KR20150092077A - Conductive material, connection structure and method for producing connection structure - Google Patents

Abstract

The present invention provides a conductive material which is less susceptible to voids in a connection portion formed by a conductive material and improves connection reliability after connection when the electrodes of the connection target member are electrically connected. The conductive material according to the present invention is used after being heated to a temperature of 120 占 폚 or less without being heated at a temperature exceeding 120 占 폚. The conductive particles 11 have a base particle 12 and a conductive layer 13 disposed on the surface of the base particle 12. When the compression elastic modulus of the conductive particles 11 have in 100 ℃ 20% compressive deformation is 500N / mm ² more than 2000N / mm ² or less. The compressive recovery rate of the conductive particles 11 at 100 캜 is 3% or more and 30% or less.

Description

TECHNICAL FIELD [0001] The present invention relates to a conductive material, a connection structure, and a method of manufacturing a connection structure,

The present invention relates to a conductive material comprising a plurality of conductive particles. More specifically, the present invention can be used for electrically connecting electrodes of various connection target members such as a flexible printed substrate, a glass substrate, a glass epoxy substrate, a semiconductor chip and a substrate for an organic electroluminescence display device And more particularly to a conductive material which can be suitably used for electrically connecting electrodes of a substrate for an organic electroluminescence display device. The present invention also relates to a connection structure using the conductive material and a manufacturing method of the connection structure.

Paste or film-like conductive materials are widely known. In the conductive material, a plurality of conductive particles are dispersed in a binder resin or the like. In addition, the conductive material including conductive particles may be used for connection between electrodes of organic electroluminescence display elements (hereinafter sometimes referred to as organic EL elements) display elements.

The organic EL display element has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes corresponding to each other. Electrons are injected from one electrode into the organic light-emitting material layer, and holes are injected from the other electrode, whereby electrons and holes combine in the organic light-emitting material layer to emit light. Since the organic EL display device performs self-luminescence, the organic EL display device is advantageous in that visibility is better and thinner than a liquid crystal display device or the like requiring a backlight, and furthermore, driving with a DC low voltage is possible.

As an example of the above-described organic EL display device, an organic EL device in which an electrode of an organic EL substrate having an organic EL element and an electrode of the sealing substrate are adhered to each other by an adhering portion is disclosed in Patent Document 1 . In the embodiment of Patent Document 1, it is described that a thermosetting epoxy adhesive containing anisotropic conductive particles is used to form the adhesive portion.

The conductive material may be formed by, for example, connecting a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), connecting a semiconductor chip and a flexible printed circuit (COF (Chip on Film)), , Connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), and connection between a flexible printed substrate and a glass epoxy board (FOB (Film on Board)).

When the electrode of the semiconductor chip and the electrode of the glass substrate are electrically connected by the conductive material, for example, a conductive material containing conductive particles is disposed on the glass substrate. Then, the semiconductor chips are laminated and heated and pressed. Thereby, the conductive material is cured, and the electrodes are electrically connected through the conductive particles to obtain a connection structure.

As an example of a conductive material that can be used for the above-described connection structure, Patent Document 2 below discloses a resin composition comprising an alicyclic epoxy resin, a diol, a styrenic thermoplastic elastomer having an epoxy group, an ultraviolet active cationic polymerization catalyst, Disclosed is an anisotropic conductive material containing particles.

In addition, Patent Document 3 below discloses a method for producing a cationically polymerizable composition which comprises adding a cationic polymerization catalyst and a cationically polymerizable organic material to a composition containing a guanidine compound, a thiazole compound, a benzothiazole compound, a thiazolecarboxylic acid compound, a sulfenamide compound, A cationic polymerizable organic material composition comprising a urea compound, an ethylenethiol compound, an imidazole compound, a benzimidazole compound or an alkylphenyl sulfide compound as a stabilizer is disclosed. Further, the cationic polymerizable organic material composition does not contain conductive particles.

Japanese Patent Application Laid-Open No. 2009-117214 Japanese Patent Application Laid-Open No. 11-060899 Japanese Patent Laid-Open No. 8-283320

When an electrode of the organic EL substrate and an electrode of the sealing substrate are adhered to each other with a bonding portion by using a thermosetting epoxy adhesive containing anisotropic conductive particles as described in Patent Document 1, The anisotropic conductive particles are compressed. However, during the curing of the adhesive, the anisotropic conductive particles tend to recover to their original shape, and the gap between the electrodes is enlarged due to the repulsive force of the anisotropic conductive particles, thereby causing voids in the adhered portion. Further, after the bonding, the organic EL substrate and the sealing substrate may not be firmly adhered by the bonding portion.

There is a case where the connection target member is not firmly adhered by the cured product of the conductive material even when various kinds of connection structures are obtained by using the conductive material as described in Patent Documents 2 and 3. [ Particularly, in the conductive materials described in Patent Documents 2 and 3, it is difficult to sufficiently increase the adhesiveness when the curing temperature is lowered.

Further, when the conventional anisotropic conductive material containing a cationic polymerization catalyst as described in Patent Document 2 is stored for a long period of time, the curability may change. That is, in a conventional anisotropic conductive material including a cationic polymerization catalyst, storage stability may be low.

In addition, in the conventional anisotropic conductive material including a cationic polymerization catalyst, there is a problem that corrosion of the conductive part of the conductive particles tends to occur. As a result, the reliability of conduction between the electrodes may be lowered.

An object of the present invention is to provide a conductive material which is hard to generate voids in a connection portion formed by a conductive material and can improve connection reliability after connection when the electrodes of the connection target member are electrically connected, And a method of manufacturing the connection structure.

A limiting object of the present invention is to provide a conductive material which is excellent in storage stability and can improve the reliability of the conduction between the electrodes when the electrodes are electrically connected to each other, And a method of manufacturing the connection structure.

According to a broad aspect of the present invention, there is provided a conductive material used by being cured by heating at a temperature of 120 DEG C or lower without heating at a temperature exceeding 120 DEG C, wherein the conductive material comprises a curable component and conductive particles, and, having a conductive layer disposed on the base particle surface, the compression elastic modulus when in the 100 ℃ 20% compressive deformation of the conductive particles 500N / mm ² more than 2000N / mm ² or less, and 100 of the conductive particles Lt; RTI ID = 0.0 > 30 C, < / RTI >

The conductive material according to the present invention is suitably used for electrical connection of electrodes in organic electroluminescence display devices.

The conductive material according to the present invention is suitably used for electrical connection between the electrode of the organic electroluminescence substrate having the organic electroluminescence device and the electrode of the sealing substrate.

In one particular aspect of the conductive material according to the present invention, the conductive material further comprises an inorganic filler.

In one particular aspect of the conductive material according to the present invention, the conductive material further comprises an inorganic filler and organic particles.

In one particular aspect of the conductive material according to the present invention, the curable component comprises a curable compound and a cation generator.

In one particular aspect of the conductive material according to the present invention, the conductive material further comprises an amine compound, the amine compound is a primary amine having an aromatic ring, and the curing component includes a curing compound and a cation generator do.

In one particular aspect of the conductive material according to the present invention, the curable compound comprises an epoxy compound which is liquid at 23 占 폚 and an epoxy compound which is solid at 23 占 폚.

According to a broad aspect of the present invention, there is provided a connector comprising a first connection target member, a second connection target member, and a connection portion electrically connecting the first and second connection target members, Is formed by heating to a temperature of 120 占 폚 or less without heating to a temperature exceeding 120 占 폚.

In one specific aspect of the connection structure according to the present invention, the first connection target member has a first electrode on its surface, the second connection target member has a second electrode on its surface, And the two electrodes are electrically connected by the conductive particles.

In one specific aspect of the connection structure according to the present invention, the first and second connection target members are substrates for an organic light emitting display device.

In one specific aspect of the connection structure according to the present invention, the first connection target member and the second connection target member are an organic electroluminescence substrate and a sealing substrate having organic electroluminescence devices.

According to a broad aspect of the present invention, there is provided a manufacturing method of the above-described connection structure, comprising the steps of: disposing a conductive material layer on the surface of the first connection target member by the conductive material; Placing the second connection target member on the surface opposite to the member side; and curing the conductive material layer by heating to a temperature of 120 DEG C or less without heating at a temperature exceeding 120 DEG C, And a step of forming a connection portion electrically connecting the two connection target members.

In one specific aspect of the method of manufacturing a connection structure according to the present invention, the manufacturing method of the connection structure is a manufacturing method of a connection structure which is an organic electroluminescence display device, And the second connection target member is a second substrate that is a substrate for an organic electroluminescence display element, and the manufacturing method of the connection structure is a step of forming a connection structure on the surface of the first substrate which is the substrate for the organic electroluminescence display element A step of disposing a conductive material layer by the conductive material; a step of disposing a second substrate, which is a substrate for the organic electroluminescence display element, on a surface of the conductive material layer opposite to the first substrate side; Irradiating light to the material layer and heating the conductive material layer to a temperature of 120 DEG C or less to cure and thermally cure the conductive material layer, And a step of forming a connecting portion that is connected to the second substrate electrically.

Conductive material according to the present invention, and contains a curable component and conductive particles, and further compression elastic modulus when in the 100 ℃ 20% compressive deformation of the conductive particles 500N / mm ² more than 2000N / mm ² or less, the conductive particles , The compression recovery rate at 100 캜 is 3% or more and 30% or less. Therefore, the conductive material is heated to a temperature of 120 캜 or less without being heated to a temperature exceeding 120 캜 and cured to form conductive particles It is possible to make it difficult to generate voids in the connection portion formed by the conductive material when the electrodes are electrically connected to each other. In addition, connection reliability after connection can be improved.

1 is a front sectional view schematically showing a connection structure using a conductive material according to an embodiment of the present invention.
2 (a) to 2 (c) are front sectional views for explaining respective steps of obtaining a connection structure using a conductive material according to an embodiment of the present invention.
3 is a cross-sectional view showing an example of conductive particles.

Hereinafter, the present invention will be described in detail.

The conductive material according to the present invention is used after being heated to a temperature of 120 占 폚 or less without being heated at a temperature exceeding 120 占 폚. The conductive material according to the present invention includes a curable component and conductive particles. (In the case of described as below, 20% K value) of the compression elastic modulus when in the 100 ℃ 20% compressive deformation of the conductive particles is, 500N / mm ² is at least 2000N / mm ² or less. The compressive recovery rate of the conductive particles at 100 캜 is 3% or more and 30% or less.

The conductive material according to the present invention has the above-described structure, and the conductive material is cured by heating to a temperature of not higher than 120 캜 without heating at a temperature exceeding 120 캜. By the conductive particles contained in the conductive material It is possible to make it difficult to generate voids in the connection portion formed by the conductive material when the electrodes of the connection target member are electrically connected. Specifically, for example, when the conductive material according to the present invention is used for electrically connecting electrodes of an organic electroluminescence (organic EL) display element, the repulsive force of the compressively deformed conductive particles is not so large, . As a result, the connection resistance between the electrodes becomes low. Also, as the contact area between the electrode and the conductive particle becomes larger, the connection resistance between the electrodes becomes lower. Further, the connection target member can be securely bonded by the connection portion. As a result, conduction reliability and connection reliability in the organic EL display device can be improved.

The 20% K value of the conductive particles and the compression recovery rate of the conductive particles are set at 100 DEG C because the conductive material according to the present invention is cured by heating to a temperature of 120 DEG C or lower and is preferably used at 60 DEG C or higher It is used by being heated and cured at a temperature of 120 ° C or lower, more preferably at a temperature of 100 ° C or lower and cured. When the 20% K value at 100 占 폚 is not less than the lower limit and not more than the upper limit, the conductive particles are suitably compressively deformed at the time of thermal curing of the conductive material between the electrodes to increase the contact area between the electrodes and the conductive particles, The repulsive force by the compressively deformed conductive particles becomes small. When the value of 20% K is lower than or equal to the lower limit and lower than or equal to the upper limit, it contributes greatly to the suppression of void generation and the reduction of the connection resistance between the electrodes. The compressive recovery rate above the lower limit and above the upper limit also contributes greatly to the suppression of void generation and the reduction of the connection resistance between the electrodes. In addition, the compression recovery rate is not less than the lower limit and not more than the upper limit, contributing greatly to firmly adhering the connection target member by the connection portion.

Further, it is preferable that the conductive material according to the present invention further comprises an inorganic filler. Moisture resistance of the cured product is increased by the use of an inorganic filler.

Further, it is more preferable that the conductive material according to the present invention further comprises an inorganic filler and organic particles. In conventional conductive materials, the viscosity of the conductive material during curing becomes too low, and the conductive material sometimes flows excessively. As a result, the conductive material may not be placed in a specific region, and further, adjacent electrodes that should not be connected may be electrically connected through a plurality of conductive particles. On the contrary, when the conductive material includes the curable component, the inorganic filler, the organic particles and the conductive particles, when the conductive material is heated to a temperature of 120 ° C or less and not cured at a temperature exceeding 120 ° C, The conductive material disposed on the object member hardly flows largely, and the connecting portion formed by the conductive material and the conductive particles can be arranged with high accuracy in a specific region. In addition, it is possible to inhibit electrical connection between adjacent electrodes, which should not be connected, through a plurality of conductive particles. As a result, the conduction reliability of the resulting connection structure can be improved. Further, the cured product of the conductive material hardly spreads excessively on the surface of the connection target member, making it more difficult to generate voids in the resulting connection structure.

When the conductive material contains a curable component, an inorganic filler, organic particles and conductive particles, when the conductive material is cured by heating to a temperature of 120 ° C or lower without heating at a temperature exceeding 120 ° C, The contamination by the connecting portion formed by the material can be effectively suppressed. Specifically, for example, when the conductive material is used for electrically connecting the electrodes of the organic electroluminescence (organic EL) display element, since the viscosity of the conductive material during curing of the conductive material is not too low, Can be arranged at a predetermined position. Further, the cured product of the conductive material hardly spreads excessively on the surface of the connection target member, making it more difficult to generate voids in the resulting connection structure. As a result, the conduction reliability of the connection structure in the organic EL display device can be effectively increased, and the operation failure of the organic EL display device can be made less likely to occur.

Further, when the conductive material includes a curable component, an inorganic filler, organic particles, and conductive particles, moisture resistance of the cured product is further increased.

From the viewpoint of further suppressing the generation of voids and further decreasing the connection resistance between the electrodes, the 20% K value at 100 캜 of the conductive particles is preferably 700 N / mm ² or more, more preferably 1000 N / mm ² or higher, preferably 1650N / mm ^2, more preferably at most 1500N / mm ² or less.

The compression modulus (20% K value) can be measured as follows.

The conductive particles are compressed at 100 캜 at a compression rate of 2.6 mN / sec and a maximum test load of 10 gf at the smooth indenter end face of a cylindrical column (diameter 50 탆, made of diamond) using a micro compression tester. At this time, the load value N and the compression displacement (mm) are measured. From the obtained measured values, the above-described compressive modulus can be obtained by the following formula. As the micro-compression tester, for example, "Fisher Scope H-100" manufactured by Fisher Company is used.

K value (N / mm ² ) = (3/2 ^1/2 ) · F · S ^-3/2 · R ^-1/2

F: load value (N) when the conductive particles are compressively deformed by 20%

S: Compressive displacement (mm) when the conductive particles are compressively deformed by 20%

R: radius of conductive particle (mm)

The compressive modulus shows the hardness of the conductive particles in a universal and quantitative manner. By using the compressive elastic modulus, the hardness of the conductive particles can be quantitatively and univocally expressed.

From the viewpoint of further suppressing the occurrence of voids and further increasing the adhesiveness by the connecting portion and further lowering the connection resistance between the electrodes, the compression recovery rate at 100 deg. C of the conductive particles is preferably 5% or more , More preferably not less than 8%, preferably not more than 20%, more preferably not more than 17%.

The compression recovery rate can be measured as follows.

Spread the conductive particles on the sample stand. (Reversed load value) is applied to the spread conductive particles until the conductive particles are 30% compressively deformed at 100 ° C in the center direction of the conductive particles, using a micro compression tester. Thereafter, the load is removed to the original point load value (0.40 mN). And the compression-recovery rate can be obtained from the following equation by measuring the load-compression displacement between them. The load speed is 0.33 mN / sec. As the micro-compression tester, for example, "Fisher Scope H-100" manufactured by Fisher Company is used.

Compression recovery rate (%) = [(L1-L2) / L1] 100

L1: Compressive displacement from the original point load value to the reverse load value when the load is applied

L2: Load removal displacement from the inverse load value to the original point load value when releasing the load

Examples of the method of curing the conductive material according to the present invention include a method of heating the conductive material, a method of heating the conductive material after the light is irradiated to the conductive material, and a method of irradiating the conductive material with light after heating the conductive material . In the case where the speed of photo-curing and the speed of thermal curing are different, light irradiation and heating may be performed at the same time. Among them, a method of heating the conductive material after irradiating the conductive material with light is preferable. The conductive material can be cured in a short time by the combination of photo-curing and thermal curing. In addition, the combination of photo-curing and thermal curing improves the curability even by heating at a low temperature. When curing the conductive material according to the present invention, at least heating is performed. That is, the conductive material according to the present invention is thermally cured.

The conductive material includes a curing agent as the curing component. It is preferable that the conductive material includes a cation generating agent as the curing agent. The curable component preferably includes a curable compound and a cation generator. The inventors of the present invention have found that the use of a cation generating agent can effectively improve conduction reliability as compared with the case where a thermosetting agent other than the cation generating agent (imidazole compound or the like) is used.

Further, it is preferable that the conductive material according to the present invention includes an amine compound, the amine compound is a primary amine having an aromatic ring, and the curing component includes a curing compound and a cation generator. If the conventional conductive material containing the cation generator is stored for a long period of time, the curability may change. That is, in a conventional conductive material containing a cation generating agent, the storage stability may be low. In addition, in the conventional conductive material containing a cation generating agent, there is a problem that corrosion of the conductive part of the conductive particles tends to occur. As a result, the reliability of conduction between the electrodes may be lowered. On the other hand, when the conductive material contains a curable compound, a cation generating agent, an amine compound, and conductive particles, and the amine compound is a primary amine having an aromatic ring, The storage stability of the conductive material can be enhanced, and the reliability of conduction between the electrodes can be effectively increased when the electrodes are electrically connected.

When the conductive material comprises a curing compound, a cation generating agent, an amine compound, and conductive particles, and when the amine compound is a primary amine having an aromatic ring, the cation generating agent and the aromatic ring The storage stability of the conductive material is considerably increased even though the cation generating agent is used. The conductive material according to the present invention hardly changes in curability even when stored for a long period of time. As a result, the adhesiveness of the connection target member bonded by the conductive material is further enhanced. In addition, in the above-described conductive material, although the cation generating agent is used, the reliability of conduction between the electrodes can be improved when the electrodes are electrically connected.

The present inventors have also found that the use of an amine compound having no aromatic ring or the use of an amine compound other than a primary amine makes it possible to use a cation generator The storage stability of the conductive material and the reliability of the conduction between the electrodes can be improved.

The curable compound may be a curable compound (a thermosetting compound, a light and a thermosetting compound) that can be cured by heating, or a curable compound (a photo-curable compound or a light and a thermosetting compound) that can be cured by irradiation of light. The curable compound is preferably a curable compound (a thermosetting compound or a light and a thermosetting compound) that can be cured by heating.

The conductive material is a conductive material that can be cured by heating, and the curable compound may include a curable compound (a thermosetting compound or a light and a thermosetting compound) that can be cured by heating. The curable compound that can be cured by the heating may be a curable compound (a thermosetting compound) that does not cure upon irradiation with light, or a curable compound (a light and a thermosetting compound) that can be cured by irradiation of light and heating.

The conductive material is preferably a conductive material that can be cured by both light irradiation and heating, and further includes a curable compound (photo-curable compound or photo-curable and thermosetting compound) that can be cured by irradiation with light desirable. In this case, after the conductive material is semi-cured (B-staged) by irradiation of light to lower the fluidity of the conductive material, the conductive material can be cured by heating. In semi-curing, the curing of the conductive material is promoted, but the conductive material is not completely cured. The curable compound that can be cured by irradiation of light may be a curable compound (photo-curable compound) that does not cure by heating, or a curable compound (photo-curable and thermosetting compound) that can be cured by both light irradiation and heating.

The cation generating agent usable in the conductive material according to the present invention may be a cation generating agent (a thermal cation generating agent or a light and thermal cation generating agent) which generates a cation by heating, and may generate a cation (A photo cation generator, or a photo- and thermal cation generator). The cation generating agent is preferably a cation generating agent (a thermal cation generating agent or a photo- and thermal cation generating agent) that generates a cation by heating. It is preferable that the conductive material is thermally cured by the action of the cation generating agent. The conductive material may be photo-cured by the action of the cation generating agent and the conductive material may be thermally cured by the action of the cation generating agent.

The conductive material according to the present invention may contain a photocuring initiator. The conductive material according to the present invention preferably contains a photo-radical generator as the photo-curing initiator.

It is preferable that the conductive material includes a thermosetting compound as the curing compound, and further includes a photo-curing compound, or a photo-curing and a thermosetting compound. It is preferable that the conductive material includes a thermosetting compound and a photo-curable compound as the curable compound.

Hereinafter, the details of each component suitably used for the conductive material according to the present invention will be described.

(Curable compound)

The curing compound contained in the conductive material is not particularly limited. As the curable compound, conventionally known curable compounds can be used. The curable compound may be used alone or in combination of two or more.

The curable compound preferably contains a curable compound having an epoxy group. The curable compound having an epoxy group is an epoxy compound. The curing compound having an epoxy group may be used alone or in combination of two or more.

The curable compound having an epoxy group preferably has an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a chrysene ring, a triphenylene ring, a tetrapentane ring, a pyrene ring, a pentacene ring, a piperazine ring and a perylene ring. Among them, the aromatic ring is preferably a benzene ring, a naphthalene ring or an anthracene ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a naphthalene ring. Since the naphthalene ring has a planar structure, it can be cured more quickly.

From the viewpoint of enhancing the curability of the conductive material, the content of the curing compound having the epoxy group in 100% by weight of the total amount of the curable compound is preferably 10% by weight or more, more preferably 20% by weight or more and 100% to be. The total amount of the curable compound may be a curable compound having the epoxy group. When the curable compound having an epoxy group and the curable compound having the epoxy group are used in combination with different curable compounds, the content of the curable compound having an epoxy group in the total 100% by weight of the curable compound is preferably 99% , More preferably not more than 95 wt%, further preferably not more than 90 wt%, particularly preferably not more than 80 wt%.

The curable compound preferably contains an epoxy compound which is in a liquid phase at 23 DEG C and preferably contains an epoxy compound which is solid at 23 DEG C and contains both an epoxy compound which is liquid at 23 DEG C and an epoxy compound which is solid at 23 DEG C .

Examples of the epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol E type epoxy compounds and bisphenol S type epoxy compounds, and hydrides of these epoxy compounds. Among them, from the viewpoint that a cured product of a conductive material is further increased, a glass transition temperature of a cured product is further increased, moisture resistance is further lowered, and furthermore a heat resistance, The epoxy compound which is liquid at 23 占 폚 is preferably a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a hydrogenated bisphenol A type epoxy compound or a hydrogenated bisphenol F type epoxy compound.

The weight average molecular weight of the epoxy compound which is in a liquid phase at 23 占 폚 is preferably 150 or more, more preferably 200 or more, preferably 1,200 or less, more preferably 1,000 or less. When the weight average molecular weight is not lower than the lower limit, the glass transition temperature of the cured product is further increased, and the humidity resistance of the cured product is further increased. When the weight average molecular weight is not more than the upper limit, the coating property and the curability of the conductive material are further improved.

The content of the epoxy compound which is liquid at 23 캜 among the total 100% by weight of the curing compound is preferably 30% by weight or more, more preferably 40% by weight or more, preferably 90% by weight or less, 80% by weight or less. When the content of the liquid epoxy compound is lower than the lower limit described above, the coating property of the conductive material becomes further higher. When the content of the liquid epoxy compound is not more than the upper limit, the coating property of the conductive material becomes further higher, and the humidity resistance of the cured product becomes further higher.

Examples of the epoxy compound which is solid at 23 占 폚 include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol E type epoxy compound, a bisphenol S type epoxy compound, and a hydride of these epoxy compounds. Among them, in view of the fact that the curing property of the conductive material is further increased, the glass transition temperature of the cured product is further increased, the moisture resistance is further lowered and the heat resistance, UV resistance and adhesiveness are excellent, The compound is preferably a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a hydrogenated bisphenol A type epoxy compound or a hydrogenated bisphenol F type epoxy compound.

The weight average molecular weight of the epoxy compound which is solid at 23 占 폚 is preferably 200 or more, more preferably 250 or more, preferably 5000 or less, more preferably 4500 or less. If the weight average molecular weight is at least the lower limit, the moisture resistance and adhesion of the cured product are further enhanced. When the weight average molecular weight is not more than the upper limit, the curability of the conductive material is further improved, the softening point of the conductive material becomes appropriate, and the compatibility of the liquid epoxy compound and the solid epoxy compound becomes further higher.

The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC). Examples of the column used for the measurement of the weight average molecular weight include "Shodex LF-804" manufactured by Showa Denko K.K.

The content of the epoxy compound which is solid at 23 DEG C out of 100% by weight of the total amount of the curable compound is preferably at least 10% by weight, more preferably at least 15% by weight, preferably at most 40% by weight, 35% by weight or less. If the content of the solid epoxy compound is lower than the lower limit described above, moisture resistance of the cured product is further increased. When the content of the solid epoxy compound is not more than the upper limit, the coating property of the conductive material becomes further higher.

In addition, the curable compound preferably contains an alicyclic epoxy compound. The alicyclic epoxy compound is preferably the liquid epoxy compound, preferably the solid epoxy compound, and more preferably both the liquid epoxy compound and the solid epoxy compound. The weight average molecular weight of the alicyclic epoxy compound is preferably 100 or more, more preferably 150 or more, preferably 1000 or less, more preferably 800 or less. The use of the alicyclic epoxy compound or the use of the alicyclic epoxy compound having a weight average molecular weight of not lower than the lower limit and not higher than the upper limit allows the curing property of the conductive material to be further improved. If the weight average molecular weight of the alicyclic epoxy compound is not lower than the lower limit described above, the volatility of the alicyclic epoxy compound is lowered, and gas generation problems are less likely to occur. When the weight average molecular weight of the alicyclic epoxy compound is not more than the upper limit, the viscosity of the conductive material becomes appropriate, and the coating property of the conductive material becomes further higher.

Examples of commercially available products of the alicyclic epoxy resin include Celloxide 2021P, Celloxide 2081P, Celloxide 2000, Celloxide 2083, Celloxide 2085 and Celloxide 3000 (all manufactured by Daicel Chemical Industries, Ltd.). Of these, Celloxide 2021P is preferred because of its low viscosity and excellent curability.

The content of the alicyclic epoxy compound is preferably 5% by weight or more, preferably 30% by weight or less, and more preferably 25% by weight or less, based on 100% by weight of the total amount of the curable compound. When the content of the alicyclic epoxy compound is lower than the lower limit described above, the curing property of the conductive material becomes further higher. When the content of the alicyclic epoxy compound is less than the upper limit, the coating property of the conductive material becomes further higher.

Further, it is preferable that the curable compound includes a phenol novolak type epoxy compound.

The curable compound may further contain another curable compound different from the curable compound having an epoxy group. Examples of the other curable compound include unsaturated double bond-containing curing compounds, phenol curing compounds, amino curing compounds, unsaturated polyester curing compounds, polyurethane curing compounds, silicone curing compounds and polyimide curing compounds. The other curable compounds may be used alone or in combination of two or more.

The curable compound preferably contains a curable compound having an unsaturated double bond from the viewpoint of easily controlling the curing of the conductive material or increasing the reliability of the conduction between the electrodes. From the standpoint of easily controlling the curing of the conductive material or increasing the reliability of the conduction between the electrodes, the curable compound having an unsaturated double bond is preferably a curable compound having a (meth) acryloyl group. By using the curable compound having the (meth) acryloyl group, the curing rate can be controlled within a suitable range in the entire B-staged conductive material (including a portion directly irradiated with light and a portion not irradiated with light directly) The reliability of conduction between the electrodes is further enhanced.

From the viewpoint of easily controlling the curing rate of the B-staged conductive material layer and further improving the conduction reliability between the electrodes, the curable compound having a (meth) acryloyl group is preferably a It is preferable to have two.

Examples of the curable compound having a (meth) acryloyl group include a curable compound having a (meth) acryloyl group and an epoxy group, and a curable compound having an epoxy group and having a (meth) acryloyl group.

Examples of the curing compound having a (meth) acryloyl group include an ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, an epoxy (meth) acrylate obtained by reacting (meth) acrylic acid with an epoxy compound, Urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group is suitably used. The "(meth) acryloyl group" represents an acryloyl group and a methacryloyl group. The term " (meth) acryl " refers to acryl and methacryl. The term "(meth) acrylate" refers to acrylate and methacrylate.

The curable compound preferably includes an epoxy (meth) acrylate. The epoxy (meth) acrylate is a compound obtained by reacting all the epoxy groups in the epoxy compound with (meth) acrylic acid.

Examples of commercial products of the above epoxy (meth) acrylate include EBECRYL 860, Ebecryl 3200, Ebecryl 3201, Ebecryl 3412, Ebecryl 3600, Ebecryl 3700, Ebecryl 3701, Ebecryl 3702, Ebecryl 3703, EA-CHD and EMA-1020 (all manufactured by Nippon Kayaku Co., Ltd.), EA-CRYL 3800, Ebcryl 6040 and Ebcryl RDX 63182 (all manufactured by Daicel Alnex), EA-1010, EA-1020, EA-5323, EA- Epoxy ester 300M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester < SEP > 300A < tb > Epoxy ester < SEP > 200A and epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.) and Denacol acrylate DA-141, Denacol acrylate DA-314 and Denacol acrylate DA-911 ) And the like.

The ester compound obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group is not particularly limited. As the ester compound, a monofunctional ester compound, a bifunctional ester compound, and a trifunctional or more ester compound can be used.

The curable compound having an epoxy group and having a (meth) acryloyl group is preferably a curable compound obtained by converting some epoxy groups of a compound having two or more epoxy groups into a (meth) acryloyl group. This curable compound is a partial (meth) acrylated epoxy compound.

The curable compound preferably contains a reaction product of (meth) acrylic acid with a compound having two or more epoxy groups. This reaction product is obtained by reacting a compound having two or more epoxy groups with (meth) acrylic acid in the presence of a catalyst according to a conventional method. It is preferable that 20% or more of the epoxy groups are converted into (meth) acryloyl groups (conversion ratio). The conversion rate is more preferably 30% or more, preferably 80% or less, more preferably 70% or less. It is most preferable that not less than 40% and not more than 60% of the epoxy groups are converted into (meth) acryloyl groups.

Examples of the aforementioned (meth) acrylated epoxy compound include bisphenol type epoxy moiety (meth) acrylate, cresol novolak type epoxy moiety (meth) acrylate, carboxylic acid anhydride modified epoxy moiety (meth) Type epoxy (meth) acrylate.

As the curable compound, a modified phenoxy resin in which some epoxy groups of a phenoxy resin having two or more epoxy groups are converted into (meth) acryloyl groups may be used. That is, a modified phenoxy resin having an epoxy group and a (meth) acryloyl group may be used.

The curable compound may be a crosslinkable compound or a non-crosslinkable compound.

Specific examples of the crosslinkable compound include, for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (Meth) acrylate, pentaerythritol di (meth) acrylate, glycerin methacrylate acrylate, pentaerythritol di (meth) acrylate, (Meth) acrylate, vinyl (meth) acrylate, divinylbenzene, polyester (meth) acrylate, urethane (meth) acrylate, .

Specific examples of the non-crosslinkable compound include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) (Meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, And the like.

When a thermosetting compound and a photocurable compound are used in combination, the blending ratio of the photocurable compound and the thermosetting compound is appropriately adjusted according to the kind of the photocurable compound and the thermosetting compound. The conductive material preferably contains the photocurable compound and the thermosetting compound in a weight ratio of 1:99 to 90:10, more preferably 5:95 to 60:40, more preferably 10:90 to 40:60 It is more preferable to include them.

(Hardener)

The conductive material includes a curing agent. The curing agent includes a thermosetting agent, and may further include a photocuring initiator. The curing agent comprises a cation generator. Conventionally known cation generators may be used as the cation generators. Further, in the present invention, it is preferable that the cation generating agent is not used as a photo-cation generating agent for only photo-curing the conductive material but is used as a thermal cation generating agent for at least thermally curing the conductive material. Further, in the present invention, it is more preferable to use the cation generating agent as a thermal cation generating agent for thermally curing the conductive material, not as a photo cation generating agent for photo-curing the conductive material. The cation generating agent may be used alone or in combination of two or more.

As the cation generating agent, an iodonium salt and a sulfonium salt are suitably used. SI-60L, SI-80L, SI-100L, SI-110L, SI-150L, and ADEKA manufactured by SANSHIN CHEMICAL INDUSTRIAL CO., LTD. Adeka Optomer SP-150 and SP-170 manufactured by Mitsui Chemicals, Inc.

Preferred examples of the anion portion of the cation generator include PF ₆ , BF ₄ and B (C ₆ F ₅ ) ₄ .

In addition, other specific examples of the cation generating agent include 2-butenyldimethylsulfonium tetrakis (pentafluorophenyl) borate, 2-butenyldimethylsulfonium tetrafluoroborate, 2-butenyldimethylsulfonium hexafluoro (Pentafluorophenyl) borate, 2-butenyltetramethylenesulfonium tetrafluoroborate, 2-butenyltetramethylenesulfonium hexafluorophosphate, 3-methyl-2-butenyltetramethylenesulfonium tetrafluoroborate, 2-butenyldimethylsulfonium tetrafluoroborate, 3-methyl-2-butenyldimethylsulfonium hexafluorophosphate, 3-methyl-2-butenyldimethylsulfonium tetrafluoroborate, 3-butenyldimethylsulfonium tetrakis (pentafluorophenyl) -Butyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, 3-methyl-2-butenyltetramethylenesulfonium tetrafluoroborate, 3-methyl-2-butenyltetramethylenesulfonium Hexaflu (Pentafluorophenyl) borate, 4-hydroxyphenylcinnamomethylsulfonium tetrafluoroborate, 4-hydroxyphenylcinnamethylmethylsulfonium hexafluoroacetate, 4-hydroxyphenylcinnamomethylsulfonium tetrakis (Pentafluorophenyl) borate,? -Naphthylmethyltetramethylenesulfonium tetrafluoroborate,? -Naphthylmethyltetramethylenesulfonium hexafluorophosphate,? -Naphthylmethyltetramethylenesulfonium hexafluorophosphate,? -Naphthylmethyltetramethylenesulfonium tetrafluoroborate, (Pentafluorophenyl) borate, cinnamyldimethylsulfonium tetrafluoroborate, cinnamyldimethylsulfonium hexafluorophosphate, cinnamyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate , Cinnamate tetramethylene sulfonium tetrafluoroborate, cinnamic tetramethylene sulfonium hexafluorophosphate, biphenyl methyl dimethate (Pentafluorophenyl) borate, biphenylmethyldimethylsulfonium tetrafluoroborate, biphenylmethyldimethylsulfonium hexafluorophosphate, biphenylmethyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate , Biphenylmethyltetramethylenesulfonium tetrafluoroborate, biphenylmethyltetramethylenesulfonium hexafluorophosphate, phenylmethyldimethylsulfonium tetrakis (pentafluorophenyl) borate, phenylmethyldimethylsulfonium tetrafluoroborate, Phenylmethyldimethylsulfonium hexafluorophosphate, phenylmethyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, phenylmethyltetramethylenesulfonium tetrafluoroborate, phenylmethyltetramethylenesulfonium hexafluorophosphate, fluororesin N-methylmethyldimethylsulfonium tetrakis (pentafluorophenyl) borane , Fluorenylmethyldimethylsulfonium tetrafluoroborate, fluorenylmethyldimethylsulfonium hexafluorophosphate, fluorenylmethyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, fluorenylmethyltetramethylene sulfone Sulfonium tetrafluoroborate, fluorenylmethyltetramethylenesulfonium hexafluorophosphate, and the like.

It is preferable that the cation generating agent releases inorganic acid ions by heating or releases organic acid ions containing boron atoms by heating. The cation generating agent is preferably a component that releases inorganic acid ions by heating, and is preferably a component that releases organic acid ions containing boron atoms by heating.

Cation generator which emits an inorganic acid ions by heating, SbF ^6-, or PF ⁶ as an anion part ^- is preferably a compound having a. The cation generating agent is preferably a compound having SbF ^{6 -} as an anion moiety and a compound having PF ^{6 -} as an anion moiety.

The anion portion of the cation generator is preferably represented by B (C ₆ X ₅ ) ₄ ^- . The cation generating agent which releases organic acid ions containing a boron atom is preferably a compound having an anion moiety represented by the following formula (1).

In the above formula (1), X represents a halogen atom. X in the above formula (1) is preferably a chlorine atom, a bromine atom or a fluorine atom, more preferably a fluorine atom.

The anion portion of the cation generator is preferably represented by B (C ₆ F ₅ ) ₄ ^- . The cation generating agent which releases the organic acid ion containing the boron atom is more preferably a compound having an anion moiety represented by the following formula (1A).

The cation generator may be an ionic photoacid generator or a nonionic photoacid generator. It is preferable that the cation generating agent is an antimony complex, a salt having a hexafluorophosphate ion, or a salt represented by the following formula (2).

In the formula (2), n represents an integer of 1 to 12, m represents an integer of 1 to 5, and Rf represents a fluoroalkyl group in which all or part of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

The antimony complex is not particularly limited, but is preferably a sulfonium salt. Examples of the sulfonium salt as the antimony complex include tetraphenyl (diphenylsulfide-4,4'-diyl) bissulfonium di (antimony hexafluoride), tetra (4-methoxyphenyl) diphenylsulfide- (4-methoxyphenyl) [4-phenylthiophenyl] sulfonium (4-phenylthiophenyl) sulfonium antimonide, and bis And antimony hexafluoride.

Examples of commercially available antimony complexes include Adeka Optomer SP170 (manufactured by Adeka Co., Ltd.).

Examples of the commercially available salt of the salt having the hexafluorophosphate ion include WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.) and CPI-100P (manufactured by San-apro Co., Ltd.).

The content of the cation generating agent is not particularly limited. The content of the cation generating agent relative to 100 parts by weight of the curable compound is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, still more preferably 5 parts by weight or more, particularly preferably 10 parts by weight or more , Preferably not more than 40 parts by weight, more preferably not more than 30 parts by weight, and most preferably not more than 20 parts by weight. When the content of the cation generating agent with respect to the curable compound is not lower than the lower limit and not higher than the upper limit, the conductive material sufficiently cures.

The content of the cation generating agent is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, still more preferably 5 parts by weight or more, particularly preferably 100 parts by weight or more per 100 parts by weight of the curable compound which can be cured by heating. Is at least 10 parts by weight, preferably at most 40 parts by weight, more preferably at most 30 parts by weight, most preferably at most 20 parts by weight. When the content of the cation generating agent with respect to the curable compound that can be cured by the heating is lower than or equal to the lower limit and below the upper limit, the conductive material sufficiently cures.

From the viewpoint of further enhancing the conduction reliability between the electrodes and the connection reliability under high humidity of the connection structure such as the organic EL display element, it is preferable that the conductive material includes both the cation generating agent and the thermal radical generating agent. The heat radical generator is not particularly limited. As the thermal radical generator, conventionally known thermal radical generators may be used. The thermal radical generator may be used alone or in combination of two or more. Here, the " thermal radical generator " means a compound that generates radical species by heating.

The heat radical generator is not particularly limited, and examples thereof include azo compounds and peroxides. Examples of the peroxide include diacyl peroxide compounds, peroxy ester compounds, hydroperoxide compounds, peroxydicarbonate compounds, peroxyketal compounds, dialkyl peroxide compounds and ketone peroxide compounds.

Other examples of the thermosetting agent include hydrazide compounds, imidazole compounds, acid anhydrides, dicyandiamides, guanidine compounds, modified aliphatic polyamines, adducts of amine compounds and epoxy compounds, and the like.

The hydrazide compound is not particularly limited and includes, for example, 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin].

The imidazole compound is not particularly limited and examples thereof include 1-cyanoethyl-2-phenylimidazole, N- [2- (2-methyl-1-imidazolyl) N, N'-bis (2-methyl-1-imidazolylethyl) urea, N, N'- (2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole Sol and the like.

The acid anhydrides are not particularly limited, and examples thereof include tetrahydrophthalic anhydride and ethylene glycol-bis (anhydrotrimellitate).

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 0.05 parts by weight or more, still more preferably 5 parts by weight or more, based on 100 parts by weight of the curable compound that can be cured by the heating in the curable compound, Particularly preferably not less than 10 parts by weight, preferably not more than 40 parts by weight, more preferably not more than 30 parts by weight, further preferably not more than 20 parts by weight. When the content of the thermosetting agent is lower than or equal to the lower limit and lower than or equal to the upper limit, the conductive material can be sufficiently thermally cured. The content of the thermosetting agent indicates the content of the cation generating agent when the thermosetting agent is only the thermosetting agent and the content of the thermosetting agent includes both of the thermosetting agent and the other thermosetting agent Represents the total content of the cation generating agent and the other thermosetting agent.

In the case where the curing agent includes a thermal radical generator, the content of the thermal radical generator is preferably 0.01 part by weight or more, more preferably 0.01 part by weight or more, Is not less than 0.05 part by weight, preferably not more than 10 parts by weight, more preferably not more than 5 parts by weight. If the content of the thermal radical generator is lower than or equal to the lower limit and below the upper limit, the conductive material can be sufficiently thermally cured.

The conductive material may contain a photo-curing initiator as the curing agent. The photo-curing initiator includes the photo-cation generator (photo-cation generator, or photo- and thermal cation generator) described above. The photocuring initiator is not particularly limited. As the photocuring initiator, conventionally known photocuring initiators may be used. From the viewpoint of further enhancing the conduction reliability between the electrodes and the connection reliability of the connection structure such as the organic EL display element, it is preferable that the conductive material includes a photo-radical generator. The photocuring initiator may be used alone or in combination of two or more.

Examples of the photo-curing initiator other than the cation generating agent include, but are not limited to, acetophenone photo-curing initiator (acetophenone photo-radical generator), benzophenone photo-curing initiator (benzophenone photo-radical generator), thioxanthone, Photo-curing initiator (ketal photo-radical generator), halogenated ketone, acylphosphine oxide and acylphosphonate.

The content of the photocuring initiator is not particularly limited. The content of the photocuring initiator is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, and preferably 2 parts by weight or less with respect to 100 parts by weight of the curable compound that can be cured by irradiation of the light in the curable compound , And more preferably 1 part by weight or less. When the content of the photocuring initiator is not less than the lower limit and not more than the upper limit, the conductive material can be appropriately photo-cured. By irradiating the conductive material with light to form a B-stage, the flow of the conductive material can be suppressed. The content of the photo-curing initiator indicates the content of the cation-generating agent when the photo-curing initiator is only a cation generating agent. When the photo-curing initiator includes both the cation generating agent and the photo-curing initiator, And the other photocurable initiator.

(Inorganic filler)

The conductive material preferably includes an inorganic filler. The inorganic filler has an effect of suppressing a decrease in viscosity during curing of the conductive material and further raising moisture resistance of the cured product. The inorganic filler may be used alone or in combination of two or more.

The average particle diameter of the inorganic filler is preferably 0.1 占 퐉 or more, more preferably 0.2 占 퐉 or more, preferably 2 占 퐉 or less, and more preferably 1.5 占 퐉 or less. The inorganic filler having an average particle diameter of not less than the lower limit and not more than the upper limit further improves moisture resistance of the cured product. When the average particle diameter of the inorganic filler is less than the upper limit, voids are less likely to occur in the cured product. The average particle diameter of the inorganic filler is a volume average particle diameter. The average particle diameter can be measured using a laser diffraction / scattering particle diameter distribution measuring apparatus or the like.

Examples of the inorganic filler include talc, asbestos, silica, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, magnesium oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, barium sulfate, Activated clay, and cericite activated clay. Among them, talc is preferable because blocking property is improved and moisture resistance is improved.

The inorganic filler is preferably in the form of a plate. The average aspect ratio of the inorganic filler is 1 or more, preferably 1.5 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less. If the average aspect ratio of the inorganic filler is less than the upper limit, it becomes difficult for the inorganic filler to be sandwiched between the electrode and the conductive particles, resulting in further lowering of the connection resistance between the electrodes. Further, since the inorganic filler can be favorably oriented even at a low pressure, the thickness of the connection portion formed by the conductive particles becomes even more uniform. The average aspect ratio means an average value of the long diameter of the inorganic filler / the short diameter of the inorganic filler.

The content of the inorganic filler is not particularly limited. The content of the inorganic filler relative to 100 parts by weight of the curable compound is preferably at least 1 part by weight, more preferably at least 2 parts by weight, preferably at most 30 parts by weight, more preferably at most 28 parts by weight. If the content of the inorganic filler is lower than the lower limit, voids are less likely to occur in the cured product. When the content of the inorganic filler is less than the upper limit, the coating property of the conductive material becomes higher.

(Organic particles)

The conductive material preferably includes organic particles. The organic particles act as a gelling agent. The organic particles swell in the conductive material at room temperature, thereby appropriately improving the viscosity of the conductive material. In addition, the organic particles have an action of suppressing a decrease in viscosity during curing of the conductive material. Further, when the organic particles are used in combination with an inorganic filler, voids are less likely to be generated in the cured product even when the substrate is bonded in a reduced-pressure atmosphere. The organic particles may be used alone or in combination of two or more.

More preferably, the organic particles are core shell particles having a core and a shell disposed on a surface of the core. The core is preferably formed by a first (meth) acrylic resin. The (meth) acrylic resin is a general term for a resin containing a (meth) acrylic acid ester as a main component, and the (meth) acrylic resin includes an acrylic rubber. The shell is preferably formed by a second acrylic resin. The glass transition temperature of the first (meth) acrylic resin is preferably 23 ° C or lower. The glass transition temperature of the second (meth) acrylic resin is preferably higher than the glass transition temperature of the first (meth) acrylic resin. The glass transition temperature of the second (meth) acrylic resin is preferably 23 ° C or higher.

More preferably, the organic particles are core shell particles having a core and a shell disposed on a surface of the core. The core is preferably formed by a first (meth) acrylic resin. The shell is preferably formed by a second acrylic resin. The glass transition temperature of the second (meth) acrylic resin is preferably higher than the glass transition temperature of the first (meth) acrylic resin.

Commercially available products of the organic particles include, for example, "Metablen W-5500, W-450A" manufactured by Mitsubishi Rayon Co., and "F-351" core shell acrylate copolymer fine particles manufactured by Gansu Gosei Co.,

The average particle diameter of the organic particles is preferably 0.05 占 퐉 or more, more preferably 0.1 占 퐉 or more, further preferably 0.2 占 퐉 or more, preferably 1 占 퐉 or less, and more preferably 0.9 占 퐉 or less. The average particle diameter of the organic particles is a volume average particle diameter. The average particle diameter can be measured using a laser diffraction / scattering particle diameter distribution measuring apparatus or the like.

The content of the organic particles is not particularly limited. The content of the organic particles relative to 100 parts by weight of the curable compound is preferably at least 1 part by weight, more preferably at least 5 parts by weight, preferably at most 30 parts by weight, more preferably at most 20 parts by weight. If the content of the organic particles is not less than the lower limit, the viscosity of the conductive material becomes moderate, and voids are not effectively generated in the cured product. When the content of the organic particles is less than the upper limit, the coating property of the conductive material becomes further higher.

(Amine compound)

The conductive material preferably includes an amine compound. The amine compound is preferably a primary amine having an aromatic ring. The use of the primary amine having the specific aromatic ring contributes greatly to the improvement of the storage stability of the conductive material containing the cation generating agent. The amine compound may be used alone or in combination of two or more.

Examples of the aromatic ring in the primary amine include an aromatic ring exemplified as an aromatic ring of the curing compound. Among them, a benzene ring is preferable.

Specific examples of the primary amine having an aromatic ring include benzylamine,?,? -Dimethylbenzylamine, aniline, 2-naphthylamine, 1-naphthylmethylamine, 2- And the like.

The content of the cation generator in the conductive material and the content of the primary amine having the aromatic ring is preferably 99.9: 0.1 to 97: 3, more preferably 99.5: 0.5 to 98: 3 in terms of weight ratio (cation generator: primary amine) : 2 is more preferable.

When the content of the primary amine having an aromatic ring is within the preferable range described above, the storage stability of the conductive material and the reliability of the conduction between the electrodes are further stabilized.

(Conductive particles)

The conductive particles may have a conductive portion on a conductive surface. The conductive portion is preferably a conductive layer. 3, the conductive particles 11 may include a base particle 12 and a conductive layer 13 disposed on the surface of the base particle 12, as shown in the sectional view of an example of the conductive particle . The conductive particles may be metal particles whose entirety is the conductive part. Among them, conductive particles having a base particle and a conductive layer disposed on the surface of the base particle are preferable from the viewpoint of reducing the cost, increasing the flexibility of the conductive particle, and enhancing the reliability of conduction between the electrodes.

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 excluding metal particles, and are preferably resin particles, inorganic particles other than metal particles, or organic-inorganic hybrid particles. The base particles may be core shell particles having 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.

The base particles are preferably resin particles formed by a resin. When the electrodes are connected using the conductive particles, the conductive particles are disposed between the electrodes and then pressed to compress the conductive particles. When the base particles are resin particles, the conductive particles are liable to be deformed during the pressing, and the contact area between the conductive particles and the electrode is increased. As a result, the reliability of conduction between the electrodes is further enhanced.

Examples of the resin for forming the resin particles include polyolefin resin, acrylic resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, And examples thereof include polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyetheretherketone, polyether sulfone, divinylbenzene polymer, and divinylbenzene copolymer. 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.

Examples of the inorganic substance for forming the inorganic particles include silica and carbon black. Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.

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.

The metal for forming the conductive part is not particularly limited. When the conductive particles are metal particles whose entirety is a conductive portion, the metal for forming the metal particles is not particularly limited. Examples of the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, And the like. Examples of the metal include indium tin oxide (ITO) and solder. Among them, an alloy including tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable because connection resistance between electrodes becomes further lower.

The conductive layer may be formed by one layer. The conductive layer may be formed of a plurality of layers. That is, the conductive layer may have a laminated structure of two or more layers. When the conductive layer is formed of a plurality of layers, it is preferable that the outermost layer is a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, more preferably a gold layer. When the outermost layer is such a preferable conductive layer, the connection resistance between the electrodes is further lowered. Further, when the outermost layer is a gold layer, the corrosion resistance is further increased.

The method of forming the conductive layer on the surface of the base particles is not particularly limited. Examples of the method of forming the conductive layer include a method of electroless plating, a method of electroplating, a method of physical vapor deposition, and a method of coating a surface of base particles with a paste containing metal powder or metal powder and a binder And the like. Among them, the electroless plating method is preferable because the formation of the conductive layer is simple. Examples of the physical deposition method include vacuum deposition, ion plating and ion sputtering.

The average particle diameter of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 500 μm or less, more preferably 100 μm or less, still more preferably 80 μm or less Or less, particularly preferably 50 mu m or less, and most preferably 20 mu m or less. When the average particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, when the electrodes are connected using the conductive particles, the contact area between the conductive particles and the electrode is sufficiently increased, and when the conductive layer is formed, Particles are hardly formed. Further, the distance between the electrodes connected via the conductive particles is not excessively large, and the conductive layer is less likely to peel off from the surface of the base particles.

The " average particle diameter " of the conductive particles indicates the number average particle diameter. The average particle diameter of the conductive particles is obtained by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.

The thickness of the conductive layer is preferably at least 0.005 탆, more preferably at least 0.01 탆, preferably at most 10 탆, more preferably at most 1 탆, further preferably at most 0.3 탆. When the thickness of the conductive layer is not less than the lower limit and not more than the upper limit, sufficient conductivity is obtained, and the conductive particles are not excessively hardened, and the conductive particles are sufficiently deformed when the electrodes are connected.

In the case where the conductive layer is formed of a plurality of layers, the thickness of the outermost conductive layer is preferably 0.001 mu m or more, more preferably 0.01 mu m or more, particularly when the outermost layer is a gold layer, Or more, preferably 0.5 탆 or less, and more preferably 0.1 탆 or less. When the thickness of the conductive layer in the outermost layer is not less than the lower limit and not more than the upper limit, the coating by the conductive layer in the outermost layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection resistance between the electrodes becomes sufficiently low. In addition, when the outermost layer is a gold layer, the thinner the thickness of the gold layer, the lower the cost.

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

From the viewpoint of increasing the contact area between the electrode and the conductive particles and further enhancing the reliability of the conduction between the electrodes, the conductive particles have the resin particles and the conductive layer (first conductive layer) disposed on the surface of the resin particles .

The surface of the conductive portion of the conductive particles may be insulated by an insulating material such as an insulating layer or insulating particles, a flux, or the like. The insulating material, flux, and the like are preferably removed from the connecting portion by softening and flowing by heat at the time of connection. As a result, a short circuit between the electrodes can be suppressed.

The content of the conductive particles is not particularly limited. The content of the conductive particles in 100 wt% of the conductive material is preferably 0.1 wt% or more, more preferably 0.5 wt% or more, further preferably 1 wt% or more, preferably 40 wt% or less Preferably 30% by weight or less, more preferably 19% by weight or less. When the content of the conductive particles is not less than the lower limit and not more than the upper limit, conductive particles can be easily disposed between the upper and lower electrodes to be connected. Further, it is difficult for the adjacent electrodes, which should not be connected, to be electrically connected through the plurality of conductive particles. That is, it is possible to further prevent a short circuit between adjacent electrodes.

In the conductive material, the ratio of the content of the conductive particles to the content of the inorganic filler is preferably 0.1 or more, more preferably 1 or more, preferably 20 or less, more preferably 10 or less. If the ratio is not less than the lower limit and not more than the upper limit, both the moisture resistance of the cured product and the connection resistance between the electrodes can be balanced better.

(Other components)

The conductive material preferably includes a sensitizer. The sensitizer is preferably a benzophenone derivative represented by the following formula (11). The sensitizer further improves the polymerization initiation efficiency by the cation generating agent and has a role of appropriately promoting the curing reaction of the conductive material.

In the formula (11), R1 and R2 each represent a hydrogen atom, a substituent represented by the following formula (11a), or a substituent represented by the following formula (11b). R1 and R2 may be the same or different.

In the formulas (11a) and (11b), R3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, Ester group. The alkyl group may be linear or branched.

Examples of the benzophenone derivative represented by the above formula (11) include benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone and 4-benzoyl- Methyl diphenylsulfide, and the like.

The content of the sensitizer is not particularly limited. The content of the sensitizer is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 3 parts by weight or less, and still more preferably 1 part by weight or less, based on 100 parts by weight of the curable compound. If the content of the sensitizer is lower than or equal to the above lower limit, a sufficient increase / decrease effect can be obtained. If the content of the sensitizer is not more than the upper limit, light absorption becomes suitable and light tends to be transmitted to the core of the conductive material layer.

The conductive material preferably includes a silane coupling agent. The silane coupling agent improves the adhesiveness of the conductive material with the cured product.

Examples of the silane coupling agent include? -Aminopropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? -Isocyanatepropyltrimethoxysilane.

The content of the silane coupling agent is not particularly limited. The content of the silane coupling agent relative to 100 parts by weight of the curable compound is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less. If the content of the silane coupling agent is not lower than the lower limit, the adhesion improving effect can be effectively obtained. If the content of the silane coupling agent is less than the upper limit, surplus silane coupling agent becomes difficult to bleed out.

The conductive material may contain a hardening retarder. By the use of the curing retarder, the usable time of the conductive material becomes long.

The curing retarder is not particularly limited, and polyether compounds and the like can be mentioned. Examples of the polyether compound include, but are not limited to, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and crown ether compounds. Among them, crown ether compounds are suitable.

The crown ether compound is not particularly limited and includes 12-crown-4, 15-crown-5, 18-crown-6, 24-crown-8 and compounds represented by the following formula (12).

In the formula (12), R 1 to R 12 each represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Provided that at least one of R 1 to R 12 represents an alkyl group having 1 to 20 carbon atoms. The substituted or unsubstituted alkyl group may be substituted with at least one functional group selected from the group consisting of an alkoxyl group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, and a carboxylic acid alkyl ester group having 1 to 20 carbon atoms, Rn and Rn + 1 (wherein n represents an even number from 1 to 12) may form a cyclic alkyl skeleton jointly. The alkoxyl group having 1 to 20 carbon atoms may be linear or branched.

Among the compounds represented by the formula (12), compounds having at least one cyclohexyl group are suitable. By the presence of the cyclohexyl group, the skeleton of the crown ether is stabilized and the delay effect is enhanced.

Specific examples of the compound represented by the formula (12) having a cyclohexyl group include a compound represented by the following formula (12A).

The compound represented by the above formula (12A) has two cyclohexyl groups at positions symmetrical with respect to the line passing through the center of the 18-crown-6-ether molecule. Thus, it is considered that the retardation effect will be enhanced without causing deformation or the like in the skeleton of the 18-crown-6-ether molecule.

The content of the curing retardant is not particularly limited. The content of the curing retarder is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 5 parts by weight or less, and still more preferably 3 parts by weight or less, based on 100 parts by weight of the curable compound. When the content of the curing retarder is lower than the lower limit, a sufficient delay effect can be obtained. When the content of the curing retarder is less than the upper limit, outgas is less likely to be generated when the conductive material is cured.

The conductive material may contain a compound or an ion exchanger that reacts with an acid generated in the cured product to improve the durability of the device electrode or the like.

Examples of the compound reacting with the generated acid include a substance capable of neutralizing with acid, for example, a carbonate or hydrogencarbonate of an alkali metal or an alkaline earth metal. Specific examples of the compound which reacts with the generated acid include calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like.

As the ion exchanger, both cation exchange type, anion exchange type and both ion exchange type can be used. In particular, a cation exchange type or a both ion exchange type capable of adsorbing chloride ions is suitable.

The conductive material may include a solvent. By using the solvent, the viscosity of the conductive material can be easily adjusted. Examples of the solvent include ethyl acetate, methyl cellosolve, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran and diethyl ether.

The conductive material may contain various known additives such as a reinforcing agent, a softening agent, a plasticizer, an ultraviolet absorber and an antioxidant, if necessary.

(Other details of the conductive material)

The method for producing the conductive material is not particularly limited. For example, using a mixer such as homodisperse, homomixer, universal mixer, planetarium mixer, kneader, triaxial roll or the like, Therefore, a method of mixing other components can be mentioned.

The conductive material is preferably an anisotropic conductive material. The conductive material is preferably a conductive material used for electrical connection of the electrode. The conductive material is preferably a paste or film-like conductive material, preferably a paste-like conductive material. The paste-like conductive material is a conductive paste. The conductive material on the film is a conductive film. When the conductive material is a conductive film, a film not containing conductive particles may be laminated on the conductive film containing the conductive particles.

From the viewpoint of suppressing thermal deterioration of the member to be connected, the conductive material according to the present invention is heated to a temperature of 120 DEG C or less without being heated to a temperature exceeding 120 DEG C, It is preferable that the material is heated and heated to a temperature of 100 占 폚 or less without being heated. In the substrate for an organic electroluminescence device, when the substrate is heated to a temperature exceeding 120 캜, thermal deterioration may be a serious problem.

From the viewpoint of further increasing the storage stability of the conductive material and further enhancing the conduction reliability between the electrodes, the pH of the conductive material at 25 DEG C is preferably 4 or more, more preferably 5 or more, 6 or more, preferably 10 or less, more preferably 9 or less, further preferably 8 or less.

The conductive material according to the present invention is preferably a conductive paste which is applied on a member to be connected in a paste state.

The viscosity of the conductive paste at 25 캜 is preferably 20 Pa · s or more, more preferably 100 Pa · s or more, preferably 700 Pa · s or less and more preferably 300 Pa · s or less. When the viscosity is lower than the lower limit, sedimentation of the conductive particles in the conductive paste can be suppressed. If the viscosity is lower than the upper limit, the dispersibility of the conductive particles is further increased. When the viscosity of the conductive paste before application is within the above range, the flow of the conductive paste before curing can be further suppressed after the conductive paste is applied on the first connection object member, and voids are further hardly generated Loses. The paste state also includes a liquid phase.

Further, the conductive material according to the present invention is suitably used for electrical connection of electrodes in an organic EL display device. The conductive material according to the present invention is more suitably used for electrical connection between the electrodes of the substrate for an organic EL display device. Examples of the substrate for the organic EL display element include an organic EL substrate having an organic EL element and a sealing substrate. The sealing substrate is a substrate for sealing the organic EL element. The conductive material according to the present invention is more suitably used for electrical connection between the electrode of the organic EL substrate having the organic EL element and the electrode of the sealing substrate.

The conductive material according to the present invention can be used for bonding various members to be connected. The conductive material is suitably used to obtain a connection structure in which the first and second connection target members are electrically connected. The conductive material is more suitably used for obtaining a connection structure in which the electrodes of the first and second connection target members are electrically connected.

Fig. 1 is a front sectional view schematically showing an example of a connection structure using a conductive material according to an embodiment of the present invention.

The connection structure 1 shown in Fig. 1 is an example in which the first connection target member 2, the second connection target member 4 and the first and second connection target members 2 and 4 are electrically connected (3). The connection portion 3 is a cured layer and is formed by curing a conductive material containing the conductive particles 11. [

The first connection target member 2 has a plurality of first electrodes 2a on its surface (upper surface). The second connection target member 4 has a plurality of second electrodes 4a on its surface (lower surface). The first electrode 2a and the second electrode 4a are electrically connected to each other by one or more conductive particles 11. [ Therefore, the first and second connection target members 2 and 4 are electrically connected by the conductive particles 11. [

The connection between the first and second electrodes 2a and 4a is usually performed by connecting the first connection target member 2 and the second connection target member 4 to each other via the conductive material between the first and second electrodes 2a and 4a And then pressing them when curing the conductive material. By pressurization, the conductive particles 11 are generally compressed.

The first and second members to be connected are not particularly limited. Specific examples of the first and second connection target members include electronic parts such as a semiconductor chip, a capacitor and a diode, and electronic parts such as a circuit board such as a printed board, a flexible printed board, a glass epoxy board and a glass board have. The conductive material is preferably a conductive material used for connection of electronic parts.

The method of manufacturing a connection structure according to the present invention includes the steps of disposing a conductive material layer on the surface of the first connection target member with the conductive material; And a step of thermally curing the conductive material layer to form a connecting portion electrically connecting the first and second connection target members to each other. In this case, the connecting portion is formed by heating the conductive material layer to a temperature of 120 占 폚 or less without heating to a temperature exceeding 120 占 폚, and curing the conductive material layer. It is more preferable that the conductive material layer is thermally cured by heating to a temperature of 100 占 폚 or less without heating to a temperature exceeding 100 占 폚.

The connection structure 1 shown in Fig. 1 can be obtained as follows, for example, through the state shown in Figs. 2 (a) to 2 (c).

As shown in Fig. 2A, a first connection target member 2 having a first electrode 2a on its surface (upper surface) is prepared. Next, a conductive material including a plurality of conductive particles 11 is disposed on the surface of the first connection target member 2, and a conductive material layer 3A is formed on the surface of the first connection target member 2. Next, At this time, it is preferable that one or more conductive particles 11 are disposed on the first electrode 2a.

Then, light is applied to the conductive material layer 3A to advance the curing of the conductive material layer 3A. 2 (a) to 2 (c), the conductive material layer 3A is irradiated with light to advance the curing of the conductive material layer 3A to make the conductive material layer 3A a B-stage. That is, as shown in Fig. 2 (b), the B-staged conductive material layer 3B is formed on the surface of the first connection target member 2. By the B stage, the first connection target member 2 and the B-staged conductive material layer 3B are bonded. The B-staged conductive material layer 3B is a semi-hardened semi-hardened material. The B-staged conductive material layer 3B is not completely cured, and thermal curing can proceed further. However, the conductive material layer 3A may be cured at once by irradiating the conductive material layer 3A with light or by heating the conductive material layer 3A without forming the conductive material layer 3A into the B stage. It is preferable to heat the conductive material layer 3A to thermally cure the conductive material layer 3A.

To effectively cure the conductive material layer 3A, it is preferable that the light irradiation intensity at the time of light irradiation is in the range of 0.1 to 8000 mW / cm < ² >. The accumulated light quantity is preferably 0.1 to 20,000 J / cm < ² >. The light source used when irradiating light is not particularly limited. As the light source, for example, a light source having a sufficient light emission distribution at a wavelength of 420 nm or less can be given. Specific examples of the light source include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, chemical lamps, black light lamps, microwave excited mercury lamps, metal halide lamps and LED lamps.

Then, as shown in Fig. 2 (c), a second connection target member 4 is provided on the surface of the B-staged conductive material layer 3B opposite to the first connection target member 2 side Laminated. The second connection target member 4 is laminated such that the first electrode 2a on the surface of the first connection target member 2 and the second electrode 4a on the surface of the second connection target member 4 face each other.

The B-staged conductive material layer 3B is further heated by heating the B-staged conductive material layer 3B at the time of laminating the second connection target member 4 to further form the connection portion 3 . However, the B-staged conductive material layer 3B may be heated before the second connection target member 4 is laminated. In addition, the B-staged conductive material layer 3B may be heated after the second connection target member 4 is laminated.

The heating temperature when the conductive material layer 3A or the B-staged conductive material layer 3B is cured by heating is preferably 50 DEG C or higher, more preferably 80 DEG C or higher, still more preferably 100 DEG C or higher Deg. C to 120 deg. C, and more preferably 110 deg. C or less. When the conductive material according to the present invention is used for electrical connection of electrodes in the organic EL display element, the heating temperature for curing the conductive material layer 3A or the B-staged conductive material layer 3B is More preferably 120 deg. C or less and 100 deg. C or less.

It is preferable to pressurize the B-staged conductive material layer 3B. The contact area between the first and second electrodes 2a and 4a and the conductive particles 11 can be increased by compressing the conductive particles 11 with the first electrode 2a and the second electrode 4a by pressurization have. As a result, conduction reliability can be enhanced. Further, by compressing the conductive particles 11, even if the distance between the first and second electrodes 2a and 4a is increased, the particle diameter of the conductive particles 11 becomes larger so as to follow this width.

The first connection target member 2 and the second connection target member 4 are connected via the connection portion 3 by curing the B-staged conductive material layer 3B. In addition, the first electrode 2a and the second electrode 4a are electrically connected through the conductive particles 11. In this way, the connection structure 1 shown in Fig. 1 using a conductive material can be obtained. Here, since the photocuring and the heat curing are used in combination, the conductive material can be cured in a short time.

The conductive material according to the present invention can be used for 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)), or connection of a flexible printed board and a glass epoxy board (FOB (Film on Board)). In particular, the conductive material is suitable for FOG or COG applications and is more suitable for COG applications. The conductive material according to the present invention is preferably a conductive material used for connection between a flexible printed circuit board and a glass substrate or for connection between a semiconductor chip and a glass substrate and is preferably a conductive material used for connection between a flexible printed circuit board and a glass substrate Is more preferable.

In the connection structure according to the present invention, it is preferable that the second connection target member and the first connection target member are a flexible printed substrate and a glass substrate, or a semiconductor chip and a glass substrate, and the flexible printed substrate and the glass substrate desirable.

It is also preferable that the connection structure according to the present invention is an organic EL display device. The electrodes in the organic EL display device may be electrically connected by the conductive particles included in the conductive material.

Preferably, the first and second connection target members are each a substrate for an organic EL display device. It is preferable that the first and second connection target members are first and second substrates which are substrates for organic EL display elements. It is preferable that the first connection target member and the second connection target member are an organic EL substrate and a sealing substrate having organic EL elements. In this case, the first connection target member may be the organic EL substrate, the second connection target member may be the sealing substrate, the first connection target member may be the sealing substrate, and the second connection target member Or may be the organic EL substrate described above. The connection structure is preferably an organic EL display element.

The electrode width (the first electrode width and the second electrode width) is preferably 5 占 퐉 or more, more preferably 10 占 퐉 or more, preferably 500 占 퐉 or less, and more preferably 300 占 퐉 or less. The inter-electrode width (first inter-electrode width and second inter-electrode width) is preferably not less than 3 탆, more preferably not less than 10 탆, preferably not more than 500 탆, more preferably not more than 300 탆. Further, the electrode width / L / S (line / space) as the width between electrodes is preferably 5 μm / 5 μm or more, more preferably 10 μm / 10 μm or more, preferably 500 μm / Preferably 300 占 퐉 / 300 占 퐉 or less.

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

(Example 1)

(1) Production of conductive material:

, 40 parts by weight of a bisphenol A modified epoxy resin ("EPICLON EXA-4850-150" manufactured by DIC Corporation), 40 parts by weight of a bisphenol F epoxy resin (EXA-835LV manufactured by DIC Corporation) and 40 parts by weight of a phenol novolac resin 3 parts by weight of a cation generator SI-60L (Sun Aid manufactured by Sanshin Chemical Industry Co., Ltd.) and 20 parts by weight of a silica (average particle diameter 0.5 mu m, 10 parts by weight of a conductive particle A (HPS-0500, aspect ratio 1.2) and 4 parts by weight of a conductive particle A having an average particle diameter of 30 탆 (20% K value at 100 캜: 1400 N / mm ² , compression recovery at 100 캜: And the mixture was stirred at 2000 rpm for 5 minutes using a planetary stirrer to obtain a conductive paste.

The electroconductive particles A and the electroconductive particles B, C, D, E, F, G, I, L, W, X, Y and Z described below all have a nickel plating layer formed on the surface of the divinylbenzene resin particles And a conductive layer in which a gold plating layer is formed on the surface of the nickel plating layer. The conductive particles H used are conductive particles having a nickel plating layer formed on the surface of resin particles and a conductive layer having a palladium plating layer formed on the surface of the nickel plating layer. The conductive particle J is a conductive particle having only a nickel plated layer formed on the surface of the resin particle. The conductive particles K are conductive particles having a nickel plating layer formed on the surface of resin particles, a palladium plating layer formed on the surface of the nickel plating layer, and protrusions rising on the outer surface of the conductive layer. The 20% K value and the compression recovery rate were adjusted by changing the composition of the divinylbenzene resin particles and the thickness of the conductive layer.

(2) Production of organic EL display device:

An organic EL substrate (first substrate, first connection target member) having an organic EL device, an Mo / Al / Mo electrode pattern with L / S of 500 m / 500 m and a length of 20 mm formed on the upper surface was prepared . Further, a sealing substrate (second substrate, second connecting member) provided with a Mo / Al / Mo electrode pattern having an L / S of 500 mu m / 500 mu m and a length of 20 mm was prepared.

On the first substrate, a conductive paste immediately after fabrication was applied using a dispenser so as to have a width of 2 mm and a thickness of 50 m to form a conductive paste layer. Subsequently, the second substrate was laminated on the conductive paste layer so that the electrodes were opposed to each other. This laminate was cured by applying a pressure of 0.3 MPa at 100 DEG C for 30 minutes using a bonding apparatus to obtain an organic EL display device.

(Example 2)

An organic EL display device was obtained in the same manner as in Example 1 except that the heating temperature of the conductive paste layer was changed from 100 占 폚 to 120 占 폚.

(Example 3)

The same procedure as in Example 1 was carried out except that the conductive particles A were changed to conductive particles B having an average particle diameter of 30 μm (20% K value at 100 ° C: 520 N / mm ² , compression recovery rate at 100 ° C: 10% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 4)

The same procedure as in Example 1 was carried out except that the conductive particles A were changed to conductive particles C having an average particle diameter of 30 μm (20% K value at 100 ° C: 1980 N / mm ² , compression recovery rate at 100 ° C: 18% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 5)

The same procedure as in Example 1 was carried out except that the conductive particles A were changed to conductive particles D having an average particle diameter of 30 탆 (20% K value at 100 캜: 1100 N / mm ² , compression recovery rate at 100 캜: 3% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 6)

The same procedure as in Example 1 was carried out except that Conductive Particle A was changed to Conductive Particle E having an average particle diameter of 30 μm (20% K value at 100 ° C: 1700 N / mm ² , compression recovery rate at 100 ° C: 30% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 7)

A conductive paste was obtained in the same manner as in Example 1, except that the inorganic filler was changed to talc having an average particle diameter of 0.8 占 퐉 ("D-800" manufactured by Nippon Talc Co., Ltd., average aspect ratio 2). Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 8)

A conductive paste was obtained in the same manner as in Example 1 except that bisphenol F epoxy resin ("EXA-835LV" manufactured by DIC Corporation) was changed to bisphenol E ("EPOX-MK R1710" manufactured by Purintech Co., Ltd.). Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 9)

A conductive paste was obtained in the same manner as in Example 1, except that SI-60L (Sun Aid manufactured by Sanshin Chemical Co., Ltd.) was changed to CXC-1612 (K-PURE CXC manufactured by K-PURE) as a cation generator. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 10)

A conductive paste was obtained in the same manner as in Example 1, except that SI-60L as a cation generator was not blended and 15 parts by weight of a heat curing agent (imidazole compound, "2P-4MZ" manufactured by Shikoku Chemicals Corporation) was blended. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 11)

A conductive paste was obtained in the same manner as in Example 1 except that no inorganic filler was added. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 12)

A conductive paste was obtained in the same manner as in Example 1, except that SI-60L (Sun Aid manufactured by Sanshin Chemical Co., Ltd.) was changed to CPI-210S (manufactured by San-Apro Co.), which is a cation generator.

First and second substrates similar to those of Example 1 were prepared. The conductive paste was applied on the first substrate using a dispenser to form a conductive paste layer. Then, ultraviolet rays of 365 nm were irradiated for 3 seconds so that the light irradiation intensity became 3000 mW / cm < ^{2 &} The layer was semi-cured and B-staged. Subsequently, the second substrate was laminated on the conductive paste layer so that the electrodes were opposed to each other. This laminate was cured by applying a pressure of 0.3 MPa at 100 DEG C for 30 minutes using a bonding apparatus to obtain an organic EL display device.

(Example 13)

The same procedure as in Example 1 was carried out except that the conductive particles A were changed to conductive particles F having an average particle diameter of 30 탆 (20% K value at 100 캜: 580 N / mm ² , compression recovery rate at 100 캜: 5% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 14)

The same procedure as in Example 1 was carried out except that the conductive particles A were changed to conductive particles G having an average particle diameter of 30 탆 (20% K value at 100 캜: 1680 N / mm ² , compression recovery rate at 100 캜: 25% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 15)

The same procedure as in Example 1 was carried out except that Conductive Particle A was changed to Conductive Particle H having an average particle diameter of 30 μm (20% K value at 100 ° C: 1520 N / mm ² , compression recovery rate at 100 ° C: 15% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 16)

The same procedure as in Example 1 was carried out except that the conductive particles A were changed to conductive particles J having an average particle diameter of 30 탆 (20% K value at 100 캜: 1480 N / mm ² , compression recovery rate at 100 캜: 15% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 17)

The same procedure as in Example 1 was carried out except that the conductive particles A were changed to conductive particles K having an average particle diameter of 30 탆 (20% K value at 100 캜: 1580 N / mm ² , compression recovery rate at 100 캜: 15% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 18)

The same procedure as in Example 1 was carried out except that the conductive particles A were changed to conductive particles L having an average particle diameter of 20 μm (20% K value at 100 ° C: 1380 N / mm ² , compression recovery rate at 100 ° C: 13% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Example 19)

(1) Production of a conductive film:

, 20 parts by weight of a naphthalene type epoxy resin ("HP4032D" manufactured by DIC), 20 parts by weight of a liquid epoxy resin ("EP-828" manufactured by Mitsubishi Chemical Corporation), 20 parts by weight of a phenoxy resin ("PKHH" , 1 part by weight of a silane coupling agent ("SH6040" manufactured by Toray Dow Corning Silicone Co., Ltd.) as a curing agent, 30 parts by weight of an imidazole curing agent (Nova Cure 3941HP manufactured by Asahi Kasei- (HPS-0500 manufactured by Toagosei Co., Ltd., aspect ratio: 1.2) and 4 parts by weight of conductive particles A having an average particle diameter of 30 mu m were added, and toluene was added so as to have a solid content of 50% by weight to obtain a resin composition.

The obtained resin composition was applied to a PET film having a thickness of 50 占 퐉 which had been subjected to a release treatment on one side and dried with hot air at 80 占 폚 for 5 minutes to prepare a conductive film. The thickness of the obtained conductive film was 50 占 퐉. The obtained conductive film was cut into a size of 2 mm in width.

(2) Production of organic EL display device:

A process for forming a conductive paste layer by coating a conductive paste with a dispenser on the first substrate was changed to a process for forming a conductive film layer by adhering a conductive film. An EL display device was obtained.

(Comparative Example 1)

The same procedure as in Example 1 was carried out except that the conductive particles A were changed to conductive particles W having an average particle diameter of 30 μm (20% K value at 100 ° C: 350 N / mm ² , compression recovery rate at 100 ° C: 5% An organic EL display device was obtained.

(Comparative Example 2)

The same procedure as in Example 1 was carried out except that the conductive particles A were changed to conductive particles X having an average particle diameter of 30 μm (20% K value at 100 ° C: 3670 N / mm ² , compression recovery rate at 100 ° C: 95% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Comparative Example 3)

The same procedure as in Example 1 was carried out except that the conductive particles A were changed to conductive particles Y having an average particle diameter of 30 탆 (20% K value at 100 캜: 600 N / mm ² , compression recovery rate at 100 캜: 1.5% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Comparative Example 4)

The same procedure as in Example 1 was carried out except that Conductive Particle A was changed to Conductive Particle Z having an average particle diameter of 30 μm (20% K value at 100 ° C: 1800 N / mm ² , compression recovery rate at 100 ° C: 40% Thereby obtaining a conductive paste. Using the obtained conductive paste, an organic EL display device was obtained in the same manner as in Example 1.

(Evaluation of Examples 1 to 19 and Comparative Examples 1 to 4)

(1) The compressive modulus at 20 deg. C (20% K value)

The compressive modulus (20% K value) of the conductive particles used at 100 캜 was measured using a micro compression tester ("Fisher Scope H-100" manufactured by Fisher Company).

(2) Compression recovery rate of conductive particles at 100 캜

The compressive recovery rate when the used conductive particles were compressed by 30% at 100 ° C was measured using a micro compression tester ("Fisher Scope H-100" manufactured by Fisher Company).

(3) presence or absence of void

In the obtained organic EL display device, it was observed whether or not voids were generated in the connection portion where the conductive material layer was cured. The presence or absence of voids was judged by the following criteria.

[Criteria for determining presence or absence of voids]

○: No void

Δ: There is void but no void larger than electrode width and inter-electrode width

X: voids larger than electrode width or inter-electrode width

(4) Moisture resistance

The obtained conductive paste was applied on a constant temperature plate with a Baker type applicator (manufactured by TESTER Co., Ltd.) so as to have a thickness of 100 mu m. Then, Examples 1 to 11, 13 to 18 and Comparative Examples 1 to 4, then in the exemplary heated at 100 ℃ 30 minutes, and Example 12 is the light intensity of ultraviolet light of 365nm irradiated three seconds so that 3000mW / cm ^2, And heated at 100 DEG C for 30 minutes to obtain a film. In Example 19, two conductive films were laminated so as to have a total thickness of 100 mu m, placed on a constant temperature plate, and heated at 100 DEG C for 30 minutes to obtain a film. The moisture permeability of the obtained film was measured according to JIS Z0208 at a temperature of 60 DEG C and 90% RH for 24 hours.

The above-mentioned moisture permeability is generally measured by a moisture permeable cup as in JIS Z0208, but it is also possible to use PERMATRAN W3 / 33 manufactured by Micon Co., USA.

From the measured values of the moisture permeability, the moisture resistance was judged by the following criteria.

[Criteria for evaluating moisture resistance]

○○: The moisture permeability is 25g / m ² or less

○: The water vapor transmission rate 25g / m ² greater than 50g / m ² or less

△: water vapor transmission rate is 50g / m ² greater than 100g / m ² or less

×: The moisture permeability exceeds 100 g / m ²

(5) Connection resistance (conduction reliability)

The connection resistance between the upper and lower electrodes of the obtained organic EL display element was measured by the four-terminal method. The average value of 100 connection resistances 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 connection resistance between the electrodes in the obtained organic EL display device was determined based on the following criteria.

[Criteria for judging connection resistance]

○○: Less than 3Ω

○: 3Ω or more and less than 4Ω

?: 4? Or more and less than 5?

△△: 5 Ω or more and less than 10 Ω

×: 10Ω or more

(6) Connection reliability

After the obtained organic EL display device was left under the conditions of 85 캜 and 85% RH for 500 hours, the connection resistance between the upper and lower electrodes was measured by the 4-terminal method. The average value of 100 connection resistances was calculated. From the connection resistance between the electrodes in the organic EL display device after being left under the high temperature and high humidity conditions, the connection reliability was judged by the following criteria.

[Criteria for judging connection reliability]

○○: Less than 3Ω

○: less than 5Ω

△: 5 Ω or more and less than 10 Ω

×: 10Ω or more

The results are shown in Table 1 below.

(Example 20)

(1) Production of conductive material:

, 40 parts by weight of a bisphenol A modified epoxy resin ("Epiclon EXA-4850-150" manufactured by DIC Corporation) and 30 parts by weight of a bisphenol F epoxy resin ("EXA-835LV" Ltd.), 20 parts by weight of an epoxy acrylate ("Ebecryl 3702" manufactured by Daicel Alynes Co., Ltd.) as a photo-curable compound, 20 parts by weight of an acylphosphine oxide-based compound , 10 parts by weight of silica having an average particle diameter of 0.25 mu m as a filler and 10 parts by weight of conductive particles A having an average particle diameter of 30 mu m (the conductive particles used in Example 1, " DAROCUR TPO " 4% by weight at 20% K value at 100 DEG C: 1400 N / mm < ² >, compression recovery at 100 DEG C: 15%) was added and stirred at 2000 rpm for 5 minutes using a planetary stirrer to obtain a conductive paste.

(2) Production of organic EL display device:

An organic EL substrate (first substrate, first connection target member) having an organic EL device, an Mo / Al / Mo electrode pattern with L / S of 500 m / 500 m and a length of 20 mm formed on the upper surface was prepared . Further, a sealing substrate (second substrate, second connecting member) provided with a Mo / Al / Mo electrode pattern having an L / S of 500 mu m / 500 mu m and a length of 20 mm was prepared.

On the first substrate, a conductive paste immediately after fabrication was applied using a dispenser so as to have a width of 2 mm and a thickness of 50 m to form a conductive paste layer. Subsequently, the second substrate was laminated on the conductive paste layer so that the electrodes were opposed to each other. Ultraviolet rays of 365 nm were irradiated for 3 seconds so that the light irradiation intensity became 3000 mW / cm ² , and the conductive paste layer was semi-cured by photopolymerization to make B stage. The stacked body was subjected to a pressure of 0.3 MPa using a bonding apparatus to cure the conductive paste layer at 100 占 폚 for 30 minutes to obtain an organic EL display element.

(Example 21)

An organic EL display device was obtained in the same manner as in Example 20 except that the heating temperature of the conductive paste layer was changed from 100 캜 to 120 캜.

(Example 22)

An organic EL display device was obtained in the same manner as in Example 20 except that the second substrate was irradiated with light before lamination and the second substrate was laminated rapidly after the irradiation of light.

(Example 23)

Except that the kind of the thermosetting compound was changed from a bisphenol A modified epoxy resin ("Epiclon EXA-4850-150" manufactured by DIC Corporation) to a phenol novolak type epoxy resin ("Epiclon N-770" A conductive paste was obtained in the same manner as in Example 20. An organic EL display device was obtained in the same manner as in Example 20, using the obtained conductive paste.

(Example 24)

The same procedure as in Example 20 was repeated except that the kind of the cation generator was changed from CXC-1612 (K-pure CXC manufactured by K-pure) to SI-60L (Sun Aid produced by Sanzuka Chemical Co., Ltd.) A paste was obtained. An organic EL display device was obtained in the same manner as in Example 20, using the obtained conductive paste.

(Example 25)

A conductive paste was obtained in the same manner as in Example 20 except that SI-60L as a cation generator was not added and 15 parts by weight of a heat curing agent (imidazole compound, "2P-4MZ" manufactured by Shikoku Chemicals Corporation) was added. An organic EL display device was obtained in the same manner as in Example 20, using the obtained conductive paste.

(Example 26)

The procedure of Example 20 was repeated except that the conductive particles A were changed to conductive particles I having an average particle diameter of 60 탆 (20% K value at 100 캜: 1,400 N / mm ² , compression recovery rate at 100 캜: 15% Thereby obtaining a conductive paste. The electrode of the first substrate was changed to a Mo / Al / Mo electrode pattern having an L / S of 500 m / 500 m and a length of 20 mm, and an electrode of the sealing substrate (second substrate) Except that the conductive paste immediately after the preparation was coated on the first substrate by a dispenser so as to have a width of 1.5 mm and a thickness of 120 占 퐉 in the same manner as in Example 20 To obtain an organic EL display element.

(Evaluation of Examples 20 to 26)

In Examples 20 to 26, the evaluation items (1) to (6) of Examples 1 to 19 and Comparative Examples 1 to 4 were evaluated in the same manner as in Examples 1 to 19 and Comparative Examples 1 to 4.

(4) In the evaluation of the moisture resistance, the obtained conductive paste was applied on a constant temperature plate with a Baker type applicator (manufactured by Testers Co., Ltd.) so as to have a thickness of 100 탆. Thereafter, ultraviolet ray of 365 nm was irradiated for 3 seconds so that the light irradiation intensity became 3000 mW / cm ² , and then heated at 100 캜 for 30 minutes to obtain a film. The moisture permeability of the obtained film was measured according to JIS Z0208 at a temperature of 60 DEG C and 90% RH for 24 hours.

The results are shown in Table 2 below.

(Example 27)

(1) Production of conductive material:

, 40 parts by weight of a bisphenol A modified epoxy resin ("Epiclon EXA-4850-150" manufactured by DIC Corporation) and 30 parts by weight of a bisphenol F epoxy resin ("EXA-835LV" Ltd.), 20 parts by weight of an epoxy acrylate ("Ebecryl 3702" manufactured by Daicel Alynes Co., Ltd.) as a photo-curable compound, 20 parts by weight of an acylphosphine oxide-based compound , 10 parts by weight of silica having an average particle diameter of 0.25 mu m as a filler, 0.05 part by weight of benzylamine, and 1 part by weight of conductive particles A having an average particle diameter of 30 mu m (in Example 1, 20% K value of the conductive particles, 100 ℃ used: 1400N / mm ^2, compression at 100 ℃ recovery rate: 15%) 4 parts by weight adding portion, by by stirring for 5 minutes at 2000rpm using a planetary stirrer to obtain a conductive paste, .

(2) Production of organic EL display device:

An organic EL substrate (first substrate, first connection target member) having an organic EL device, an Mo / Al / Mo electrode pattern with L / S of 500 m / 500 m and a length of 20 mm formed on the upper surface was prepared . Further, a sealing substrate (second substrate, second connecting member) provided with a Mo / Al / Mo electrode pattern having an L / S of 500 mu m / 500 mu m and a length of 20 mm was prepared.

On the first substrate, a conductive paste immediately after fabrication was applied using a dispenser so as to have a width of 2 mm and a thickness of 50 m to form a conductive paste layer. Subsequently, the second substrate was laminated on the conductive paste layer so that the electrodes were opposed to each other. Ultraviolet rays of 365 nm were irradiated for 3 seconds so that the light irradiation intensity became 3000 mW / cm ² , and the conductive paste layer was semi-cured by photopolymerization to make B stage. Using this laminate and applying a pressure of 0.3 MPa using a bonding apparatus, the conductive paste layer was cured at 100 占 폚 for 30 minutes to obtain an organic EL display element (connection structure X).

The conductive paste was allowed to stand in a shading plastic container at 30 DEG C for 72 hours. An organic EL display element (connection structure Y) was obtained in the same manner as the connection structure X except that the conductive paste after being left at 30 캜 for 72 hours was used instead of the conductive paste immediately after the preparation.

(Example 28)

A conductive paste was obtained in the same manner as in Example 27 except that the amount of benzylamine was changed from 0.05 part by weight to 0.09 part by weight. Using the obtained conductive paste, connection structures X and Y were obtained in the same manner as in Example 27. [

(Example 29)

A conductive paste was obtained in the same manner as in Example 27 except that the addition amount of benzylamine was changed from 0.05 parts by weight to 0.003 parts by weight. Using the obtained conductive paste, connection structures X and Y were obtained in the same manner as in Example 27. [

(Example 30)

A conductive paste was obtained in the same manner as in Example 27 except that the kind of the amine compound was changed from benzylamine to?,? - dimethylbenzylamine. Using the obtained conductive paste, connection structures X and Y were obtained in the same manner as in Example 27. [

(Example 31)

A conductive paste was prepared in the same manner as in Example 27 except that the kind of the thermosetting compound was changed from bisphenol E ("EPOX-MK R1710" manufactured by Purintech) to bisphenol F epoxy resin ("EXA-835LV" . Using the obtained conductive paste, connection structures X and Y were obtained in the same manner as in Example 27. [

(Example 32)

Except that the kind of the cation generator was changed from SI-60L (Sun Aid manufactured by San-Shin Kagaku Co., Ltd.) to CXC-1612 (K-PURE CXC manufactured by K-PURE Co., Ltd.) . Using the obtained conductive paste, connection structures X and Y were obtained in the same manner as in Example 27. [

(Example 33)

A conductive paste was obtained in the same manner as in Example 27 except that benzylamine was not added. Using the obtained conductive paste, connection structures X and Y were obtained in the same manner as in Example 27. [

(Example 34)

A conductive paste was obtained in the same manner as in Example 27 except that the kind of the amine compound was changed from benzylamine to N-methylbenzylamine (secondary amine having an aromatic ring). Using the obtained conductive paste, connection structures X and Y were obtained in the same manner as in Example 27. [

(Example 35)

A conductive paste was obtained in the same manner as in Example 27 except that the kind of the amine compound was changed from the benzylamine to n-hexylamine (primary amine having an aliphatic skeleton). Using the obtained conductive paste, connection structures X and Y were obtained in the same manner as in Example 27. [

(Example 36)

A conductive paste was obtained in the same manner as in Example 27 except that SI-60L as a cation generator was not added and 15 parts by weight of a thermosetting agent (imidazole compound, "2P-4MZ" manufactured by Shikoku Chemicals Corporation) was added. Using the obtained conductive paste, connection structures X and Y were obtained in the same manner as in Example 27. [

(Example 37)

Except that 15 parts by weight of a thermosetting agent (imidazole compound, " 2P-4MZ " manufactured by Shikoku Chemicals Corporation) was added without adding SI-60L as a cation generator and that no benzylamine was added. , A conductive paste was obtained. Using the obtained conductive paste, connection structures X and Y were obtained in the same manner as in Example 27. [

(Evaluation of Examples 27 to 37)

In Examples 27 to 37, evaluation items (1) to (6) of Examples 1 to 19 and Comparative Examples 1 to 4 were evaluated in the same manner as in Examples 1 to 19 and Comparative Examples 1 to 4. In Examples 27 to 37, the following evaluation items (7) to (9) were also evaluated.

(4) In the evaluation of the moisture resistance, the obtained conductive paste was applied on a constant temperature plate with a Baker type applicator (manufactured by Testers Co., Ltd.) so as to have a thickness of 100 탆. Thereafter, ultraviolet ray of 365 nm was irradiated for 3 seconds so that the light irradiation intensity became 3000 mW / cm ² , and then heated at 100 캜 for 30 minutes to obtain a film. The moisture permeability of the obtained film was measured according to JIS Z0208 at a temperature of 60 DEG C and 90% RH for 24 hours.

(7) pH of conductive material

The pH of the conductive paste immediately after preparation was measured at 25 캜. The pH was determined according to the following criteria.

[Criteria for judging pH]

A: pH is 6 or more and 8 or less

B: pH is 4 or more and less than 6 or 8 or more and 10 or less

C: pH less than 4 or more than 10

(8) Storage stability (curability)

The conductive paste immediately after preparation was prepared, and the conductive paste was allowed to stand in a shading plastic container at 30 DEG C for 72 hours. The conductive paste immediately before production (before being allowed to stand) and the conductive paste after being left standing were cured in an oven at 100 DEG C for 1 hour to obtain a cured product (diameter 10 mm, thickness 1 mm).

The curability of the conductive paste was determined on the basis of the following criteria based on the hardness (D1) of the cured product of the conductive paste immediately after the preparation (before being left) and the hardness (D2) of the cured product of the conductive paste after being left with the Shore durometer (D type).

[Criteria for storage stability (curability)] [

?: The ratio of hardness D2 to hardness D1 of 0.9 or more

DELTA: ratio of hardness D2 to hardness D1 of 0.8 or more and less than 0.9

?: The ratio of the hardness D2 to the hardness D1 is 0.6 or more and less than 0.8

X: ratio of hardness D2 to hardness D1 of less than 0.6

(9) Storage stability (viscosity)

The conductive paste immediately after the preparation was prepared, and the conductive paste was allowed to stand at 30 DEG C for 72 hours. The storage stability of the conductive paste was judged by the following criteria based on the viscosity (eta 1) of the conductive paste immediately after the preparation (before being left) and the viscosity (eta 2) of the conductive paste after being left. The viscosities? 1 and? 2 were measured at 2.5 rpm and 25 ° C using an E-type viscosity measuring apparatus ("VISCOMETER TV-22" manufactured by TOKI SANGYO CO. Value.

[Criteria for storage stability (viscosity)] [

?: The ratio of the viscosity? 2 to the viscosity? 1 is less than 1.2

?: The ratio of the viscosity? 2 to the viscosity? 1 was 1.2 or more and less than 1.4

?: The ratio of the viscosity? 2 to the viscosity? 1 is 1.4 or more and less than 1.6

DELTA: The ratio of the viscosity? 2 to the viscosity? 1 is 1.6 or more and less than 2.0

X: a ratio of the viscosity? 2 to the viscosity? 1 of not less than 2.0

The results are shown in Table 3 below.

(Example 38)

(1) Production of conductive material:

50 parts by weight of a multifunctional epoxy resin ("1032H60" manufactured by Mitsubishi Chemical Corporation) solid at 23 ° C and 50 parts by weight of a bisphenol F epoxy resin ("EXA-835LV" 3 parts by weight of SI-60L (Sun Aid manufactured by Sanshin Chemical Co., Ltd.), 10 parts by weight of core-shell acrylic rubber particles ("Metablen W-5500" manufactured by Mitsubishi Rayon Co., Ltd., average particle diameter: 0.4 μm) an inorganic filler of silica (average particle diameter 0.25㎛) 10 parts by weight, 20% K value of the conductive particles, 100 ℃ used in the embodiment mean particle diameter of the conductive particles a 30㎛ (example ^{1: 1400N / mm 2, 100} ℃ , 15%), and the mixture was stirred at 2000 rpm for 5 minutes using a planetary stirrer to obtain a conductive paste.

(2) Production of organic EL display device:

An organic EL substrate (first substrate, first connection target member) having an organic EL device, an Mo / Al / Mo electrode pattern with L / S of 250 m / 250 m and a length of 20 mm formed on the upper surface was prepared . Further, a sealing substrate (second substrate, second connecting member) provided with a Mo / Al / Mo electrode pattern having an L / S of 250 mu m / 250 mu m and a length of 20 mm was prepared.

On the first substrate, a conductive paste immediately after fabrication was applied using a dispenser so as to have a width of 2 mm and a thickness of 50 m to form a conductive paste layer. Subsequently, the second substrate was laminated on the conductive paste layer so that the electrodes were opposed to each other. This laminate was cured by applying a pressure of 0.2 MPa at 100 캜 for 30 minutes using a bonding apparatus to obtain an organic EL display device.

(Example 39)

An organic EL display device was obtained in the same manner as in Example 38 except that the heating temperature of the conductive paste layer was changed from 100 占 폚 to 120 占 폚.

(Example 40)

A conductive paste was obtained in the same manner as in Example 38, except that the organic particles were changed to core-shell structure fine particles (" F351 ", manufactured by Gansu Chemical Industry Co., Ltd., average particle diameter 0.3 탆). An organic EL display device was obtained in the same manner as in Example 38, using the obtained conductive paste.

(Example 41)

A conductive paste was obtained in the same manner as in Example 38 except that the inorganic filler was changed to talc ("D-800" manufactured by Nippon Talc Co., Ltd., average particle diameter 0.8 μm). An organic EL display device was obtained in the same manner as in Example 38, using the obtained conductive paste.

(Example 42)

Except that 50 parts by weight of a bisphenol F epoxy resin ("EXA-835LV" manufactured by DIC Corporation) was replaced by 50 parts by weight of a bisphenol E epoxy resin ("EPOX-MK R1710" , A conductive paste was obtained. An organic EL display device was obtained in the same manner as in Example 38, using the obtained conductive paste.

(Example 43)

The same procedure as in Example 38 was repeated except that the kind of the cation generator was changed from SI-60L (Sun Aid manufactured by Sanshin Chemical Co., Ltd.) to CXC-1612 (K-pure CXC manufactured by K- A paste was obtained. An organic EL display device was obtained in the same manner as in Example 38, using the obtained conductive paste.

(Example 44)

A conductive paste was obtained in the same manner as in Example 38 except that SI-60L as a cation generator was not added and 15 parts by weight of a heat curing agent (imidazole compound, "2P-4MZ" manufactured by Shikoku Chemicals Corporation) was added. An organic EL display device was obtained in the same manner as in Example 38, using the obtained conductive paste.

(Example 45)

A conductive paste was obtained in the same manner as in Example 38 except that the organic particles and the inorganic filler were not mixed. An organic EL display device was obtained in the same manner as in Example 38, using the obtained conductive paste.

(Example 46)

A conductive paste was obtained in the same manner as in Example 38 except that no organic particles were added. An organic EL display device was obtained in the same manner as in Example 38, using the obtained conductive paste.

(Example 47)

A conductive paste was obtained in the same manner as in Example 38 except that no inorganic filler was added. An organic EL display device was obtained in the same manner as in Example 38, using the obtained conductive paste.

(Evaluation of Examples 38 to 47)

In Examples 38 to 47, evaluation items (1) to (6) of Examples 1 to 19 and Comparative Examples 1 to 4 were evaluated in the same manner as in Examples 1 to 19 and Comparative Examples 1 to 4. In Examples 38 to 47, the following evaluation items (10) were also evaluated.

(4) In the evaluation of the moisture resistance, the obtained conductive paste was applied on a constant temperature plate with a Baker type applicator (manufactured by Testers Co., Ltd.) so as to have a thickness of 100 탆. Thereafter, the film was heated at 100 DEG C for 30 minutes to obtain a film. The moisture permeability of the obtained film was measured according to JIS Z0208 at a temperature of 60 DEG C and 90% RH for 24 hours.

(10) The lowest melt viscosity during curing of the conductive material

The minimum melt viscosity during curing of the conductive material was measured using a rotary rheometer (manufactured by STRESSTECH, REOLOGICA) at a gap of 500 μm, a frequency of 1 Hz, a deformation amount of 1 rad, a temperature raising rate of 10 ° C./minute and a measurement temperature range of 30 ° C. to 120 ° C. Was evaluated as the lowest melt viscosity. The viscosity of the conductive material during curing was determined based on the following criteria.

[Minimum melt viscosity during curing of conductive material]

?: Minimum melt viscosity of 2 Pa · s or more and 10 Pa · s or less

DELTA: minimum melt viscosity of not less than 0.4 Pa · s and not more than 2 Pa · s, or not less than 10 Pa · s and not more than 50 Pa · s

X: minimum melt viscosity of less than 0.4 Pa · s, or greater than 50 Pa · s

The results are shown in Table 4 below.

1: connection structure 2: first connection object member
2a: first electrode 3: connection
3A: conductive material layer 3B: B-staged conductive material layer
4: second connection target member 4a: second electrode
11: conductive particles 12: base particles
13: conductive layer

Claims (14)

Is a conductive material used by being cured by heating to a temperature of 120 占 폚 or less without heating to a temperature exceeding 120 占 폚,
A curable component, and conductive particles,
Wherein the conductive particles have a base particle and a conductive layer disposed on a surface of the base particle,
And a compression modulus when in 100 ℃ 20% compressive deformation of the conductive particles 500N / mm ² more than 2000N / mm ² or less,
Wherein the compression recovery rate of the conductive particles at 100 占 폚 is 3% or more and 30% or less. The conductive material according to claim 1, used for electrical connection of an electrode in an organic electroluminescence display device. 3. The conductive material according to claim 1 or 2, used for electrical connection between an electrode of an organic electroluminescence substrate having an organic electroluminescence device and an electrode of a sealing substrate. 4. The conductive material according to any one of claims 1 to 3, further comprising an inorganic filler. The conductive material according to any one of claims 1 to 3, further comprising an inorganic filler and organic particles. 6. The conductive material according to any one of claims 1 to 5, wherein the curable component comprises a curable compound and a cation generator. 6. The method according to any one of claims 1 to 5, further comprising an amine compound,
Wherein the amine compound is a primary amine having an aromatic ring,
Wherein the curable component comprises a curable compound and a cation generator. The conductive material according to any one of claims 1 to 7, wherein the curable compound comprises an epoxy compound which is liquid at 23 占 폚 and an epoxy compound which is solid at 23 占 폚. And a connection section for electrically connecting the first connection target member, the second connection target member, and the first and second connection target members,
Wherein the connecting portion is formed by heating the conductive material according to any one of claims 1 to 8 to a temperature of not higher than 120 캜 and not more than 120 캜 and curing the conductive material. The apparatus according to claim 9, wherein the first connection object member has a first electrode on a surface thereof,
The second connection target member has a second electrode on its surface,
Wherein the first electrode and the second electrode are electrically connected by the conductive particles. The connection structure according to claim 9 or 10, wherein the first and second connection target members are substrates for an organic light emitting display device. 12. The connection structure according to any one of claims 9 to 11, wherein the first connection target member and the second connection target member are an organic electroluminescence substrate and a sealing substrate, each of which comprises an organic electroluminescence device. 11. A method of manufacturing a connection structure according to any one of claims 9 to 11,
Disposing a conductive material layer on the surface of the first connection target member by the conductive material;
Disposing the second connection target member on a surface of the conductive material layer opposite to the first connection target member side;
Forming a connection portion electrically connecting the first and second connection target members by heating the conductive material layer to a temperature of 120 DEG C or less without heating to a temperature exceeding 120 DEG C, A method of manufacturing a connection structure. The manufacturing method of a connection structure according to claim 13, wherein the connection structure is an organic electroluminescence display device,
Wherein the first connection target member is a first substrate which is a substrate for an organic light emitting display device,
And the second connection target member is a second substrate which is a substrate for an organic light emitting display device,
A step of disposing a conductive material layer on the surface of the first substrate which is the substrate for the organic electroluminescence display element by the conductive material,
Disposing a second substrate as the substrate for the organic electroluminescence display device on a surface of the conductive material layer opposite to the first substrate side;
The conductive material layer is irradiated with light and the conductive material layer is heated to a temperature of 120 DEG C or less to cure and thermally cure the conductive material layer to electrically connect the first and second substrates And forming a connection portion.

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