KR20180132031A - Conductive material and connection structure - Google Patents

Abstract

The present invention provides a conductive material capable of efficiently disposing solder between electrodes to be connected and capable of improving conduction reliability and insulation reliability. The conductive material according to the present invention includes a plurality of first conductive particles having solder on the outer surface portion of the conductive portion and a second conductive particle having silver, ruthenium, iridium, gold, palladium or platinum on the outer surface portion of the conductive portion, A thermosetting compound, and a thermosetting agent.

Description

Conductive material and connection structure

The present invention relates to a conductive material comprising conductive particles having solder. The present invention also relates to a connection structure using the conductive material.

Anisotropic conductive paste such as anisotropic conductive paste and anisotropic conductive film are widely known. In the anisotropic conductive material, the conductive particles are dispersed in the binder. The content of the solder particles in the anisotropic conductive material is, for example, 80% by weight or less.

The anisotropic conductive material can be used for various connection structures, for example, a flexible printed circuit board and a glass substrate (FOG (Film on Glass), a semiconductor chip and a flexible printed circuit (COF (Chip on Film) (COG (Chip on Glass)) connection between a chip and a glass substrate, and connection (FOB (Film on Board)) between a flexible printed substrate and a glass epoxy substrate.

For example, when an electrode of a flexible printed circuit board and an electrode of a glass epoxy substrate are electrically connected by the anisotropic conductive material, an anisotropic conductive material containing conductive particles is disposed on a glass epoxy substrate. Subsequently, the flexible printed circuit board is laminated and heated and pressed. Thereby, the anisotropic conductive material is cured, and the electrodes are electrically connected through the conductive particles to obtain a connection structure.

As an example of the anisotropic conductive material, Patent Document 1 below discloses an anisotropic conductive material containing conductive particles and a resin component that is not completely cured at the melting point of the conductive particles. Specific examples of the conductive particles include tin (Sn), indium (In), bismuth (Bi), silver (Ag), copper (Cu), zinc (Zn), lead (Pb), cadmium (Cd) (Ga) and thallium (Tl), and alloys of these metals.

Patent Document 1 discloses a resin heating step of heating an anisotropic conductive material at a temperature higher than the melting point of the conductive particles and not curing the resin component and a resin component curing step of curing the resin component, And the electrodes are electrically connected to each other. In addition, Patent Document 1 describes that mounting is performed in accordance with the temperature profile shown in Fig. 8 of Patent Document 1. In Patent Document 1, the conductive particles are melted in the resin component in which curing is not completed at the temperature at which the anisotropic conductive material is heated.

The following Patent Document 2 discloses a solder paste in which solder powder and flux are mixed. The flux contains 1% by mass or more and 2% by mass or less of polyalkyl methacrylate. The flux includes stearic acid amide in an amount of 5 mass% or more and less than 15 mass%. The viscosity of the solder paste is not less than 50Pa s and not more than 150Pa s.

Japanese Patent Application Laid-Open No. 2004-260131 Japanese Patent Application Laid-Open No. 2013-132654

The conventional anisotropic conductive material may not be efficiently arranged between the upper and lower electrodes to be connected. In the conventional anisotropic conductive material, there is a problem that when the curing is carried out, the moving speed of the solder on the electrode is slow and the viscosity is elevated before the solder sufficiently moves on the electrode, so that the solder tends to remain in the region free of electrodes .

An object of the present invention is to provide a conductive material capable of efficiently disposing solder between electrodes to be connected and capable of improving conduction reliability and insulation reliability. It is also an object of the present invention to provide a connection structure using the conductive material.

According to a broad aspect of the present invention, there is provided a method of manufacturing a semiconductor device comprising a plurality of first conductive particles each having solder on an outer surface portion of a conductive portion, a second conductive particle having silver, ruthenium, iridium, gold, palladium or platinum on an outer surface portion of the conductive portion, A conductive material comprising a thermosetting compound and a thermosetting agent is provided.

In a specific aspect of the conductive material according to the present invention, the second conductive particles have gold, palladium or platinum on the outer surface portion of the conductive portion.

In a specific aspect of the conductive material according to the present invention, the viscosity of the conductive material at the melting point of the solder in the first conductive particle is not less than 2Pa s and not more than 10Pa s.

In a specific aspect of the conductive material according to the present invention, the average particle diameter of the second conductive particles is smaller than the average particle diameter of the first conductive particles.

In a specific aspect of the conductive material according to the present invention, the content of the second conductive particles is 10% by weight or less.

In a specific aspect of the conductive material according to the present invention, the ratio of the content of the first conductive particles to the content of the second conductive particles is 3 or more and 80 or less based on the weight.

In a specific aspect of the conductive material according to the present invention, the thermosetting compound includes a thermosetting compound that is liquid at 25 占 폚.

In a specific aspect of the conductive material according to the present invention, the thermosetting compound includes a thermosetting compound having a polyether skeleton.

In a specific aspect of the conductive material according to the present invention, the flux includes a flux having a melting point of 50 DEG C or more and 190 DEG C or less.

In a specific aspect of the conductive material according to the present invention, a carboxyl group or an amino group is present on the outer surface of the first conductive particles.

In a specific aspect of the conductive material according to the present invention, the first conductive particles are solder particles having a solder in the center portion and the outer surface portion.

In a specific aspect of the conductive material according to the present invention, the surface of the first conductive particles and the insulating particles not attached to the surface of the second conductive particles are included.

According to a broad aspect of the present invention, there is provided a display device comprising: a first connection object member having at least one first electrode on its surface; a second connection object member having at least one second electrode on a surface; And a connection portion connecting the second connection target member, wherein the material of the connection portion is the above-described conductive material, and the connection portion has a cured product portion, a solder portion, and the second conductive particles, And the first electrode and the second electrode are electrically connected to each other by the solder portion in the connection portion.

According to a broad aspect of the present invention, there is provided a display device comprising: a first connection object member having at least one first electrode on its surface; a second connection object member having at least one second electrode on a surface; And a connecting portion connecting the second connection target member, wherein the connecting portion includes a cured product, a solder portion, and a second conductive particle having silver, ruthenium, iridium, gold, palladium or platinum on the outer surface portion of the conductive portion Wherein the second conductive particles are disposed in the solder portion, and the first electrode and the second electrode are electrically connected by the solder portion in the connection portion.

In a specific aspect of the connection structure according to the present invention, the second conductive particles have gold, palladium or platinum on the outer surface portion of the conductive portion.

In a specific aspect of the connection structure according to the present invention, when the mutually opposing portions of the first electrode and the second electrode in the stacking direction of the first electrode, the connection portion, and the second electrode are viewed, And the solder portion in the connection portion is disposed at 50% or more of the area 100% of the portions facing each other of the second electrode.

The conductive material according to the present invention includes a plurality of first conductive particles having solder on the outer surface portion of the conductive portion and a second conductive particle having silver, ruthenium, iridium, gold, palladium or platinum on the outer surface portion of the conductive portion, Since the thermosetting compound and the thermosetting agent are contained, the solder can be efficiently disposed between the electrodes to be connected, and conduction reliability and insulation reliability can be improved.

A connection structure according to the present invention includes a first connection target member having at least one first electrode on its surface, a second connection target member having at least one second electrode on its surface, And a connecting portion connecting the second connection target member, wherein the connecting portion includes a cured product, a solder portion, and a second conductive particle having silver, ruthenium, iridium, gold, palladium or platinum on the outer surface portion of the conductive portion The second conductive particles are disposed in the solder portion, and the first electrode and the second electrode are electrically connected to each other by the solder portion in the connection portion, so that conduction reliability and insulation reliability can be improved.

1 is a cross-sectional view schematically showing a connection structure obtained by using a conductive material according to an embodiment of the present invention.
2 (a) to 2 (c) are cross-sectional views for explaining respective steps of a method of manufacturing a connection structure using a conductive material according to an embodiment of the present invention.
3 is a cross-sectional view showing a modification of the connection structure.
4 is a cross-sectional view showing a first example of the first conductive particles usable for the conductive material.
5 is a cross-sectional view showing a second example of the first conductive particles usable in the conductive material.
6 is a cross-sectional view showing a third example of the first conductive particles usable in the conductive material.

Hereinafter, the details of the present invention will be described.

(Conductive material)

The conductive material according to the present invention includes a first conductive particle, a second conductive particle, a thermosetting compound, and a thermosetting agent.

The first conductive particle has a conductive portion. The first conductive particles have solder on the outer surface portion of the conductive portion. The solder is contained in the conductive portion, and is part or all of the conductive portion.

The second conductive particle has a conductive portion. The second conductive particles have silver, ruthenium, iridium, gold, palladium or platinum on the outer surface portion of the conductive portion. Silver, ruthenium, iridium, gold, palladium or platinum are included in the conductive part and are part or all of the conductive part.

According to the present invention, since the above structure is provided, the moving speed of the solder over the electrodes is increased, and the solder can be efficiently disposed between the electrodes to be connected, and the reliability of conduction and the reliability of insulation can be improved. When the electrode width or the inter-electrode width is narrow, it tends to be difficult to collect the solder on the electrode. However, in the present invention, even if the electrode width or the inter-electrode width is narrow, the solder can be sufficiently collected on the electrode. According to the present invention, when the electrodes are electrically connected to each other, the solder easily collects between the upper and lower opposing electrodes, and the solder can be efficiently disposed on the electrode (line). Further, in the present invention, when the width of the electrode having the electrode is wide, the solder is more efficiently arranged on the electrode.

The above effect is manifested because the second conductive particles are present between the plurality of first conductive particles at the time of conductive connection so that the first conductive particles are pulled close to the other first conductive particles through the second conductive particles to be. The second conductive particles have silver, ruthenium, iridium, gold, palladium or platinum on the outer surface portion of the conductive portion, so that the second conductive particles have a function of pulling the solder close to each other.

Further, in the present invention, a part of the solder is hardly arranged in a region where no electrode is formed (space), and the amount of solder disposed in an area where no electrode is formed can be significantly reduced. According to the present invention, solder not located between opposing electrodes can be efficiently moved between opposing electrodes. Therefore, the conduction reliability between the electrodes can be improved. In addition, it is possible to prevent electrical connection between the adjacent electrodes in the transverse direction which should not be connected, and the insulation reliability can be improved.

Further, in the present invention, positional deviation between electrodes can be prevented. In the present invention, in the state where the electrode of the first connection target member and the electrode of the second connection target member are out of alignment when the second connection target member is superimposed on the first connection target member having the conductive material arranged on the upper surface, Even if the one connection target member and the second connection target member overlap each other, the misalignment can be corrected and the electrodes of the first connection target member and the electrodes of the second connection target member can be connected (self-alignment effect).

In order to more effectively arrange the solder on the electrode, the conductive material is preferably liquid at 25 DEG C and is preferably a conductive paste. In order to more effectively arrange the solder on the electrode, the viscosity (? 25) of the conductive material at 25 占 폚 is preferably 10 Pa · s or more, more preferably 50 Pa · s or more, further preferably 100 Pa S or more, preferably 800 Pas or less, more preferably 600 Pas or less, and further preferably 500 Pas or less. The viscosity (? 25) can be appropriately adjusted depending on the type and blending amount of the compounding ingredients.

The viscosity (? 25) can be measured at 25 ° C and 5 rpm using, for example, an E-type viscometer ("TVE22L" manufactured by Toki San Pharmaceutical Co., Ltd.).

In order to more effectively arrange the solder on the electrode, the viscosity of the conductive material at the melting point of the solder in the first conductive particle is preferably 2 Pa s or more, more preferably 3 Pa s More preferably 4 Pa s or more, preferably 10 Pa s or less, more preferably 9 Pa s or less, and further preferably 8 Pa s or less. The viscosity [eta] mp can be appropriately adjusted depending on the type and blending amount of the compounding ingredients.

The melting point of the solder is a temperature that tends to affect the movement of the first conductive particles over the electrode.

The viscosity ηmp can be measured under the conditions of a strain control 1 rad, a frequency of 1 Hz, a temperature raising rate of 20 ° C./minute, a measuring temperature range of 40 ° C. to a melting point of solder ° C. using STRESSTECH (manufactured by EOLOGICA) Do. In this measurement, the viscosity at the melting point of the solder is read.

The conductive material may be used as a conductive paste and a conductive film. The conductive film is preferably an anisotropic conductive film. From the standpoint of more efficiently placing the solder on the electrode, the conductive material is preferably a conductive paste. The conductive material is suitably used for electrical connection of the electrode. The conductive material is preferably a circuit connecting material.

Hereinafter, each component contained in the conductive material will be described. In the present specification, "(meth) acryl" means one or both of "acrylic" and "methacryl", and "(meth) acrylate" means one or both of "acrylate" (Meth) acryloyl " means either or both of " acryloyl " and " methacryloyl ".

(First conductive particle)

The first conductive particles electrically connect the electrodes of the member to be connected. The first conductive particles have solder on the outer surface portion of the conductive portion. The first conductive particles may be solder particles formed by solder. The solder particles have solder on the outer surface portion of the conductive portion. The solder particles are formed by solder in both the center portion and the outer surface portion of the conductive portion. The solder particles are particles in which both the central portion and the outer surface of the conductive portion are solder. The solder particles are core particles and do not have base particles. The solder particles are different from the conductive particles having the base particles and the conductive portions disposed on the surface of the base particles. The solder particles preferably contain, for example, at least 80% by weight, more preferably at least 90% by weight, more preferably at least 95% by weight of solder. The first conductive particles may have base particles and a conductive portion disposed on the surface of the base particles. In this case, the first conductive particles have solder on the outer surface portion of the conductive portion.

In addition, in the case of using the first conductive particles having the base particles not formed by solder and the solder portions disposed on the surface of the base particles, as compared with the case of using the solder particles, the first conductive particles are hardly collected on the electrode The first conductive particles moved on the electrode tends to move out of the electrode because the solder jointability between the first conductive particles is low and the effect of suppressing the positional displacement between the electrodes tends to be lowered. Therefore, it is preferable that the first conductive particles are solder particles formed by solder.

It is preferable that a carboxyl group or an amino group is present on the outer surface (outer surface of the solder) of the first conductive particles from the viewpoint of effectively lowering the connection resistance in the connection structure and effectively suppressing the generation of voids, , And it is preferable that an amino group is present. It is preferable that a carboxyl group or a group containing an amino group is covalently bonded to the outer surface (outer surface of the solder) of the first conductive particle via a Si-O bond, an ether bond, an ester bond or a group represented by the following formula (X) Do. The carboxyl group or the group containing an amino group may include both a carboxyl group and an amino group. In the following formula (X), the right end and the left end represent binding sites.

There is a hydroxyl group on the surface of the solder. By covalently bonding the hydroxyl group and the group containing a carboxyl group, it is possible to form a stronger bond than in the case of bonding in other coordinate bond (chelate coordination) or the like, so that the connection resistance between the electrodes can be lowered and the generation of voids can be suppressed The first conductive particles are obtained.

In the first conductive particle, the surface of the solder and the bond form of the group containing a carboxyl group may or may not contain a bond due to the chelate coordination.

From the viewpoint of effectively lowering the connection resistance in the connection structure and effectively suppressing the generation of voids, the first conductive particles are preferably a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group or an amino group Is preferably obtained by reacting the hydroxyl group of the surface of the solder with the functional group capable of reacting with the hydroxyl group. In this reaction, a covalent bond is formed. The first conductive particles in which a carboxyl group or a group containing an amino group is covalently bonded to the surface of the solder can be easily obtained by reacting the hydroxyl group on the surface of the solder with the functional group capable of reacting with the hydroxyl group in the compound X, A first conductive particle in which a carboxyl group or a group containing an amino group is covalently bonded to the surface through an ether bond or an ester bond can be obtained. The compound X can be chemically bonded to the surface of the solder in the form of a covalent bond by reacting the hydroxyl group of the surface of the solder with the functional group capable of reacting with the hydroxyl group.

Examples of the functional group capable of reacting with the hydroxyl group include a hydroxyl group, a carboxyl group, an ester group, and a carbonyl group. A hydroxyl group or a carboxyl group is preferable. The functional group capable of reacting with the hydroxyl group may be a hydroxyl group or a carboxyl group.

Examples of the compound having a functional group capable of reacting with a hydroxyl group include compounds having a functional group reactive with a hydroxyl group such as levulic acid, glutaric acid, glycolic acid, succinic acid, malic acid, oxalic acid, malonic acid, adipic acid, , 3-mercaptopropionic acid, 3-mercaptopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid, 4-phenylbutyric acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecane (9,12,15) -linolenic acid, nonadecanoic acid, arachidic acid, decanedioic acid, and dodecanedioic acid, such as acetic acid, hexadecanoic acid, 9-hexadecanoic acid, heptadecanoic acid, stearic acid, oleic acid, And the like. Glutaric acid or glycolic acid is preferred. The compound having a functional group capable of reacting with the hydroxyl group may be used alone, or two or more compounds may be used in combination. The compound having a functional group capable of reacting with the hydroxyl group is preferably a compound having at least one carboxyl group.

The compound X preferably has a flux action, and the compound X preferably has a flux action in a state bonded to the surface of the solder. The compound having a flux action is capable of removing the oxide film on the surface of the solder and the surface oxide film of the electrode. The carboxyl group has a flux action.

Examples of the compound having a flux action include levulic acid, glutaric acid, glycolic acid, succinic acid, 5-ketohexanoic acid, 3-hydroxypropionic acid, 4-aminobutyric acid, 3- mercaptopropionic acid, 3- , 3-methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid, and 4-phenylbutyric acid. Glutaric acid or glycolic acid is preferred. The above-mentioned compounds having a flux action may be used alone, or two or more thereof may be used in combination.

It is preferable that the functional group capable of reacting with the hydroxyl group in the compound X is a hydroxyl group or a carboxyl group from the viewpoint of effectively lowering the connection resistance in the connection structure and effectively suppressing the generation of voids. The functional group capable of reacting with the hydroxyl group in the compound X may be a hydroxyl group or a carboxyl group. When the functional group capable of reacting with the hydroxyl group is a carboxyl group, the compound X preferably has at least two carboxyl groups. A first conductive particle in which a carboxyl group-containing group is covalently bonded to the surface of the solder is obtained by reacting a part of the carboxyl group of the compound having at least two carboxyl groups with the hydroxyl group on the surface of the solder.

The method for producing the first conductive particles includes a step of mixing the first conductive particles, a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group, a catalyst, and a solvent using, for example, first conductive particles. In the method for producing the first conductive particles, the first conductive particles in which a group containing a carboxyl group is covalently bonded to the surface of the solder can be easily obtained by the mixing step.

In the method for producing the first conductive particles, mixing the first conductive particles, a compound having a functional group capable of reacting with the hydroxyl group and a carboxyl group, the catalyst and the solvent, and heating the mixture using the first conductive particles desirable. By the mixing and heating process, the first conductive particles in which a group containing a carboxyl group is covalently bonded to the surface of the solder can be further easily obtained.

Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol and butanol, acetone, methyl ethyl ketone, ethyl acetate, toluene and xylene. The solvent is preferably an organic solvent, more preferably toluene. The solvent may be used alone, or two or more solvents may be used in combination.

Examples of the catalyst include p-toluenesulfonic acid, benzenesulfonic acid and 10-camphorsulfonic acid. The catalyst is preferably p-toluenesulfonic acid. The catalyst may be used alone or in combination of two or more.

It is preferable to heat at the time of mixing. The heating temperature is preferably 90 占 폚 or higher, more preferably 100 占 폚 or higher, preferably 130 占 폚 or lower, more preferably 110 占 폚 or lower.

From the viewpoint of effectively lowering the connection resistance in the connection structure and effectively suppressing the generation of voids, the first conductive particles can be produced by a step of reacting the isocyanate compound with the hydroxyl group on the surface of the solder using an isocyanate compound . In this reaction, a covalent bond is formed. The first conductive particle in which the nitrogen atom of the group derived from the isocyanate group is covalently bonded to the surface of the solder can be easily obtained by reacting the hydroxyl group on the surface of the solder with the isocyanate compound. By reacting the hydroxyl group of the surface of the solder with the isocyanate compound, the group derived from the isocyanate group can be chemically bonded to the surface of the solder in the form of a covalent bond.

A silane coupling agent can be easily reacted with a group derived from an isocyanate group. The first conductive particles can be easily obtained. Therefore, when the group containing the carboxyl group is introduced by a reaction using a silane coupling agent having a carboxyl group, or after a reaction using a silane coupling agent, a group derived from a silane coupling agent It is preferably introduced by reacting a compound having at least one carboxyl group. It is preferable that the first conductive particles are obtained by reacting the isocyanate compound with the hydroxyl group on the surface of the solder by using the isocyanate compound and then reacting the compound having at least one carboxyl group.

From the viewpoint of effectively lowering the connection resistance in the connection structure and effectively suppressing the generation of voids, it is preferable that the compound having at least one carboxyl group has a plurality of carboxyl groups.

Examples of the isocyanate compound include diphenylmethane-4,4'-diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI) and isophorone diisocyanate (IPDI). Isocyanate compounds other than these may be used. The surface of the solder is reacted with the isocyanate compound through the group represented by the formula (X) to react with a compound having a residual isocyanate group, a residual isocyanate group, and a carboxyl group and reacting the isocyanate compound with the surface of the solder. Can be introduced.

As the isocyanate compound, a compound having an unsaturated double bond and having an isocyanate group may be used. For example, 2-acryloyloxyethyl isocyanate and 2-isocyanatoethyl methacrylate. (X) on the surface of the solder by reacting an isocyanate group of the compound with the surface of the solder and then reacting the compound having a functional group having reactivity with the remaining unsaturated double bond and having a carboxyl group , A carboxyl group can be introduced.

Examples of the silane coupling agent include 3-isocyanate propyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Silicone Co., Ltd.) and 3-isocyanatepropyltrimethoxysilane (Y-5187 manufactured by MOMENTIVE). The silane coupling agent may be used alone or in combination of two or more.

Examples of the compound having at least one carboxyl group include at least one compound selected from the group consisting of levulic acid, glutaric acid, glycolic acid, succinic acid, malic acid, oxalic acid, malonic acid, adipic acid, 5-ketohexanoic acid, 3-hydroxypropionic acid, 3-mercaptopropionic acid, 3-phenylisobutyric acid, 4-phenylbutyric acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, 3-mercaptopropionic acid, 3-mercaptopropionic acid, 3- (9,12,15) -linolenic acid, nonadecanoic acid, arachidic acid, decanoic acid, and dodecanedioic acid, and the like can be used in the present invention. . Glutaric acid, adipic acid or glycolic acid are preferable. The compound having at least one carboxyl group may be used alone, or two or more compounds may be used in combination.

The isocyanate compound may be used to react with the isocyanate compound on the hydroxyl group on the surface of the solder and then react a part of the carboxyl group of the compound having a plurality of carboxyl groups with the hydroxyl group on the surface of the solder to leave a group containing a carboxyl group have.

In the method for producing the first conductive particles, the isocyanate compound is reacted with the hydroxyl group on the surface of the solder by using the first conductive particles and the isocyanate compound, and then the compound having at least one carboxyl group is reacted, On the surface of the solder, a first conductive particle to which a group containing a carboxyl group is bonded is obtained through a group represented by the formula (X). In the method for producing the first conductive particles, the first conductive particles into which a group containing a carboxyl group is introduced can be easily obtained on the surface of the solder by the above process.

Specific examples of the method for producing the first conductive particles include the following methods. The first conductive particles are dispersed in an organic solvent, and a silane coupling agent having an isocyanate group is added. Thereafter, a silane coupling agent is covalently bonded to the surface of the solder by using a reaction catalyst of a hydroxyl group and an isocyanate group on the surface of the solder of the first conductive particles. Subsequently, the alkoxy group bonded to the silicon atom of the silane coupling agent is hydrolyzed to generate a hydroxyl group. The carboxyl group of the compound having at least one carboxyl group is reacted with the resulting hydroxyl group.

Specific examples of the method for producing the first conductive particles include the following methods. The first conductive particles are dispersed in an organic solvent, and a compound having an isocyanate group and an unsaturated double bond is added. Thereafter, a covalent bond is formed using a reaction catalyst of a hydroxyl group and an isocyanate group on the surface of the solder of the first conductive particles. Thereafter, a compound having an unsaturated double bond and a carboxyl group is reacted with the introduced unsaturated double bond.

Examples of the reaction catalyst of the hydroxyl group and the isocyanate group on the surface of the solder of the first conductive particles include tin catalysts such as dibutyltin dilaurate, amine catalysts such as triethylenediamine, carboxylate catalysts such as naphthenene- Potassium acetate and the like) and a trialkylphosphine catalyst (triethylphosphine and the like).

From the viewpoint of effectively lowering the connection resistance in the connection structure and effectively suppressing the generation of voids, the compound having at least one carboxyl group is preferably a compound represented by the following formula (1). The compound represented by the following formula (1) has a flux action. Further, the compound represented by the following formula (1) has a flux action in a state of being introduced to the surface of the solder.

In the formula (1), X represents a functional group capable of reacting with a hydroxyl group, and R represents a divalent organic group having 1 to 5 carbon atoms. The organic group may contain a carbon atom, a hydrogen atom and an oxygen atom. The organic group may be a divalent hydrocarbon having 1 to 5 carbon atoms. The main chain of the organic group is preferably a divalent hydrocarbon group. In the corresponding organic group, a carboxyl group or a hydroxyl group may be bonded to a bivalent hydrocarbon group. The compound represented by the above formula (1) includes, for example, citric acid.

The compound having at least one carboxyl group is preferably a compound represented by the following formula (1A) or (1B). The compound having at least one carboxyl group is preferably a compound represented by the following formula (1A), more preferably a compound represented by the following formula (1B).

In the formula (1A), R represents a divalent organic group having 1 to 5 carbon atoms. R in the formula (1A) is the same as R in the formula (1).

In the above formula (1B), R represents a divalent organic group having 1 to 5 carbon atoms. R in the formula (1B) is the same as R in the formula (1).

It is preferable that a group represented by the following formula (2A) or a group represented by the following formula (2B) is bonded to the surface of the solder. It is preferable that the group represented by the formula (2A) is bonded to the surface of the solder, and it is more preferable that the group represented by the formula (2B) is bonded to the surface of the solder. In the following formula (2A), the left end represents a bonding site.

In the formula (2A), R represents a divalent organic group having 1 to 5 carbon atoms. R in the formula (2A) is the same as R in the formula (1). In the following formula (2B), the left end represents a bonding site.

In the formula (2B), R represents a divalent organic group having 1 to 5 carbon atoms. R in the formula (2B) is the same as R in the formula (1).

From the viewpoint of enhancing the wettability of the surface of the solder, the molecular weight of the compound having at least one carboxyl group is preferably 10000 or less, more preferably 1000 or less, still more preferably 500 or less.

The molecular weight means a molecular weight that can be calculated from the structural formula when the compound having at least one carboxyl group is not a polymer and when the structural formula of the compound having at least one carboxyl group can be specified. When the compound having at least one carboxyl group is a polymer, it means a weight average molecular weight.

It is preferable that the first conductive particles have a first conductive particle body and an anionic polymer disposed on the surface of the first conductive particle body in that the cohesiveness of the solder particles can be effectively increased at the time of conductive connection. It is preferable that the first conductive particles are obtained by surface-treating the first conductive particle body with an anionic polymer or a compound to be an anionic polymer. It is preferable that the first conductive particles are surface-treated with a compound which is an anionic polymer or an anionic polymer. The anionic polymer and the compound to be the anionic polymer may be used alone or in combination of two or more. The anionic polymer is a polymer having an acidic group.

Examples of the method for surface-treating the first conductive particle body with the anionic polymer include a method in which an anionic polymer such as a (meth) acrylic polymer copolymerized with (meth) acrylic acid, a A polyester polymer obtained by an intermolecular dehydration condensation reaction of a dicarboxylic acid and having a carboxyl group at both terminals, a polyester polymer synthesized from a dicarboxylic acid and a diamine and having a carboxyl group at both terminals, and a modified polymer having a carboxyl group And a method in which the carboxyl group of the anionic polymer and the hydroxyl group on the surface of the first conductive particle body are reacted with each other using POVAL ("Goseinex T" manufactured by Nippon Gosei Chemical Industry Co., Ltd.).

Examples of the anion moiety of the anionic polymer include the carboxyl groups described above, and other groups include a tosyl group (pH ₃ CC ₆ H ₄ S (═O) ₂ -), a sulfonic acid ionic group (-SO ₃ -), PO ₄ -).

Another method of surface-treating the first conductive particle body with an anionic polymer is to use a compound having a functional group reactive with the hydroxyl group on the surface of the first conductive particle body and having a functional group capable of polymerization by addition or condensation reaction , And a method of polymerizing the compound on the surface of the first conductive particle body. Examples of the functional group that reacts with the hydroxyl group on the surface of the first conductive particle body include a carboxyl group and an isocyanate group. Examples of the functional group that is polymerized by addition and condensation include a hydroxyl group, a carboxyl group, an amino group, and a (meth) .

The weight average molecular weight of the anionic polymer is preferably 2000 or more, more preferably 3000 or more, preferably 10000 or less, more preferably 8000 or less. If the weight average molecular weight is not less than the lower limit and not more than the upper limit, a sufficient amount of charge and flux can be introduced into the surface of the first conductive particles. Thereby, the cohesiveness of the first conductive particles can be effectively increased at the time of conductive connection, and the oxide film on the surface of the electrode can be effectively removed at the time of connection of the member to be connected.

When the weight average molecular weight is not less than the lower limit and not more than the upper limit, it is easy to dispose the anionic polymer on the surface of the first conductive particle body, effectively increase the cohesiveness of the first conductive particles at the time of conductive connection, 1 conductive particles can be arranged more efficiently.

The weight average molecular weight represents the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The weight average molecular weight of the polymer obtained by subjecting the first conductive particle body to surface treatment with a compound to be an anionic polymer is obtained by dissolving the solder in the first conductive particles and removing the first conductive particles with dilute hydrochloric acid or the like which does not cause decomposition of the polymer, And measuring the weight average molecular weight of the remaining polymer.

Next, specific examples of the first conductive particles will be described with reference to the drawings.

4 is a cross-sectional view showing a first example of the first conductive particles usable for the conductive material.

The first conductive particles 21 shown in Fig. 4 are solder particles. The first conductive particles 21 are entirely formed of solder. The first conductive particles 21 do not have base particles in the core and are not core shell particles. In the first conductive particles 21, both the center portion and the outer surface portion of the conductive portion are formed by solder.

5 is a cross-sectional view showing a second example of the first conductive particles usable in the conductive material.

The first conductive particles 31 shown in Fig. 5 include base particles 32 and conductive portions 33 disposed on the surface of the base particles 32. The conductive portion 33 covers the surface of the base particle 32. The first conductive particles 31 are coated particles in which the surface of the base particle 32 is covered with the conductive portion 33.

The conductive portion 33 has a second conductive portion 33A and a solder portion 33B (first conductive portion). The first conductive particles 31 have the second conductive portions 33A between the base particles 32 and the solder portions 33B. Therefore, the first conductive particles 31 include the base particles 32, the second conductive portions 33A disposed on the surface of the base particles 32, and the second conductive portions 33A disposed on the outer surfaces of the second conductive portions 33A. And a lead portion 33B.

6 is a cross-sectional view showing a third example of the first conductive particles usable in the conductive material.

As described above, the conductive portions 33 of the first conductive particles 31 have a two-layer structure. The first conductive particles 41 shown in Fig. 6 has a solder portion 42 as a single-layer conductive portion. The first conductive particles 41 include a base particle 32 and a soldering portion 42 disposed on the surface of the base particle 32.

Examples of the base particles include resin particles, inorganic particles other than metal particles, organic-inorganic hybrid particles and metal particles. The base particles are preferably base particles other than metal, and are preferably resin particles, inorganic particles other than metal particles, or organic-inorganic hybrid particles. The base particles may be copper particles. The base particles may be core shell particles comprising a core and a shell disposed on the surface of the core. The core may be an organic core, and the shell may be an inorganic shell.

As the resin for forming the resin particles, various organic materials are suitably used. Examples of the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; Acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester A resin, a saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyetheretherketone, polyether sulfone, divinylbenzene polymer, and divinylbenzene copolymer And the like. Examples of the divinylbenzene-based copolymer and the like include a divinylbenzene-styrene copolymer and a divinylbenzene- (meth) acrylate copolymer. It is preferable that the resin for forming the resin particles is a polymer obtained by polymerizing at least one polymerizable monomer having an ethylenic unsaturated group.

When the resin particles are obtained by polymerizing a polymerizable monomer having an ethylenic unsaturated group, examples of the polymerizable monomer having the ethylenic unsaturated group include a monomer that is incompatible with the monomer and a monomer that is crosslinkable.

Examples of the non-crosslinkable monomer include styrene-based monomers such as styrene and? -Methylstyrene; Carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl Alkyl (meth) acrylate compounds such as acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; (Meth) acrylate compounds such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate; Nitrile-containing monomers such as (meth) acrylonitrile; Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; Acid vinyl ester compounds such as vinyl acetate, vinyl butyrate, vinyl laurate and vinyl stearate; Unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; Halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride and chlorostyrene.

Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane di (meth) acrylate, trimethylolpropane tri (meth) (Meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di Polyfunctional (meth) acrylate compounds such as (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate and 1,4-butanediol di (meth) acrylate; (Meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, trimethylolpropane trimethoxysilane, triallyl trimellitate, divinyl benzene, diallyl phthalate, diallyl acrylamide, diallyl ether, , Silane-containing monomers such as vinyltrimethoxysilane, and the like.

The above-mentioned resin particles can be obtained by polymerizing the above-mentioned polymerizable monomer having an ethylenic unsaturated group by a known method. This method includes, for example, suspension polymerization in the presence of a radical polymerization initiator, and polymerization in which monomer is swollen together with a radical polymerization initiator using non-crosslinked seed particles.

When the base particles are inorganic particles other than metal particles or organic-inorganic hybrid particles, silica, alumina, barium titanate, zirconia and carbon black can be given as an inorganic substance for forming base particles. The inorganic material is preferably not a metal. The particles formed by the silica are not particularly limited. For example, particles obtained by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, and then firing if necessary, . Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

The organic-inorganic hybrid particle is preferably a core-shell type organic-inorganic hybrid particle having a core and a shell disposed on the surface of the core. The core is preferably an organic core. Preferably, the shell is an inorganic shell. From the viewpoint of further effectively lowering the connection resistance between the electrodes, the base particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core.

As the material of the organic core, the above-mentioned materials of the resin particles and the like can be mentioned.

As the material of the inorganic shell, an inorganic substance exemplified as the material of the above base particles can be mentioned. The material of the inorganic shell is preferably silica. It is preferable that the inorganic shell is formed on the surface of the core by converting the metal alkoxide into a shell by a sol-gel method and then baking the shell shell. The metal alkoxide is preferably a silane alkoxide. The inorganic shell is preferably formed by silane alkoxide.

In the case where the base particles are metal particles, silver, copper, nickel, silicon, gold, titanium and the like can be given as metals for forming the metal particles. When the base particles are metal particles, the metal particles are preferably copper particles. However, it is preferable that the base particles are not metal particles.

The particle diameter of the base particles is preferably 0.5 占 퐉 or more, more preferably 1 占 퐉 or more, further preferably 3 占 퐉 or more, preferably 100 占 퐉 or less, more preferably 60 占 퐉 or less, Or less. When the particle diameter of the base particles is at least the lower limit, the contact area between the conductive particles and the electrode is increased, so that the reliability of the connection between the electrodes is further increased, and the connection resistance between the electrodes connected through the conductive particles can be further effectively lowered . Further, when the conductive part is formed on the surface of the base particles, it is difficult to coagulate, and cohesive conductive particles are hardly formed. When the particle diameter of the base particles is less than the upper limit, the conductive particles are easily compressed sufficiently, and the connection resistance between the electrodes connected through the conductive particles can be further effectively lowered.

Particle diameter of the base particles is particularly preferably 5 탆 or more and 40 탆 or less. If the particle diameter of the base particles is in the range of 5 占 퐉 or more and 40 占 퐉 or less, the interval between the electrodes can be further reduced, and even if the thickness of the conductive portion is increased, small conductive particles can be obtained.

The particle diameter of the base particles shows a diameter when base particles are spherical, and shows a maximum diameter when base particles are not spherical.

The particle diameter of the base particles indicates the number average particle diameter. The particle diameter of the base particles is obtained by using a particle size distribution measuring apparatus or the like. The particle diameter of the base particles is preferably determined by observing 50 arbitrary base particles with an electron microscope or an optical microscope and calculating an average value. In the case of measuring the particle diameter of the base particles in the conductive particles, the measurement can be carried out, for example, as follows.

TechnoBit 4000 " manufactured by Kulzer Co., Ltd., so that the content of the conductive particles is 30% by weight, and dispersed to prepare a buried resin for conductive particle inspection. The cross section of the conductive particles is cut out using an ion milling apparatus ("IM4000" manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the conductive particles dispersed in the embedding resin for inspection. Then, using a field emission scanning electron microscope (FE-SEM), image magnification was set at 25000 times, and 50 conductive particles were randomly selected to observe base particles of each conductive particle. The particle diameters of the base particles in each conductive particle are measured and arithmetically averaged to determine the particle diameter of the base particles.

A method of forming a conductive portion on the surface of the base particle and a method of forming a solder portion on the surface of the base particle or on the surface of the second conductive portion are not particularly limited. Examples of the method for forming the conductive portion and the solder portion include a method by electroless plating, a method by electroplating, a method by physical impact, a method by mechanochemical reaction, a method by physical vapor deposition or physical adsorption A method of coating a surface of a base particle with a paste containing a metal powder or a metal powder and a binder, and the like. The conductive part and the solder part are preferably formed by electroless plating, electroplating or physical impact. Examples of the physical deposition method include vacuum deposition, ion plating and ion sputtering. Further, in the above-mentioned physical collision method, for example, Seitar Composer (manufactured by Tokushu Kousaku Co., Ltd.) is used.

The melting point of the base particles is preferably higher than the melting point of the conductive portion and the soldering portion. The melting point of the base particles preferably exceeds 160 캜, more preferably exceeds 300 캜, more preferably exceeds 400 캜, and particularly preferably exceeds 450 캜. The melting point of the base particles may be lower than 400 占 폚. The melting point of the base particles may be 160 캜 or less. The base particles preferably have a softening point of 260 캜 or higher. The softening point of the base particles may be less than 260 캜.

The first conductive particles may have a single-layer solder portion. The first conductive particles may have a plurality of conductive portions (solder portions, second conductive portions). That is, in the first conductive particles, two or more conductive portions may be laminated. When the conductive portion is two or more layers, it is preferable that the first conductive particles have solder on the outer surface portion of the conductive portion.

The solder is preferably a metal having a melting point of 450 DEG C or less (low melting point metal). The solder portion is preferably a metal layer (low-melting-point metal layer) having a melting point of 450 캜 or less. The low melting point metal layer is a layer containing a low melting point metal. The solder in the first conductive particle is preferably a metal particle (low-melting-point metal particle) having a melting point of 450 캜 or lower. The low melting point metal particles are particles containing a low melting point metal. The low melting point metal means a metal having a melting point of 450 캜 or lower. The melting point of the low melting point metal is preferably 300 DEG C or lower, more preferably 160 DEG C or lower. It is preferable that the solder in the first conductive particle contains tin. The tin content in the solder is preferably 30 wt% or more, more preferably 40 wt% or more, in 100 wt% of the metal contained in the soldering portion and 100 wt% of the metal contained in the solder in the first conductive particle , More preferably not less than 70 wt%, particularly preferably not less than 90 wt%. When the content of tin in the solder in the first conductive particles is not lower than the lower limit described above, the conductivity reliability of the first conductive particles and the electrode is further enhanced.

The content of the tin was determined using a high frequency inductively coupled plasma emission spectrochemical analyzer ("ICP-AES" manufactured by Horiba Seisakusho Co., Ltd.) or a fluorescent X-ray analyzer ("EDX-800HS" available from Shimadzu Corporation) It is measurable.

By using the first conductive particles having the solder on the outer surface portion of the conductive portion, the solder is melted and bonded to the electrode, and the solder makes the electrodes conductive. For example, if the solder and the electrode are not in point contact, they are likely to come into contact with each other, so that the connection resistance is lowered. Further, by using the first conductive particles having the solder on the outer surface portion of the conductive portion, the bonding strength between the solder and the electrode is increased, and as a result, the solder and the electrode are less likely to be peeled off, and the reliability of conduction is effectively increased.

The soldering portion and the low melting point metal constituting the solder particle are not particularly limited. The low melting point metal is preferably an alloy containing tin or tin. The alloys include tin-silver alloys, tin-copper alloys, tin-silver-copper-copper tin-bismuth alloys, tin-zinc alloys, and tin-indium alloys. The low melting point metal is preferably tin, a tin-silver alloy, a tin-silver-copper alloy, a tin-bismuth alloy, or a tin-indium alloy in view of excellent wettability to electrodes. Tin-bismuth alloy, and tin-indium alloy.

The material constituting the solder (soldering portion) is preferably a filler material having a liquidus line of 450 DEG C or less based on JIS Z3001: welding terminology. Examples of the composition of the solder include a metal composition including zinc, gold, silver, lead, copper, tin, bismuth, indium and the like. Tin-indium based (117 占 폚) or tin-bismuth (139 占 폚) low melting point and lead-free are preferable. That is, it is preferable that the solder does not contain lead, and is preferably solder containing tin and indium, or solder containing tin and bismuth.

The solder in the first conductive particles may be at least one selected from the group consisting of nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, Manganese, chromium, molybdenum, palladium, and the like. From the viewpoint of further increasing the bonding strength between the solder and the electrode, it is preferable that the solder in the first conductive particle includes nickel, copper, antimony, aluminum or zinc. From the viewpoint of further increasing the bonding strength between the solder and the electrode in the solder portion or the first conductive particles, the content of these metals for increasing the bonding strength is preferably 100% by weight or less Is 0.0001% by weight or more, preferably 1% by weight or less.

The melting point of the second conductive part is preferably higher than the melting point of the soldering part. The melting point of the second conductive portion is preferably more than 160 ° C, more preferably more than 300 ° C, more preferably more than 400 ° C, even more preferably more than 450 ° C, Gt; 500 C, < / RTI > and most preferably greater than 600 C. < / RTI > Since the solder portion has a low melting point, it is melted at the time of conductive connection. It is preferable that the second conductive portion is not melted at the time of conductive connection. It is preferable that the first conductive particles are used by melting the solder. Preferably, the first conductive particles are used by melting the solder portion, and the solder portion is preferably melted and the second conductive portion is not melted. The melting point of the second conductive portion is higher than the melting point of the soldering portion so that the soldering portion alone can be melted without melting the second conductive portion at the time of conductive connection.

The maximum value of the difference between the melting point of the soldering portion and the melting point of the second conductive portion is more than 0 ° C, preferably 5 ° C or more, more preferably 10 ° C or more, still more preferably 30 ° C or more, 50 DEG C or higher, and most preferably 100 DEG C or higher.

The second conductive part preferably includes a metal. The metal constituting the second conductive portion is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, . As the metal, tin-doped indium oxide (ITO) may be used. The metal may be used alone or in combination of two or more.

The second conductive portion is preferably a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer or a gold layer, and more preferably a copper layer. The first conductive particles preferably have a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer or a gold layer, and more preferably a copper layer. By using the first conductive particles having these preferable conductive portions for connection between the electrodes, the connection resistance between the electrodes is further lowered. Further, a solder portion can be formed more easily on the surface of these preferable conductive portions.

The thickness of the soldering portion is preferably 0.005 탆 or more, more preferably 0.01 탆 or more, preferably 10 탆 or less, more preferably 1 탆 or less, further preferably 0.3 탆 or less. When the thickness of the solder portion is not less than the lower limit and not more than the upper limit, sufficient conductivity is obtained and the first conductive particles are not excessively hardened, and the first conductive particles are sufficiently deformed at the time of connection between the electrodes.

The average particle diameter of the first conductive particles is preferably 0.5 占 퐉 or more, more preferably 1 占 퐉 or more, further preferably 3 占 퐉 or more, preferably 100 占 퐉 or less, more preferably 50 占 퐉 or less Preferably 40 mu m or less, particularly preferably 30 mu m or less. When the average particle diameter of the first conductive particles is not less than the lower limit and not more than the upper limit, solder in the first conductive particles can be more efficiently arranged on the electrode, and solder in the first conductive particles It is easy to arrange a large number of electrodes, and the conduction reliability is further increased.

The " average particle diameter " of the first conductive particles indicates the number average particle diameter. The average particle diameter of the first conductive particles can be obtained by, for example, observing 50 pieces of the first conductive particles with an electron microscope or an optical microscope and calculating an average value.

The CV value of the particle diameter of the first conductive particles is preferably 5% or more, more preferably 10% or more, preferably 40% or less, more preferably 30% or less. When the CV value of the particle diameter is not less than the lower limit and not more than the upper limit, solder can be more efficiently arranged on the electrode. However, the CV value of the particle diameter of the conductive particles may be less than 5%.

The CV value (coefficient of variation) of the particle diameter of the first conductive particles can be measured as follows.

CV value (%) = (rho / Dn) x100

ρ: standard deviation of the particle diameters of the first conductive particles

Dn: Average value of the particle diameters of the first conductive particles

The shape of the first conductive particles is not particularly limited. The shape of the first conductive particles may be a spherical shape or a shape other than a spherical shape such as a flat shape.

The acid value of the first conductive particles is preferably 0.1 mg / KOH or more, more preferably 1 mg / KOH or more, preferably 10 mg / KOH or less, more preferably 7 mg / KOH or less. If the acid value is higher than or equal to the lower limit and lower than or equal to the upper limit, the heat resistance of the cured product is further increased, and the discoloration of the cured product is further suppressed.

The acid value can be measured in the following manner. Phenolphthalein was added to ethanol, and 50 ml of the solution neutralized with 0.1 N-KOH was added with 1 g of the first conductive particles, dispersed by ultrasonic treatment, and titrated with 0.1 N-KOH.

The content of the first conductive particles in 100 wt% of the conductive material is preferably 1 wt% or more, more preferably 2 wt% or more, further preferably 10 wt% or more, particularly preferably 20 wt% or more , Most preferably not less than 30 wt%, preferably not more than 90 wt%, more preferably not more than 80 wt%, more preferably not more than 60 wt%, particularly preferably not more than 50 wt%. When the content of the first conductive particles is not less than the lower limit and not more than the upper limit, the solder in the first conductive particles can be more efficiently arranged on the electrode, and the solder in the first conductive particles It is easy to arrange them, and the conduction reliability is further enhanced. From the viewpoint of further enhancing conduction reliability, the content of the first conductive particles is preferably large.

(Second conductive particle)

The second conductive particle has silver, ruthenium, iridium, gold, palladium or platinum (conductive portion including silver, ruthenium, iridium, gold, palladium or platinum) on the outer surface portion of the conductive portion. The second conductive particles may be metal particles formed by silver, ruthenium, iridium, gold, palladium or platinum. The metal particles have silver, ruthenium, iridium, gold, palladium or platinum on the outer surface portion of the conductive portion. The metal particles are particles in which both the center portion and the outer surface of the conductive portion are silver, ruthenium, iridium, gold, palladium or platinum. The metal particles are core particles and do not have base particles. The metal particles are different from the conductive particles having the base particles and the conductive portions disposed on the surface of the base particles. The conductive portion including the outer surface portion of the conductive portion and the silver, ruthenium, iridium, gold, palladium or platinum is preferably 80 wt% or more, more preferably 80 wt% or more, for example, silver, ruthenium, By weight or more, 90% by weight or more, and more preferably 95% by weight or more. The second conductive particles may have base particles and a conductive portion disposed on the surface of the base particles. In this case, the second conductive particles have silver, ruthenium, iridium, gold, palladium or platinum on the outer surface portion of the conductive portion.

The outer surface portion of the conductive portion of the second conductive particle is higher than the melting point of the outer surface portion of the conductive portion of the first conductive particle. It is preferable that the conductive portion including the outer surface portion of the conductive portion of the second conductive particle and the silver, ruthenium, iridium, gold, palladium or platinum is higher than the melting point of the outer surface portion of the conductive portion of the first conductive particle by 50 ° C or more And preferably 100 占 폚 or higher. The melting point of the outer surface portion of the conductive portion of the second conductive particles and the conductive portion containing silver, ruthenium, iridium, gold, palladium or platinum is preferably 300 ° C or higher, more preferably 400 ° C or higher, Lt; / RTI >

The base particles in the second conductive particles may be the same base particles as the base particles in the first conductive particles.

The second conductive particles may be the conductive particles instead of silver, ruthenium, iridium, gold, palladium or platinum in the solder in the conductive particles 21 shown in Fig. The second conductive particles may be the conductive particles instead of silver, ruthenium, iridium, gold, palladium or platinum in the solder of the second conductive portion 33B in the conductive particles 31 shown in Fig. The second conductive particles may be solder of the solder portion 42 in the conductive particles 41 shown in Fig. 6 instead of silver, ruthenium, iridium, gold, palladium or platinum.

The conductive portion containing silver, ruthenium, iridium, gold, palladium or platinum may contain at least one metal selected from the group consisting of silver, ruthenium, iridium, gold, palladium and platinum. Silver, ruthenium, iridium, gold, palladium or platinum may contain two or more metals selected from the group consisting of silver, ruthenium, iridium, gold, palladium and platinum. Silver, ruthenium, iridium, gold, palladium and platinum may be alloyed in the conductive portion including silver, ruthenium, iridium, gold, palladium or platinum.

From the viewpoint of more efficiently arranging the solder in the first conductive particles on the electrode, it is preferable that the second conductive particles have silver, gold, palladium or platinum on the outer surface portion of the conductive portion, It is more preferable to have silver, gold or palladium, more preferably gold or palladium on the outer surface portion of the conductive portion, and particularly preferably gold on the outer surface portion of the conductive portion.

The thickness of the conductive part including silver, ruthenium, iridium, gold, palladium or platinum is preferably 0.005 탆 or more, more preferably 0.01 탆 or more, preferably 10 탆 or less, more preferably 1 탆 or less, More preferably not more than 0.3 mu m. When the thickness of the conductive part including ruthenium, iridium, gold, palladium or platinum is not less than the lower limit and not more than the upper limit, sufficient conductivity is obtained.

The average particle diameter of the second conductive particles is preferably not less than 3 mu m, preferably not more than 50 mu m, more preferably not more than 20 mu m, further preferably not more than 10 mu m. If the second conductive particles are above the lower limit and above the upper limit, solder in the first conductive particles can be more efficiently arranged on the electrode by the second conductive particles.

The ratio of the average particle diameter of the first conductive particles to the average particle diameter of the second conductive particles (average particle diameter of the first conductive particles / average particle diameter of the second conductive particles) is preferably 1 or more, more preferably Is preferably 2 or more, more preferably 3 or more, and is preferably 4 or less. When the ratio (the average particle diameter of the first conductive particles / the average particle diameter of the second conductive particles) is not less than the lower limit and not more than the upper limit, solder in the first conductive particles is formed on the electrode by the second conductive particles, It can be placed more efficiently.

From the viewpoint of efficiently disposing the solder on the electrode, it is particularly preferable that the average particle diameter of the second conductive particles is smaller than the average particle diameter of the first conductive particles.

The " average particle diameter " of the second conductive particles indicates the number average particle diameter. The average particle diameter of the second conductive particles can be obtained, for example, by observing 50 arbitrary second conductive particles with an electron microscope or an optical microscope and calculating an average value.

The shape of the second conductive particles is not particularly limited. The shape of the second conductive particles may be spherical or may be a shape other than a spherical shape such as a flattened shape.

The content of the second conductive particles in 100 wt% of the conductive material is preferably 1 wt% or more, and more preferably 3 wt% or more. When the content of the second conductive particles is not lower than the lower limit, solder in the first conductive particles can be more efficiently arranged on the electrode by the second conductive particles.

The content of the second conductive particles in 100 wt% of the conductive material is preferably 10 wt% or less, more preferably 5 wt% or less. When the content of the second conductive particles is not lower than the lower limit, solder in the first conductive particles can be more efficiently arranged on the electrode by the second conductive particles, and the bonding strength by the connecting portion can be further increased .

The ratio of the content of the first conductive particles to the content of the second conductive particles is preferably 3 or more, more preferably 3 or more, in terms of weight, from the viewpoint of more efficiently arranging the solder in the first conductive particles on the electrode. Preferably 10 or more, preferably 80 or less, and more preferably 70 or less.

(Thermosetting compound)

The thermosetting compound is a compound that can be cured by heating. Examples of the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenol compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds and polyimide compounds. An epoxy compound or an episulfide compound is preferable from the viewpoint of further improving the curability and viscosity of the conductive material and further improving the connection reliability. The thermosetting compound may be used alone or in combination of two or more.

From the viewpoint of more effectively placing the solder on the electrode, it is preferable that the thermosetting compound includes a thermosetting compound having a polyether skeleton.

As the thermosetting compound having a polyether skeleton, a compound having a glycidyl ether group at both terminals of an alkyl chain having 3 to 12 carbon atoms and a polyether skeleton having 2 to 4 carbon atoms and having 2 to 10 polyether skeletons continuously And polyether-type epoxy compounds having bonded structural units.

From the viewpoint of effectively increasing the heat resistance of the cured product and effectively lowering the dielectric constant of the cured product, it is preferable that the thermosetting compound includes a thermosetting compound having a triazine skeleton.

Examples of the thermosetting compound having a triazine skeleton include triazine triglycidyl ether and the like, and TEPIC series (TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, TEPIC- -PAS, TEPIC-VL, TEPIC-UC).

Examples of the epoxy compound include aromatic epoxy compounds. A crystalline epoxy compound such as a resorcinol-type epoxy compound, a naphthalene-type epoxy compound, a biphenyl-type epoxy compound, and a benzophenone-type epoxy compound is preferable. An epoxy compound which is solid at normal temperature (23 캜) and whose melting temperature is lower than the melting point of the solder is preferable. The melting temperature is preferably 100 占 폚 or lower, more preferably 80 占 폚 or lower, and preferably 40 占 폚 or higher. By using the above-mentioned preferable epoxy compound, at the step of joining the members to be connected, when the viscosity is high and acceleration is given by impact such as transportation, the positional deviation of the first connection object member and the second connection object member The viscosity of the conductive material can be greatly lowered by the heat at the time of curing, and the agglomeration of the solder can be efficiently promoted.

From the viewpoint of more effectively placing the solder on the electrode, it is preferable that the thermosetting compound includes a thermosetting compound that is liquid at 25 占 폚.

The content of the thermosetting compound in 100 wt% of the conductive material is preferably 20 wt% or more, more preferably 40 wt% or more, further preferably 50 wt% or more, preferably 99 wt% or less Preferably 98% by weight or less, more preferably 90% by weight or less, particularly preferably 80% by weight or less. If the content of the thermosetting compound is lower than or equal to the lower limit and lower than or equal to the upper limit, solder in the conductive particles can be more efficiently disposed on the electrode, further suppressing positional displacement between the electrodes, have. From the viewpoint of further improving the impact resistance, the content of the above-mentioned thermosetting compound is preferably large.

(Thermosetting agent)

The thermosetting agent thermally cures the thermosetting compound. Examples of the heat curing agent include an imidazole curing agent, a phenol curing agent, a thiol curing agent, an amine curing agent, an acid anhydride curing agent, a thermal cationic initiator, and a thermal radical generator. The thermosetting agent may be used alone or in combination of two or more.

The imidazole curing agent is not particularly limited, and examples thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl- Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s-triazine and 2,4- diamino-6- [2 '-Methylimidazolyl- (1')] - ethyl-s-triazine isocyanuric acid adduct.

The thiol curing agent is not particularly limited, and trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate and dipentaerythritol hexa-3-mercaptopropionate And the like.

The solubility parameter of the thiol curing agent is preferably 9.5 or more, and preferably 12 or less. The solubility parameter is calculated by the Fedors method. For example, the solubility parameter of trimethylolpropane tris-3-mercaptopropionate is 9.6 and the solubility parameter of dipentaerythritol hexa-3-mercaptopropionate is 11.4.

The amine curing agent is not particularly limited and includes hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5] undecane, Bis (4-aminocyclohexyl) methane, metaphenylenediamine and diaminodiphenylsulfone.

Examples of the thermal cationic initiator include an iodonium cation curing agent, an oxonium cation curing agent, and a sulfonium cation curing agent. Examples of the iodonium-based cationic curing agent include bis (4-tert-butylphenyl) iodonium hexafluorophosphate and the like. Examples of the oxonium-based cation curing agent include trimethyloxonium tetrafluoroborate and the like. Examples of the sulfonium cation-based curing agent include tri-p-tolylsulfonium hexafluorophosphate and the like.

The heat radical generator is not particularly limited, and examples thereof include an azo compound and an organic peroxide. Examples of the azo compound include azobisisobutyronitrile (AIBN) and the like. Examples of the organic peroxide include di-tert-butyl peroxide and methyl ethyl ketone peroxide.

The reaction initiation temperature of the thermosetting agent is preferably 50 占 폚 or higher, more preferably 70 占 폚 or higher, further preferably 80 占 폚 or higher, preferably 250 占 폚 or lower, more preferably 200 占 폚 or lower 150 DEG C or less, particularly preferably 140 DEG C or less. When the reaction initiation temperature of the thermosetting agent is not lower than the lower limit and not higher than the upper limit, the first conductive particles are more efficiently disposed on the electrode. The reaction initiation temperature of the thermosetting agent is particularly preferably 80 deg. C or more and 140 deg. C or less.

The reaction initiation temperature of the heat curing agent is preferably higher than the melting point of the solder in the first conductive particle, more preferably 5 deg. C or higher, more preferably 10 deg. C or higher Higher is more preferable.

The reaction initiation temperature of the thermosetting agent means the temperature at which the exothermic peak in DSC starts rising.

The content of the thermosetting agent is not particularly limited. The content of the thermosetting agent is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, preferably 200 parts by weight or less, more preferably 100 parts by weight or less, based on 100 parts by weight of the total amount of the thermosetting compound Or less, more preferably 75 parts by weight or less. When the content of the heat curing agent is lower than the lower limit, it is easy to sufficiently cure the conductive material. If the content of the thermosetting agent is less than the upper limit, an excess of the thermosetting agent which is not involved in curing after curing is hardly left, and the heat resistance of the cured product is further increased.

(Flux)

The conductive material preferably includes a flux. By using the flux, the solder can be arranged more effectively on the electrode. The flux is not particularly limited. As the flux, a flux generally used for solder bonding or the like can be used.

Examples of the flux include zinc chloride, a mixture of zinc chloride and an inorganic halide, a mixture of zinc chloride and an inorganic acid, a molten salt, a phosphoric acid, a derivative of phosphoric acid, an organic halide, a hydrazine, an organic acid and a resin. The flux may be used alone, or two or more fluxes may be used in combination.

Examples of the molten salt include ammonium chloride and the like. Examples of the organic acid include lactic acid, citric acid, stearic acid, glutamic acid and glutaric acid. Examples of the above-mentioned rosin include activated rosin and inactivated rosin. It is preferable that the flux is an organic acid having two or more carboxyl groups, and a resin. The flux may be an organic acid having two or more carboxyl groups, or may be a resin. By using an organic acid having two or more carboxyl groups and a resinous ring, the reliability of conduction between the electrodes is further enhanced.

The rosin is rosin mainly containing abietic acid. The flux is preferably rosin, more preferably abietic acid. By using this preferable flux, the reliability of conduction between the electrodes is further enhanced.

The active temperature (melting point) of the flux is preferably 50 ° C or more, more preferably 70 ° C or more, further preferably 80 ° C or more, preferably 200 ° C or less, more preferably 190 ° C or less, Preferably 160 DEG C or lower, more preferably 150 DEG C or lower, even more preferably 140 DEG C or lower. When the active temperature of the flux is higher than or equal to the lower limit and lower than or equal to the upper limit, the flux effect is more effectively exerted, and the first conductive particles are disposed more efficiently on the electrode. The active temperature (melting point) of the flux is preferably 80 ° C or more and 190 ° C or less. It is particularly preferable that the activation temperature (melting point) of the flux is 80 ° C or more and 140 ° C or less.

(Melting point: 186 占 폚), glutaric acid (melting point: 96 占 폚), adipic acid (melting point: 152 占 폚), pimelic acid (melting point: 104 占 폚), and the like, (Melting point: 122 占 폚), malic acid (melting point: 130 占 폚), and the like.

The boiling point of the flux is preferably 200 ° C or lower.

From the viewpoint of more efficiently placing the solder on the electrode, the melting point of the flux is preferably higher than the melting point of the solder in the first conductive particle, more preferably 5 ° C or higher, and more preferably 10 ° C or higher desirable.

From the viewpoint of more efficiently placing the solder on the electrode, the melting point of the flux is preferably higher than the reaction initiation temperature of the thermosetting agent, more preferably 5 ° C or higher, and still more preferably 10 ° C or higher.

The flux may be dispersed in the conductive material or attached on the surface of the first conductive particle.

When the melting point of the flux is higher than the melting point of the solder, the first conductive particles can be agglomerated efficiently on the electrode portion. This is because, when the electrode is formed on the connection target member and the portion of the connection target member around the electrode is compared, the thermal conductivity of the electrode portion is higher than the thermal conductivity of the connection target member portion around the electrode, It is due to the rapid increase in temperature. In the step where the melting point of the first conductive particles is exceeded, the inside of the first conductive particles dissolves, but the oxide film formed on the surface does not reach the melting point (active temperature) of the flux and is not removed. In this state, since the temperature of the electrode portion first reaches the melting point (active temperature) of the flux, the oxide film on the surface of the first conductive particles on the electrode is preferentially removed, and the first conductive particles spread on the surface of the electrode . Thereby, the first conductive particles can be agglomerated efficiently on the electrode.

The flux is preferably a flux that releases cations by heating. By using the flux that releases the positive ions by heating, the first conductive particles can be arranged more efficiently on the electrode.

As the flux that releases the cation by the heating, the thermal cationic initiator may be mentioned.

The content of the flux in 100 wt% of the conductive material is preferably 0.5 wt% or more, preferably 30 wt% or less, more preferably 25 wt% or less. The conductive material may not contain a flux. If the content of the flux is above the lower limit and below the upper limit, it is difficult to further form an oxide film on the surface of the solder and the electrode, and furthermore, the oxide film formed on the surface of the solder and the electrode can be removed more effectively.

(Insulating particles)

It is preferable that the conductive material includes insulating particles. In the conductive material, the insulating particles may not be attached to the surface of the first conductive particles and to any surface of the surface of the second conductive particles. In the conductive material, it is preferable that the insulating particles are spaced apart from the first conductive particles, and the insulating particles are preferably spaced apart from the second conductive particles. By including the insulating particles, the interval between the connection target members connected by the cured product of the conductive material and the interval between the connection target members connected by the solder in the first conductive particles can be controlled with high accuracy.

The average particle diameter of the insulating particles is preferably 10 占 퐉 or more, more preferably 20 占 퐉 or more, further preferably 25 占 퐉 or more, preferably 100 占 퐉 or less, more preferably 75 占 퐉 or less, Is not more than 50 mu m. The distance between the connection target members connected by the cured product of the conductive material and the distance between the connection target members connected by the solder in the first conductive particle when the average particle diameter of the insulating particles is not less than the lower limit and not more than the upper limit, Is more appropriate.

Examples of the material of the insulating particles include an insulating resin and an insulating inorganic material.

Specific examples of the insulating resin that is the material of the insulating particles include polyolefin compounds, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, .

Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer. Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate. Examples of the block polymer include polystyrene, styrene-acrylic acid ester copolymer, SB type styrene-butadiene block copolymer and SBS type styrene-butadiene block copolymer, and hydrogenated products thereof. Examples of the thermoplastic resin include a vinyl polymer and a vinyl copolymer. Examples of the thermosetting resin include an epoxy resin, a phenol resin, and a melamine resin. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, methylcellulose and the like. Soluble resin is preferable, and polyvinyl alcohol is more preferable.

Specific examples of the insulating inorganic material that is the material of the insulating particles include silica and organic-inorganic hybrid particles. The particles formed by the silica are not particularly limited. For example, particles obtained by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, and then firing if necessary, . Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

The content of the insulating particles in 100 wt% of the conductive material is preferably 0.1 wt% or more, more preferably 0.5 wt% or more, preferably 10 wt% or less, more preferably 5 wt% or less. The conductive material may not contain insulating particles. When the content of the insulating particles is not less than the lower limit and not more than the upper limit, the interval between the connection target members connected by the cured product of the conductive material and the interval between the connection target members connected by the solder are more appropriate.

(Other components)

The conductive material may contain various additives such as fillers, extenders, softeners, plasticizers, polymerization catalysts, curing catalysts, colorants, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, .

(Connection structure and manufacturing method of connection structure)

A connection structure according to the present invention includes a first connection target member having at least one first electrode on its surface, a second connection target member having at least one second electrode on its surface, the first connection target member, And a connecting portion connecting the second connection target member. In the connection structure according to the present invention, the material of the connecting portion is the above-described conductive material. The connecting portion is a cured product of the above-described conductive material. The connection portion is formed by the above-described conductive material. In the connection structure according to the present invention, the first electrode and the second electrode are electrically connected by the solder portion in the connection portion.

The connection portion has a cured product, a solder portion, and second conductive particles having silver, ruthenium, iridium, gold, palladium or platinum on the outer surface portion of the conductive portion. In the connection structure, the second conductive particles are disposed in the solder portion. The second conductive particles preferably have gold, palladium or platinum on the outer surface portion of the conductive portion.

The method for manufacturing the connection structure includes the steps of disposing the conductive material on the surface of the first connection target member having at least one first electrode on the surface thereof using the conductive material described above, Disposing a second connection target member having at least one second electrode on its surface on a surface opposite to the object member side so that the first electrode and the second electrode face each other; The connecting member connecting the first connection target member and the second connection target member is formed by the conductive material and the first electrode and the second connection target member are connected to each other by heating the conductive material at a temperature equal to or higher than the melting point of the solder, And electrically connecting the two electrodes to each other by a soldering portion in the connecting portion. Preferably, the conductive material is heated above the curing temperature of the thermosetting component, the thermosetting compound. In the resulting connecting structure, the second conductive particles are disposed in the solder portion.

In the connection structure according to the present invention and the method for manufacturing the connection structure, since a specific conductive material is used, the solder in the plurality of first conductive particles is sandwiched between the first electrode and the second electrode So that the solder can be efficiently arranged on the electrode (line). In addition, a part of the solder is hardly arranged in a region where no electrode is formed (space), and the amount of solder disposed in an area where no electrode is formed can be significantly reduced. Therefore, the conduction reliability between the first electrode and the second electrode can be improved. In addition, it is possible to prevent electrical connection between the adjacent electrodes in the transverse direction which should not be connected, and the insulation reliability can be improved.

In addition, in order to efficiently dispose the solder in the plurality of first conductive particles on the electrode and considerably reduce the amount of the solder disposed in the region where no electrode is formed, a conductive paste is used instead of the conductive film .

The thickness of the solder portion between the electrodes is preferably 10 占 퐉 or more, more preferably 20 占 퐉 or more, preferably 100 占 퐉 or less, and more preferably 80 占 퐉 or less. The area of the solder wetting area on the surface of the electrode (the area where the solder contacts with the exposed area of 100% of the electrode, the exposed portion of the second electrode, which is electrically connected to the first electrode and the first electrode before forming the connection portion, Is an area in contact with the solder portion after forming the connecting portion with respect to 100% of the area) is preferably 50% or more, more preferably 70% or more, and preferably 100% or less.

The average particle diameter of the second conductive particles may be equal to or less than the thickness of the solder portion between the electrodes or may be less than the thickness of the solder portion between the electrodes or less than or equal to 1/2 of the thickness of the solder portion between the electrodes And may be 1/3 or less of the thickness of the soldering portion between the electrodes.

Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.

1 is a cross-sectional view schematically showing a connection structure obtained by using a conductive material according to an embodiment of the present invention.

The connection structure 1 shown in Fig. 1 connects the first connection target member 2, the second connection target member 3, the first connection target member 2 and the second connection target member 3 (4). The connecting portion 4 is formed by the above-described conductive material. In the present embodiment, the conductive material is the first conductive particles and includes solder particles.

The connecting portion 4 has a soldering portion 4A in which a plurality of solder particles are gathered and joined together, a hardened portion 4B in which a thermosetting component is thermally cured, and second conductive particles 11C.

The first connection target member 2 has a plurality of first electrodes 2a on its surface (upper surface). The second connection target member 3 has a plurality of second electrodes 3a on its surface (lower surface). The first electrode 2a and the second electrode 3a are electrically connected by the soldering portion 4A. Therefore, the first connection target member 2 and the second connection target member 3 are electrically connected by the solder portion 4A. In the connection structure 1, the second conductive particles 11C are disposed in the solder portion 4A.

In the region (cured portion 4B) different from the soldering portion 4A gathered between the first electrode 2a and the second electrode 3a in the connecting portion 4, there is no solder. There is no solder spaced apart from the soldering portion 4A in the region different from the soldering portion 4A (portion of the cured portion 4B). In the case of a small amount, solder may be present in a region (cured portion 4B) different from the soldering portion 4A gathered between the first electrode 2a and the second electrode 3a. In the connecting portion 4, the second conductive particles 11C are formed in the region (cured portion 4B) other than the soldering portion 4A gathered between the first electrode 2a and the second electrode 3a, Does not exist. In the area of the soldering portion 4A (the portion of the hardened portion 4B), there is no second conductive particles 11C spaced apart from the soldering portion 4A. In the case of a small amount, the second conductive particles 11C may exist in a region (cured portion 4B) other than the soldering portion 4A gathered between the first electrode 2a and the second electrode 3a .

As shown in Fig. 1, in the connection structure 1, a plurality of solder particles are collected between the first electrode 2a and the second electrode 3a, and after a plurality of solder particles are melted, After the surface of the electrode is expanded, it solidifies and a soldering portion 4A is formed. This increases the connection area between the solder portion 4A and the first electrode 2a and between the solder portion 4A and the second electrode 3a. As a result, conduction reliability and connection reliability in the connection structure 1 are enhanced. Further, the flux included in the conductive material is generally deactivated by heating.

In the connection structure 1 shown in Fig. 1, all of the soldering portions 4A are located in areas facing each other between the first and second electrodes 2a, 3a. The connection structure 1X of the modified example shown in Fig. 3 differs from the connection structure 1 shown in Fig. 1 only in the connection portion 4X. The connecting portion 4X has a soldering portion 4XA and a cured portion 4XB. Most of the soldering portion 4XA is located in the region where the first and second electrodes 2a and 3a are opposed to each other and the soldering portion 4XA is part of the first and second electrodes 2a and 3a, But may be sideways from the opposing area of the electrodes 2a and 3a. The soldering portion 4XA that is laterally released from the region where the first and second electrodes 2a and 3a face each other is a part of the soldering portion 4XA and is not solder spaced apart from the soldering portion 4XA. In the present embodiment, the amount of solder spaced apart from the solder portion can be reduced, but solder spaced from the solder portion may be present in the hardened portion. In addition, even in the connection structure 1X, the second conductive particles 11C are disposed in the solder portion 4XA.

When the usage amount of the solder particles is reduced, it is easy to obtain the connection structure 1. If the amount of solder particles used is increased, it is easy to obtain the connection structure 1X.

When viewed from mutually facing portions of the first electrode and the second electrode in the stacking direction of the first electrode, the connection portion, and the second electrode, from the viewpoint of further enhancing conduction reliability, (Preferably 60% or more, and more preferably 70% or more) of 100% of the areas of the two electrodes facing each other.

When viewed from mutually facing portions of the first electrode and the second electrode in a direction orthogonal to the lamination direction of the first electrode, the connection portion, and the second electrode, from the viewpoint of further enhancing conduction reliability, (Preferably 70% or more, more preferably 90% or more, and more preferably 99% or more) of the solder portion in the connection portion is arranged in the mutually opposing portion of the electrode and the second electrode .

The ratio of the number of the second conductive particles arranged in the solder portion among the total number 100% of the second conductive particles in the connection portion is preferably 50% or more, more preferably 50% or more, , Preferably at least 80%, more preferably at least 90%, particularly preferably at least 95%.

Next, an example of a method of manufacturing the connection structure 1 using the conductive material according to one embodiment of the present invention will be described.

First, a first connection target member 2 having a first electrode 2a on its surface (upper surface) is prepared. 2 (a), a thermosetting component 11B, a plurality of solder particles 11A, and a plurality of second conductive particles 11C are formed on the surface of the first connection target member 2, (The first step). The conductive material used is a thermosetting component 11B, which includes a thermosetting compound and a thermosetting agent.

The conductive material 11 is disposed on the surface of the first connection target member 2 on which the first electrode 2a is provided. After the conductive material 11 is disposed, the solder particles 11A are arranged on both the first electrode 2a (line) and on the region (space) where the first electrode 2a is not formed.

The method for disposing the conductive material 11 is not particularly limited, and examples thereof include coating with a dispenser, screen printing, and ejection with an inkjet apparatus.

Furthermore, a second connection target member 3 having a second electrode 3a on its surface (lower surface) is prepared. 2 (b), in the conductive material 11 on the surface of the first connection target member 2, the conductive material 11 is bonded to the first connection target member 2 side And the second connection target member 3 is arranged on the surface on the opposite side (second step). The second connection target member 3 is disposed on the surface of the conductive material 11 from the second electrode 3a side. At this time, the first electrode 2a and the second electrode 3a are opposed to each other.

Subsequently, the conductive material 11 is heated to a temperature equal to or higher than the melting point of the solder particles 11A (third step). Preferably, the conductive material 11 is heated above the curing temperature of the thermosetting component 11B (binder). During this heating, the solder particles 11A existing in the region where no electrode is formed are gathered between the first electrode 2a and the second electrode 3a (magnetic cohesion effect). At this time, the second conductive particles 11C existing between the plurality of solder particles 11A pull the solder particles 11A close to each other, thereby promoting the movement of the solder particles 11A. When a conductive paste is used instead of a conductive film, solder particles 11A are effectively gathered between the first electrode 2a and the second electrode 3a. Further, the solder particles 11A are melted and bonded to each other. Further, the thermosetting component 11B thermally cures. As a result, as shown in Fig. 2 (c), the connection portion 4 connecting the first connection target member 2 and the second connection target member 3 is formed by the conductive material 11 . The connecting portion 4 is formed by the conductive material 11 and the plurality of solder particles 11A are joined together to form the solder portion 4A and the thermosetting component 11B is thermally cured to form the cured portion 4B . In addition, the second conductive particles 11C are arranged and introduced into the solder portion 4A. When the solder particles 11A sufficiently move, the movement of the solder particles 11A which are not located between the first electrode 2a and the second electrode 3a starts, and then the first electrode 2a and the second electrode 3a, It is not necessary to keep the temperature constant until the movement of the solder particles 11A is completed between the upper and lower substrates 3a.

In the present embodiment, it is preferable that no pressure is applied in the second step and the third step. In this case, the weight of the second connection target member 3 is applied to the conductive material 11. This allows the solder particles 11A to effectively gather between the first electrode 2a and the second electrode 3a at the time of forming the connection portion 4. When the pressing is performed in at least one of the second step and the third step, the tendency that the action of the solder particles 11A to gather between the first electrode 2a and the second electrode 3a is inhibited .

Further, in this embodiment, since the pressing is not performed, when the second connection target member is overlapped with the first connection target member coated with the conductive material, the electrode of the first connection target member and the electrode Even if the first connection target member and the second connection target member are overlapped with each other in the state where the alignment of the first connection target member and the second connection target member are misaligned, the shift can be corrected and the electrodes of the first connection target member and the electrodes of the second connection target member can be connected (Self-alignment effect). This is because the molten solder magnetically agglomerated between the electrodes of the first connection target member and the electrodes of the second connection target member is soldered between the electrodes of the first connection target member and the electrodes of the second connection target member and the other components This is because the minimum contact area is stabilized energetically, so that a connecting structure having a minimum area becomes a force of a connection structure having alignment. In this case, it is preferable that the conductive material is not cured and that the viscosity of components other than the conductive particles of the conductive material is sufficiently low at the temperature and time.

In this manner, the connection structure 1 shown in Fig. 1 is obtained. Further, the second step and the third step may be performed continuously. After the second step is performed, the resulting laminate of the first connection target member 2, the conductive material 11, and the second connection target member 3 is moved to the heating portion, and the third step is performed . In order to perform the heating, the laminate may be disposed on the heating member, or the laminate may be disposed in the heated space.

The heating temperature in the third step is preferably 140 占 폚 or higher, more preferably 160 占 폚 or higher, preferably 450 占 폚 or lower, more preferably 250 占 폚 or lower, still more preferably 200 占 폚 or lower.

As the heating method in the third step, the entire connection structure may be heated by using a reflow furnace or using an oven at a temperature equal to or higher than the melting point of the solder and the curing temperature of the thermosetting compound, And then heating the mixture.

The first and second connection target members are not particularly limited. Specific examples of the first and second connection target members include semiconductor chips, semiconductor packages, LED chips, LED packages, electronic components such as capacitors and diodes, resin films, printed boards, flexible printed boards, flexible flat cables, An electronic component such as a rigid flexible substrate, a glass epoxy substrate, and a circuit substrate such as a glass substrate. It is preferable that the first and second connection target members are electronic parts.

It is preferable that at least one of the first connection target member and the second connection target member is a resin film, a flexible printed circuit board, a flexible flat cable, or a rigid flexible substrate. It is preferable that the second connection target member is a resin film, a flexible printed circuit board, a flexible flat cable, or a rigid flexible substrate. Resin films, flexible printed boards, flexible flat cables and rigid flexible boards have high flexibility and relatively light weight properties. When a conductive film is used for connecting the connection target member, the solder tends to be difficult to collect on the electrode. On the other hand, by using the conductive paste, even when a resin film, a flexible printed circuit board, a flexible flat cable, or a rigid flexible substrate is used, the reliability of conduction between the electrodes can be sufficiently improved by efficiently collecting the solder on the electrode. In the case of using a resin film, a flexible printed circuit board, a flexible flat cable, or a rigid flexible substrate, the effect of improving the conduction reliability between the electrodes due to no pressing is further improved as compared with the case of using other members to be connected such as semiconductor chips .

Examples of the electrode provided on the member to be connected include metal electrodes such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, copper electrodes, molybdenum electrodes, silver electrodes, SUS electrodes and tungsten electrodes. When the connection target member is a flexible printed circuit board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode, or a copper electrode. When the connection target member is a glass substrate, it is preferable that the electrode is an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode. When the electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode in which an aluminum layer is laminated on the surface of the metal oxide layer. Examples of the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. The present invention is not limited to the following examples.

Polymer A:

(1) Synthesis of first reaction product of bisphenol F, 1,6-hexanediol diglycidyl ether and bisphenol F type epoxy resin:

72 parts by weight of bisphenol F (containing 4,4'-methylenebisphenol and 2,4'-methylenebisphenol and 2,2'-methylenebisphenol in a weight ratio of 2: 3: 1), 1,6-hexanediol di 270 parts by weight of glycidyl ether and 30 parts by weight of bisphenol F type epoxy resin ("EPICLON EXA-830CRP" manufactured by DIC Corporation) were placed in a three-necked flask and dissolved at 100 ° C under a nitrogen flow. Thereafter, 0.1 part by weight of tetra-n-butylsulfonium bromide as an addition reaction catalyst between a hydroxyl group and an epoxy group was added and an addition polymerization reaction was conducted at 130 占 폚 for 6 hours under a nitrogen flow to obtain a first reaction product.

NMR confirmed that the addition polymerization reaction had proceeded and that the first reaction product contained a structural unit in which a hydroxyl group derived from bisphenol F and an epoxy group of 1,6-hexanediol diglycidyl ether and bisphenol F type epoxy resin were bonded to each other, And an epoxy group at both ends.

(2) Synthesis of polymer A:

100 parts by weight of the first reaction product was placed in a three-necked flask and dissolved at 120 캜 under a nitrogen flow. Thereafter, 2 parts by weight of "KBE-9007" (3-isocyanate propyltriethoxysilane) manufactured by Shin-Etsu Silicone Co., Ltd. was added, and the reaction product of the side chain hydroxyl group of the first reactant and the isocyanate group of 3-isocyanatepropyltriethoxysilane And 0.002 parts by weight of dibutyl tin dilaurate were added, and the mixture was reacted at 120 占 폚 for 4 hours under a nitrogen flow. Thereafter, it was vacuum-dried at 110 DEG C for 5 hours to remove unreacted KBE-9007.

NMR confirmed that the reaction of the side chain hydroxyl group of the first reactant and the isocyanate group of the 3-isocyanatepropyltriethoxysilane proceeded, and that the resulting compound had a hydroxyl group derived from bisphenol F and 1,6-hexanediol diglycidyl It was confirmed that the main chain had a structural unit in which an epoxy group of a cystyl ether and a bisphenol F type epoxy resin was bonded, and an epoxy group at both ends and a propyltriethoxysilane group in the side chain. Thus, a phenoxy resin (polymer A) was obtained.

Thermosetting compound 1: Resorcinol-type epoxy compound, "Epolite TDC-LC" manufactured by Kyowa Chemical Co., Ltd., epoxy equivalent weight 120 g / eq

Thermosetting compound 2: Epoxy compound "EP-3300" manufactured by ADEKA, epoxy equivalent weight 160 g / eq

Photopolymerization initiator: acylphosphine oxide compound, "DAROCUR TPO" manufactured by Shiba Japan

Chain transfer agent: pentaerythritol tetrakis (3-mercaptobutyrate), "CALENS MT PE1" manufactured by Showa Denko KK

Latent epoxy thermosetting agent: "Fuji Cure 7000" manufactured by T & K TOKA

Flux 1:

25 parts by weight of glutaric acid and 25 parts by weight of monomethyl glutarate were placed in a three-necked flask and dissolved at 80 占 폚 under a nitrogen flow. Thereafter, 57 parts by weight of benzylamine was added and reacted at 80 DEG C under reduced pressure (4 Torr or less) for 2 hours to obtain Flux 1, which was solid at 25 DEG C.

Insulating particles: average particle diameter 30 占 퐉, CV value 5%, softening point 330 占 폚, divinylbenzene crosslinked particles manufactured by Sekisui Chemical Co., Ltd.

Solder Particle 1:

(Trade name: ST-5, average particle diameter (median diameter) 30 占 퐉) and citric acid ("citric acid" manufactured by Wako Pure Chemical Industries, Ltd.) were mixed with a Sn-3Ag-0.5Cu solder particle Was used and stirred for 8 hours while being dehydrated in a toluene solvent at 90 deg. C to obtain a solder particle 1 (CV value: 20%) in which a group containing a carboxyl group was covalently bonded to the surface of the solder.

Solder Particle 2:

200 g of Sn-3Ag-0.5Cu solder particles ("ST-5" manufactured by Mitsui Kinzoku Co., average particle diameter (median diameter) 30 μm) and 10 g of a silane coupling agent having an isocyanate group ("KBE- And 70 g of acetone were weighed into a three-necked flask. While stirring at room temperature, 0.25 g of dibutyltin dilaurate, which is a reaction catalyst between the hydroxyl group and isocyanate group on the surface of the solder particles, was added and heated at 100 ° C for 2 hours under nitrogen atmosphere with stirring. Thereafter, 50 g of methanol was added, and the mixture was heated at 60 占 폚 for 1 hour under a nitrogen atmosphere with stirring.

Thereafter, the resultant was cooled to room temperature, the solder particles were filtered with a filter paper, and the solvent was vacuum-dried at room temperature for 1 hour.

The solder particles were put in a three-necked flask, and 70 g of acetone, 30 g of trimethyl citrate, and 0.5 g of monobutyltin oxide as an ester exchange reaction catalyst were added and reacted at 60 ° C for 1 hour under nitrogen atmosphere with stirring.

As a result, the ester group of trimethyl citrate was covalently bonded to the silanol group derived from the silane coupling agent through transesterification reaction.

Thereafter, 10 g of citric acid was added and the mixture was reacted at 60 DEG C for 1 hour to add citric acid to the remaining methyl ester groups which had not reacted with the silanol groups of the trimethyl citrate.

Thereafter, the resultant was cooled to room temperature, and the solder particles were filtered with a filter paper. The solder particles were washed with hexane on a filter paper to remove residual trimethyl citrate and citric acid remaining on the surfaces of the unreacted and solder particles by non- In vacuum drying, the solvent was removed at room temperature for 1 hour.

After the obtained solder particles were broken with a ball mill, a sieve was selected so as to have a predetermined CV value. Thus, solder particles 2 (CV value: 20%) were obtained.

(CV value of the particle diameter of the solder particles and the conductive particles)

The CV value was measured by a laser diffraction particle size distribution analyzer (" LA-920 " manufactured by Horiba Seisakusho Co., Ltd.).

Second conductive particle 1: conductive particles (average particle diameter 15 占 퐉) having a gold layer (thickness: 0.02 占 퐉) disposed on the surface of the divinylbenzene resin particle,

Second conductive particles 2: conductive particles (average particle diameter 15 占 퐉) in which a palladium layer (thickness: 0.02 占 퐉) was disposed on the surface of the divinylbenzene resin particles;

Second conductive particles 3: conductive particles (average particle diameter 15 占 퐉) having a platinum layer (thickness: 0.02 占 퐉) disposed on the surface of the divinylbenzene resin particle,

Second conductive particles 6: Conductive particles (average particle diameter 15 占 퐉) having a ruthenium layer (thickness: 0.02 占 퐉) disposed on the surface of the divinylbenzene resin particle,

Second conductive particles 7: conductive particles (average particle diameter 15 占 퐉) in which an iridium layer (thickness: 0.02 占 퐉) was disposed on the surface of the divinylbenzene resin particle,

Second conductive particles 4: conductive particles (average particle diameter 10 占 퐉) in which a gold layer (thickness: 0.02 占 퐉) was arranged on the surface of the divinylbenzene resin particles;

Second conductive particles 5: conductive particles (average particle diameter 30 占 퐉) in which a gold layer (thickness: 0.02 占 퐉) was disposed on the surface of the divinylbenzene resin particles;

(Examples 1 to 13 and Comparative Examples 1 and 2)

(1) Fabrication of conductive material

The components shown in the following Tables 1 and 2 were compounded in amounts shown in Tables 1 and 2 below to obtain a conductive material (conductive paste).

(2) Fabrication of connection structure

A long carrier tape having a copper electrode pattern (having a copper electrode thickness of 12 mu m) having an L / S of 45 mu m / 45 mu m and an electrode length of 3 mm on its upper surface and a plurality of copper foil lands formed around the copper electrode pattern was prepared. Further, a semiconductor element having an L / S ratio of 45 占 퐉 / 45 占 퐉 was prepared. On the upper surface of the long carrier tape, the conductive paste was coated on the copper electrode pattern to a thickness of 100 mu m to form a conductive paste layer. Then, the semiconductor element was mounted with a mount. Further, a solder paste ("M705-GRN360-K2V" manufactured by Senjing Kogyo Kogyo Co., Ltd.) was applied to the plurality of copper foil lands, and a chip resistance component of 1005 size was mounted on the coating film of the copper foil land with a mount. Thereafter, reflow processing was performed in a reflow furnace to obtain a connection structure in which semiconductor elements and chip resistance parts were connected to electrodes.

(evaluation)

(1) Viscosity (? 25)

The viscosity (? 25) of the conductive paste at 25 占 폚 was measured under the conditions of 25 占 폚 and 5 rpm using an E-type viscometer ("TVE22L" manufactured by Tokushu Sangyo Co., Ltd.)).

(2) Viscosity

The viscosity (eta mmp) of the conductive paste at the melting point of the solder in the first conductive particle was measured at a strain rate of 1 rad, a frequency of 1 Hz, a temperature raising rate of 20 占 폚 / min, a measuring temperature range of 40 占 폚 using STRESSTECH (manufactured by EOLOGICA) Or the melting point of the solder. In this measurement, the viscosity at the melting point of the solder was read.

(3) Thickness of the soldering portion

The thicknesses of the soldering portions positioned between the upper and lower electrodes were evaluated by observing cross sections of the obtained connection structure.

(4) Arrangement accuracy of solder on electrode 1

In the obtained connecting structure, when the mutually opposing portions of the first electrode and the second electrode are viewed in the stacking direction of the first electrode, the solder portion and the second electrode, the area of the portions facing each other between the first electrode and the second electrode 100%, the ratio X of the area where the solder portions were arranged was evaluated. The placement accuracy 1 of the solder on the electrode was determined based on the following criteria.

[Criteria for Arrangement Accuracy 1 of Solder on Electrode]

○○: ratio X is 70% or more

○: ratio X is 60% or more and less than 70%

DELTA: ratio X is 50% or more and less than 60%

X: ratio X is less than 50%

(5) Arrangement Accuracy of Second Conductive Particles in Soldering Portion 2

In the resulting connection structure, the number ratio Y of the second conductive particles disposed in the solder portion among the total number 100% of the second conductive particles in the connection portion was evaluated. And the placement accuracy 2 of the second conductive particles in the soldering portion was determined based on the following criteria.

[Judgment Criteria of Arrangement Accuracy 2 of Second Conductive Particle in Soldering Portion]

○○○: the ratio Y is 95% or more

○○: The ratio of the number Y is more than 90% and less than 95%

○: the ratio Y of the number is 80% or more and less than 90%

?: The ratio Y of the number is 50% or more and less than 80%

X: the ratio Y of the number is less than 50%

(6) Reliability of conduction between the upper and lower electrodes

In the obtained connection structures (n = 15), the connection resistances per connection portion between the upper and lower electrodes were measured by the four-terminal method. And the average value of the connection resistance was calculated. From the relationship of voltage = current x resistance, the connection resistance can be obtained by measuring the voltage when a constant current is passed. The conduction reliability was judged based on the following criteria. However, when at least one of n = 15 electrodes was not conducting between the upper and lower electrodes, it was judged " x ".

[Criteria for reliability of conduction]

○○: Average value of connection resistance is less than 50mΩ

○: Average value of connection resistance is more than 50 mΩ and less than 70 mΩ

?: Average value of connection resistance is more than 70 m? And not more than 100 m?

×: Average value of connection resistance exceeds 100 mΩ, or connection failure occurs

(7) Reliability of insulation between electrodes adjacent to each other in the transverse direction

In the obtained connecting structure (n = 15), after being left in an atmosphere at 85 캜 and 85% humidity for 100 hours, 15 V was applied between the electrodes adjacent in the transverse direction, and the resistance value was measured at 25 points. The insulation reliability was judged based on the following criteria. However, when at least one of n = 15 electrodes in the transverse direction was conductive, it was judged " x ".

[Judgment Criteria of Insulation Reliability]

○○○: Average value of connection resistance is more than 10 ¹⁴ Ω

○○: average value of connection resistance is more than 10 ⁸ Ω and less than 10 ¹⁴ Ω

○: The average value of the contact resistance more than 10 ⁶ Ω is less than 10 ⁸ Ω

△: average value of connection resistance is 10 ⁵ Ω or more and less than 10 ⁶ Ω

X: Average value of connection resistance is less than 10 ⁵ Ω

The results are shown in Tables 1 and 2 below.

1, 1X: connection structure
2: first connection object member
2a: first electrode
3: second connection object member
3a: second electrode
4, 4X: connection
4A, 4XA: soldering portion
4B and 4XB:
11: Conductive material
11A: solder particles (first conductive particles)
11B: Thermosetting component
11C: Second conductive particle
21: First conductive particles (solder particles)
31: First conductive particle
32: Base particles
33: conductive part (conductive part having solder)
33A: second conductive part
33B: soldering portion
41: First conductive particle
42: soldering portion

Claims (16)

A plurality of first conductive particles having a solder on an outer surface portion of the conductive portion,
A second conductive particle having silver, ruthenium, iridium, gold, palladium or platinum on the outer surface portion of the conductive portion,
Thermosetting compounds,
A conductive material comprising a thermosetting agent. The conductive material according to claim 1, wherein the second conductive particles have gold, palladium or platinum on the outer surface portion of the conductive portion. The conductive material according to claim 1 or 2, wherein the viscosity of the conductive material at the melting point of the solder in the first conductive particle is not less than 2Pa s and not more than 10Pa s. The conductive material according to any one of claims 1 to 3, wherein the average particle diameter of the second conductive particles is smaller than the average particle diameter of the first conductive particles. The conductive material according to any one of claims 1 to 4, wherein the content of the second conductive particles is 10% by weight or less. The conductive material according to any one of claims 1 to 5, wherein the content of the first conductive particles is in the range of 3 to 80 based on the weight of the content of the second conductive particles. 7. The conductive material according to any one of claims 1 to 6, wherein the thermosetting compound comprises a thermosetting compound that is liquid at 25 占 폚. 8. The conductive material according to any one of claims 1 to 7, wherein the thermosetting compound comprises a thermosetting compound having a polyether skeleton. 9. The conductive material according to any one of claims 1 to 8, comprising a flux having a melting point of not lower than 50 占 폚 but not higher than 190 占 폚. The conductive material according to any one of claims 1 to 9, wherein a carboxyl group or an amino group is present on the outer surface of the first conductive particles. 11. The conductive material according to any one of claims 1 to 10, wherein the first conductive particles are solder particles having a solder in a center portion and an outer surface portion. 12. The conductive material according to any one of claims 1 to 11, comprising insulating particles not attached to the surface of the first conductive particles and the surface of the second conductive particles. A first connection target member having at least one first electrode on its surface,
A second connection object member having at least one second electrode on its surface,
And a connection unit connecting the first connection target member and the second connection target member,
Wherein the material of the connecting portion is the conductive material according to any one of claims 1 to 12,
Wherein the connecting portion has a hardened portion, a solder portion, and the second conductive particles,
The second conductive particles are disposed in the solder portion,
And the first electrode and the second electrode are electrically connected to each other by the solder portion in the connection portion. A first connection target member having at least one first electrode on its surface,
A second connection object member having at least one second electrode on its surface,
And a connection unit connecting the first connection target member and the second connection target member,
Wherein the connecting portion has a cured product, a solder portion, and second conductive particles having silver, ruthenium, iridium, gold, palladium or platinum on the outer surface portion of the conductive portion,
The second conductive particles are disposed in the solder portion,
And the first electrode and the second electrode are electrically connected to each other by the solder portion in the connection portion. 15. The connection structure according to claim 14, wherein the second conductive particles have gold, palladium or platinum on the outer surface portion of the conductive portion. The method according to any one of claims 13 to 15, wherein when the mutually facing portions of the first electrode and the second electrode facing each other in the lamination direction of the first electrode, the connection portion and the second electrode, Wherein a solder portion in the connection portion is disposed at 50% or more of an area of 100% of mutually facing portions of the first electrode and the second electrode.

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