reactive auxiliary agents, epoxy resin curing agents, metal oxides, photoinitiators, sensitizers, curing agents, vulcanizing agents, deterioration inhibitors, heat-resistant additives, thermal conductivity improvers, softeners, colorants, various coupling agents, or metal inerts. etc. can be exemplified.

Examples of the tackifier include rosin, rosin derivatives, terpene resins, terpene phenol resins, petroleum resins, coumarone-indene resins, styrene resins, isoprene resins, alkylphenol resins, and xylene resins. Examples of the reactive auxiliary agent, that is, the crosslinking agent, include polyols, isocyanates, melamine resins, urea resins, utropines, amines, acid anhydrides, and peroxides. The epoxy resin curing agent can be used without particular limitation as long as it has two or more active hydrogens in one molecule. Specific examples thereof include polyamino compounds such as diethylenetriamine, triethylenetetramine, metaphenylenediamine, dicyandiamide, and polyamideamine; organic acid anhydrides such as phthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride; Novolac resins, such as a phenol novolak and a cresol novolak, etc. are mentioned. These can be used individually by 1 type or in mixture of 2 or more types. Moreover, you may use a latent hardening|curing agent as needed. Examples of the latent curing agent that can be used include imidazole-based, hydrazide-based, boron trifluoride-amine complexes, sulfonium salts, amineimides, polyamine salts, dicyandiamide, and the like, and modified products thereof. . These can be used individually by 1 type or as a mixture of 2 or more types.

Said anisotropically conductive adhesive agent is manufactured using the manufacturing apparatus normally used in the said technical field. For example, by mixing the conductive particles and adhesive resin of the present invention and, if necessary, a curing agent or various additives, and mixing in an organic solvent when the adhesive resin is a thermosetting resin, in the case of a thermoplastic resin, at a temperature equal to or higher than the softening point of the adhesive resin , Specifically, it is preferably prepared by melt-kneading at about 50 to 130 ℃, more preferably about 60 to 110 ℃. The anisotropically conductive adhesive obtained in this way may be apply|coated, and it may apply it as a film form.

Example

Hereinafter, the present invention will be further described by way of Examples. However, the scope of the present invention is not limited to these examples. The properties in the examples were measured by the following method.

(1) Compression hardness (K value) of conductive particles

The K value was calculated|required by the method mentioned above using the micro compression tester (The Shimadzu Corporation make, MCTM-500).

In addition, the K value when a compression rate is X % may be described as "X% K value".

(2) average particle diameter

From the scanning electron microscope (SEM) photograph of the measurement object, 200 particle|grains were arbitrarily extracted, the particle diameter was measured at 10000 times magnification, and the arithmetic mean value was made into the average particle diameter.

[Example 1]

(1) Pretreatment

Spherical benzoguanamine-based soft resin particles having an average particle diameter of 3.0 µm were used as core material particles. The 9 g was put into 200 mL of a conditioner aqueous solution ("Cleaner Conditioner 231" manufactured by Rohm & Haas Denshi Zeyro) while stirring. The concentration of the conditioner aqueous solution was 40 mL/L. Subsequently, the core material particles were surface-modified and dispersed by stirring for 30 minutes while applying ultrasonic waves at a liquid temperature of 60°C. This aqueous solution was filtered, and the core material particle|grains which were repulped and washed once were made into 200 mL slurry. 0.1 g of stannous chloride was added to this slurry. It stirred at room temperature for 5 minutes, and the sensitization process which made tin ion adsorb|suck to the surface of the core material particle|grain was performed. Subsequently, this aqueous solution was filtered, and the core material particle|grains which were repulped and washed once were made into 200 mL slurry, and it maintained at 60 degreeC. 1.5 mL of 0.11 mol/L palladium chloride aqueous solution was thrown into this slurry. It stirred at 60 degreeC for 5 minute(s), and the activation process which capture|acquired palladium ion on the surface of the core material particle|grain was performed. Subsequently, this aqueous solution is filtered, the core material particles that have been repulped and rinsed once are made into a slurry of 100 mL, and 10 mL of a 0.5 g/L dimethylamine borane aqueous solution is added, followed by stirring for 2 minutes while applying ultrasonic waves for pretreatment A slurry of finished core material particles was obtained.

(2) Preparation of plating bath

Electroless nickel- containing 5 g/L sodium tartrate, 2 g/L nickel sulfate hexahydrate, 10 g/L trisodium citrate, 0.1 g/L sodium hypophosphite and 2 g/L polyethylene glycol in an aqueous solution 3 L of phosphorus plating baths were prepared, and it heated up at 70 degreeC.

(3) Electroless plating treatment

To this electroless plating bath, the slurry of the pre-treated core material particles was charged and stirred for 5 minutes, confirming that hydrogen foaming was stopped.

To this slurry, 420 mL of a 224 g/L aqueous nickel sulfate aqueous solution and 420 mL of a mixed aqueous solution containing 210 g/L sodium hypophosphite and 80 g/L sodium hydroxide were added at a rate of 2.5 mL/min by a metering pump. Fractional additions were continued and electroless plating was initiated. After 10 minutes from the start, 2-mercaptobenzothiazole is added in 1 second so that the concentration in the solution finally obtained becomes 7.5 mass ppm, and 40 minutes after the start, the addition rates of the two types of aqueous solutions are all adjusted. 4.7 mL/min. After adding each total amount of the nickel sulfate aqueous solution and the mixed aqueous solution of sodium hypophosphite and sodium hydroxide, stirring was continued for 5 minutes, maintaining the temperature of 70 degreeC. Then, after filtering a liquid and washing|cleaning a filtrate 3 times, it was made to dry with a 110 degreeC vacuum dryer, and the electroconductive particle which has a conductive layer containing a nickel- phosphorus alloy was obtained. The average particle diameter of the obtained electroconductive particle was 3.22 micrometers, and the thickness of the conductive layer was 110 nm, and had a large processus|protrusion part. An SEM image is shown in FIG. 1 . As for the obtained electroconductive particle, compression hardness showed the highest value at 3% of compressibility. Table 1 shows the compression hardness at each compression ratio.

[Example 2]

In Example 1, it replaced with 2-mercaptobenzothiazole of (3) electroless-plating process, and manufactured electroconductive particle by the method similar to Example 1 except adding 2-mercaptobenzoxazole. The average particle diameter of the obtained electroconductive particle was 3.22 micrometers, and the thickness of the conductive layer was 110 nm, and had a large processus|protrusion part. As for the obtained electroconductive particle, compression hardness showed the highest value at 4% of compressibility. Table 1 shows the compression hardness at each compression ratio.

[Example 3]

In Example 1, (2) electroconductive particle was manufactured by the method similar to Example 1 except having changed the density|concentration of nickel sulfate hexahydrate of preparation of a plating bath from 2 g/L to 0.1 g/L. The average particle diameter of the obtained electroconductive particle was 3.22 micrometers, the thickness of the conductive layer was 110 nm, and it was the smooth shape which does not have a processus|protrusion part. As for the obtained electroconductive particle, compression hardness showed the highest value at 3% of compressibility. Table 1 shows the compression hardness at each compression ratio.

[Comparative Example 1]

(1) Pretreatment

Spherical benzoguanamine-based soft resin particles having an average particle diameter of 3.0 µm were used as core material particles. The 9 g was put into 200 mL of a conditioner aqueous solution ("Cleaner Conditioner 231" manufactured by Rohm & Haas Denshi Zeyro) while stirring. The concentration of the conditioner aqueous solution was 40 mL/L. Subsequently, the core material particles were surface-modified and dispersed by stirring for 30 minutes while applying ultrasonic waves at a liquid temperature of 60°C. This aqueous solution was filtered, and the core material particle|grains which were repulped and washed once were made into 200 mL slurry. 0.1 g of stannous chloride was added to this slurry. It stirred at room temperature for 5 minutes, and the sensitization process which made tin ion adsorb|suck to the surface of the core material particle|grain was performed. Subsequently, this aqueous solution was filtered, and the core material particle|grains which were repulped and washed once were made into 200 mL slurry, and it maintained at 60 degreeC. 1.5 mL of 0.11 mol/L palladium chloride aqueous solution was thrown into this slurry. It stirred at 60 degreeC for 5 minute(s), and the activation process which capture|acquired palladium ion on the surface of the core material particle|grain was performed. Subsequently, this aqueous solution is filtered, the core material particles that have been repulped and washed once are made into a slurry of 100 mL, and 10 mL of a 0.5 g/L dimethylamine borane aqueous solution is added and stirred for 2 minutes while applying ultrasonic waves to complete pretreatment core material particles of the slurry was obtained.

(2) Preparation of plating bath

Electroless nickel- containing an aqueous solution in which 5 g/L sodium tartrate, 2 g/L nickel sulfate hexahydrate, 10 g/L trisodium citrate, 0.1 g/L sodium hypophosphite and 2 g/L polyethylene glycol are dissolved 3 L of phosphorus plating baths were prepared, and it heated up at 70 degreeC.

(3) Electroless plating treatment

To this electroless plating bath, the slurry of the pre-treated core material particles was charged and stirred for 5 minutes, confirming that hydrogen foaming was stopped.

To this slurry, 420 mL of a 224 g/L aqueous nickel sulfate aqueous solution and 420 mL of a mixed aqueous solution containing 210 g/L sodium hypophosphite and 80 g/L sodium hydroxide were added at a rate of 2.5 mL/min by a metering pump. Fractional additions were continued and electroless plating was initiated. After adding each total amount of the nickel sulfate aqueous solution and the mixed aqueous solution of sodium hypophosphite and sodium hydroxide, stirring was continued for 5 minutes, maintaining the temperature of 70 degreeC. Then, after filtering a liquid and wash|cleaning a filtrate 3 times, it was made to dry with a 110 degreeC vacuum dryer, and the electroconductive particle which has a conductive layer containing a nickel- phosphorus alloy was obtained. The average particle diameter of the obtained electroconductive particle was 3.22 micrometers, and the thickness of the conductive layer was 110 nm, and had a projection part. Moreover, as for the obtained electroconductive particle, compression hardness showed the highest value at 2% of compressibility. Table 1 shows the compression hardness at each compression ratio.

[Comparative Example 2]

(1) Pretreatment

Spherical benzoguanamine-based soft resin particles having an average particle diameter of 3.0 µm were used as core material particles. The 9 g was put into 200 mL of a conditioner aqueous solution ("Cleaner Conditioner 231" manufactured by Rohm & Haas Denshi Zeyro) while stirring. The concentration of the conditioner aqueous solution was 40 mL/L. Subsequently, the core material particles were surface-modified and dispersed by stirring for 30 minutes while applying ultrasonic waves at a liquid temperature of 60°C. This aqueous solution was filtered, and the core material particle|grains which were repulped and washed once were made into 200 mL slurry. 0.1 g of stannous chloride was added to this slurry. It stirred at room temperature for 5 minutes, and the sensitization process which made tin ion adsorb|suck to the surface of the core material particle|grain was performed. Subsequently, this aqueous solution was filtered, and the core material particle|grains which were repulped and washed once were made into 200 mL slurry, and it maintained at 60 degreeC. 1.5 mL of 0.11 mol/L palladium chloride aqueous solution was thrown into this slurry. It stirred at 60 degreeC for 5 minute(s), and the activation process which capture|acquired palladium ion on the surface of the core material particle|grain was performed. Subsequently, this aqueous solution is filtered, the core material particles that have been repulped and washed once are made into a slurry of 100 mL, and 10 mL of a 0.5 g/L dimethylamine borane aqueous solution is added and stirred for 2 minutes while applying ultrasonic waves to complete pretreatment core material particles of the slurry was obtained.

(2) Preparation of plating bath

Electroless nickel- containing an aqueous solution in which 5 g/L sodium tartrate, 2 g/L nickel sulfate hexahydrate, 10 g/L trisodium citrate, 0.1 g/L sodium hypophosphite and 2 g/L polyethylene glycol are dissolved 3 L of phosphorus plating baths were prepared, 2-mercaptobenzothiazole was added and it heated up at 70 degreeC so that the density|concentration in the liquid finally obtained might be 7.5 mass ppm.

(3) Electroless plating treatment

To this electroless plating bath, the slurry of the pre-treated core material particles was charged and stirred for 5 minutes, confirming that hydrogen foaming was stopped.

To this slurry, 420 mL of a 224 g/L aqueous nickel sulfate aqueous solution and 420 mL of a mixed aqueous solution containing 210 g/L sodium hypophosphite and 80 g/L sodium hydroxide were added at a rate of 2.5 mL/min by a metering pump. Fractional additions were continued and electroless plating was initiated. After adding each total amount of the nickel sulfate aqueous solution and the mixed aqueous solution of sodium hypophosphite and sodium hydroxide, stirring was continued for 5 minutes, maintaining the temperature of 70 degreeC. Subsequently, after filtering a liquid and washing|cleaning a filtrate 3 times, it was made to dry with a 110 degreeC vacuum dryer, and the electroconductive particle which has a nickel- phosphorus alloy film was obtained. The average particle diameter of the obtained electroconductive particle was 3.05 micrometers, and the thickness of the conductive layer was 25 nm, and had a processus|protrusion part. Moreover, as for the obtained electroconductive particle, compression hardness showed the highest value at 2% of compressibility. Table 1 shows the compression hardness at each compression ratio.

[Evaluation of connection resistance and connection reliability]

Evaluation of connection resistance and connection reliability was performed with the following method using the electroconductive particle of an Example and a comparative example.

The insulating adhesive which mixed 100 mass parts of epoxy resins, 150 mass parts of hardening|curing agents, and 70 mass parts of toluene, and 15 mass parts of coated particles obtained by the Example and the comparative example were mixed, and the insulating paste was obtained. This paste was applied on a silicone-treated polyester film using a bar coater, and then the paste was dried to form a thin film on the film. The obtained thin film-forming film was placed between a glass substrate on which aluminum was deposited on the entire surface and a polyimide film substrate on which copper patterns were formed at a pitch of 50 µm, to prepare a sample for measurement of conduction resistance, and electrically connect this sample. The connection resistance value of was measured under room temperature (25 degreeC, 50%RH). It can be evaluated that it is excellent in the connection resistance of electroconductive particle, so that a connection resistance value is low. A result is shown in Table 2.

Moreover, the pressure cooker test which arrange|positioned the said sample for conduction resistance measurement in an airtight container, and processed it in the environment of temperature 121 degreeC, 100% of relative humidity, and 2 atmospheres for 10 hours was done. After the pressure cooker test, the connection resistance value of the sample was measured at room temperature (25°C and 50%RH). It can be evaluated that the connection reliability of electroconductive particle is high, so that the difference of the connection resistance value before and behind a pressure cooker test is small. A result is shown in Table 2.

It turns out that the resistance value is low compared with the electroconductive particle obtained by the comparative examples 1 and 2 of the electroconductive particle obtained by Examples 1-3 from this result. Moreover, it turns out that the electroconductive particle obtained in Examples 1-3 does not have a raise of a connection resistance value even after a pressure cooker test, and is maintaining favorable electrical conductivity.

Claims (10)

The electroconductive particle by which the conductive layer is formed in the surface of the core material particle WHEREIN:
The highest value of the compression hardness of the said electroconductive particle is 14700 N/mm< ² > or more, and compression hardness shows the highest value in less than 5% of compressibility,
The average value of the compression hardness in the compressibility of 20% or more and 50% or less is 1300N/mm ² or more and less than 5000N/mm ² ,
Electroconductive particle whose ratio of the highest value of compression hardness with respect to the average value of compression hardness in 20% or more of compressibility and 50% or less is 1.5 or more and 50 or less. The electroconductive particle of Claim 1 whose ratio of the compression hardness at the time of 3% of compression rates with respect to the compression hardness at the time of 40% of compressibility is 1.5 or more and 70 or less. The electroconductive particle of Claim 1 or 2 whose thickness of the said conductive layer is 0.1 nm or more and 2000 nm or less. Electroconductive particle of any one of Claims 1-3 which has a processus|protrusion on the outer surface. Electroconductive particle of any one of Claims 1-3 with which an outer surface is smooth. The electroconductive material containing the electroconductive particle in any one of Claims 1-5, and insulating resin. It is the manufacturing method of the electroconductive particle which forms a conductive layer on the surface of core material particle by electroless-plating, The manufacturing method of electroconductive particle which has the process of adding a sulfur compound to the electroless-plating reaction liquid during formation of the said conductive layer. The method for producing conductive particles according to claim 7, wherein the sulfur compound is at least one selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, and 2-mercaptobenzimidazole. The manufacturing method of electroconductive particle of Claim 7 or 8 which performs addition of a sulfur compound within 30 second. The manufacturing method of electroconductive particle as described in any one of Claims 7-9 whose addition amount of the said sulfur compound is a quantity from which the total sulfide concentration in an electroless-plating reaction liquid becomes 0.01 ppm or more and 500 ppm or less.

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