JP2003168323A - Anisotropic conductive paste and its using method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide anisotropic conductive paste with high storage stability, high dispenser coating workability, no generation of lost resin, bubbles, and exudation in thermo compression bonding, high bonding reliability and high connection reliability even in high temperature and high humidity, and high repairing capability, and to provide a using method of the anisotropic conductive paste. <P>SOLUTION: This anisotropic conductive paste contains (I) 30-80 percentage by mass of epoxy resin; (II) 10-50 percentage by mass of a phenol base curing agent; (III) 5-25 percentage by mass of high softening point fine particles; and (IV) 0.1-25 percentage by mass of conductive particles. This anisotropic conductive paste is used to connect an electric circuit wiring formed on one board to an electric circuit wiring formed on the other board. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flat panel display such as a liquid crystal display, an electroluminescence display and a plasma display, and a charge coupled device (CCD).
And CMOS (Complementary Metal Oxide Semicondu)
The present invention relates to an anisotropic conductive paste used for joining fine wiring of an electric circuit used for a semiconductor device such as a ctor) and a method of using the anisotropic conductive paste used for connecting electric circuit wiring.

[0002]

2. Description of the Related Art In recent years, liquid crystal displays used in television receivers, personal computers, mobile phones, etc. have been made finer and smaller, and accordingly, the wiring of integrated circuits of drivers has a narrow pitch. It has become. Also, in order to maintain high productivity, the temperature is 200 ℃,
TCP (TapeCarr) mounted with an integrated circuit under severe thermocompression bonding conditions such as pressure of 2 MPa and time of 10 to 30 seconds.
ier Package) and the liquid crystal display board wiring.

Conventionally, in order to connect such a wiring, an anisotropic method in which fine conductive particles as described in JP-A-3-46707 are dispersed in a resin to give anisotropy. Conductive film is used. However, since this anisotropic conductive film is manufactured by forming it into a film using a release film, the manufacturing cost is high and expensive, and it is necessary to install a dedicated automatic peeling machine at the time of use. There was a problem in terms of cost. Further, this anisotropic conductive film also has a problem that sufficient adhesive strength cannot be obtained and the connection reliability is lowered under high temperature and high humidity.

Materials for solving these problems are disclosed in Japanese Patent Laid-Open Nos. 62-40183 and 62-76215.
An anisotropic conductive paste or an anisotropic conductive adhesive which is liquid at room temperature as disclosed in JP-A No. 62-176139 and JP-A No. 62-176139. However, these anisotropic conductive pastes or anisotropic conductive adhesives
In the thermocompression bonding process that involves a rapid temperature rise, the viscosity drops sharply. Therefore, there has been a problem that resin leakage due to the generation of liquid flow during thermocompression bonding or bleeding contamination occurs. In the anisotropic conductive paste or anisotropic conductive adhesive, the conductive particles are partially aggregated,
There is also a problem that conduction failure occurs in the crimping direction. Further, there is a problem that after the anisotropic conductive paste or the like is hardened, the connection reliability at the time of high temperature and high humidity cannot be maintained due to the bubbles remaining in the hardened material. Further, the cured product had sufficient strength, but had a problem that it did not have repairability.

Therefore, in particular, no bubbles remain in the cured product even under severe thermocompression bonding conditions such as a temperature of 200 ° C., a pressure of 2 MPa, and a time of 10 seconds to 30 seconds, and high adhesion reliability, connection reliability and repairability can be obtained. The material possessed was desired.

[0006]

The object of the present invention is excellent in storage stability and workability of dispenser application, and there is no resin dropout, bubble and exudation during thermocompression bonding, and the cured product thereof has high temperature and high humidity. An object of the present invention is to provide an anisotropic conductive paste having high adhesion reliability and connection reliability and repairability, and a method of using the same.

[0007]

The anisotropic conductive paste of the present invention comprises (I) an epoxy resin of 30 to 80% by mass, (II)
Phenolic curing agent 10 to 50% by mass, (III) high softening point fine particles 5 to 25% by mass, (IV) conductive particles 0.1 to 2
It is characterized by containing 5% by mass.

Further, the anisotropic conductive paste of the present invention is
(I) Epoxy resin 30 to 79.9 mass%, (II) Phenolic curing agent 10 to 50 mass%, (III) High softening point fine particles 5 to 25 mass%, (IV) Conductive particles 0.1 to 25 %, And (V) antifoaming agent 0.1 to 20% by mass.

Further, the anisotropic conductive paste of the present invention is
(I) Epoxy resin 30 to 79.8 mass%, (II) Phenolic curing agent 10 to 50 mass%, (III) High softening point fine particles 5 to 25 mass%, (IV) Conductive particles 0.1 to 25 %, And (VI) coupling agent 0.1 to 5% by mass.

Furthermore, the anisotropic conductive paste of the present invention is (I) epoxy resin 30 to 79.8 mass%, (II)
Phenolic curing agent 10 to 50% by mass, (III) high softening point fine particles 5 to 25% by mass, (IV) conductive particles 0.1 to 2
5% by mass, (V) antifoaming agent 0.1 to 20% by mass, and (VI) coupling agent 0.1 to 5% by mass.

Furthermore, the anisotropic conductive paste of the present invention further comprises a curing catalyst (VI
It is characterized by including I). The epoxy resin (I) has at least an average of 1 to 1 epoxy groups in one molecule.
It is preferable to have 6 and have a polystyrene-converted average molecular weight by GPC of 100 to 7,000.

The phenolic curing agent (II) is preferably a phenol novolac type curing agent. It is preferable that the high softening point fine particles (III) have a softening point temperature of 60 to 150 ° C. and a primary particle diameter of 0.01 to 2 μm, and further, methyl (meth) acrylate and High softening point fine particles obtained by copolymerizing a copolymerizable monomer other than methyl (meth) acrylate, and preferably containing 30 to 70% by mass of the methyl (meth) acrylate.

It is preferable that the surface component of the conductive particles (IV) is composed of gold or nickel. The defoaming agent (V) is preferably polysilicone, and the polysilicone is a silicone-modified elastomer and has a softening point temperature of -80 to 0.
It is also preferable that the temperature is at 0 ° C., and the particles are present in the anisotropic conductive paste as particles, and the primary particle diameter thereof is 0.05 to 5 μm. Furthermore, the silicone-modified elastomer is an epoxy resin. Desirably, the silicone-containing group is a grafted elastomer.

The viscosity of this anisotropic conductive paste at 25 ° C. is preferably 30 to 400 Pa · s. In the method of using the anisotropic conductive paste of the present invention, the anisotropic conductive paste connects the electrical wiring formed on one substrate and the electrical circuit wiring formed on the other substrate. It is characterized by that.

According to the present invention, since the anisotropic conductive paste which can obtain high adhesion reliability and connection reliability even at high temperature and high humidity is used, the wirings can be surely connected to each other. Furthermore, the method of using the anisotropic conductive paste of the present invention is characterized in that it is used in any one of a circuit material, a liquid crystal display, an organic electroluminescence display, a plasma display, a charge coupled device, and a semiconductor device.

According to the present invention, the storage stability and dispenser coating workability are excellent, there is no resin dropout, bubbles and exudation during thermocompression bonding, and the cured product thereof has reliable adhesion even at high temperature and high humidity. Also, an anisotropic conductive paste having high connection reliability and repairability can be obtained. In addition, by using such an anisotropic conductive paste, a short circuit of wiring does not occur, and the insulation between adjacent wirings is maintained.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The anisotropic conductive paste according to the present invention is the resin composition described below. In the present invention, the resin composition 1, the resin composition 2, the resin composition 3, and the resin composition 4 described below are collectively referred to as an anisotropic conductive paste (resin composition).

The first anisotropic conductive paste of the present invention is
(I) Epoxy resin 30 to 80% by mass, (II) Phenolic curing agent 10 to 50% by mass, (III) High softening point fine particles 5 to 25% by mass, (IV) Conductive particles 0.1 to 25% by mass.
(Hereinafter, resin composition 1). The second anisotropic conductive paste of the present invention is (I) epoxy resin 30.
~ 79.9% by mass, (II) phenolic curing agent 10-5
0 mass%, (III) high softening point fine particles 5 to 25 mass%, (I
V) 0.1 to 25% by mass of conductive particles, (V) antifoaming agent 0.
1 to 20 mass% is contained (hereinafter, resin composition 2).

Further, the third anisotropic conductive paste of the present invention is (I) epoxy resin 30 to 79.8 mass%, (I)
I) Phenolic curing agent 10 to 50% by mass, (III) High softening point fine particles 5 to 25% by mass, (IV) Conductive particles 0.1 to
25% by mass and 0.1 to 5% by mass of (VI) coupling agent (hereinafter referred to as resin composition 3). Furthermore, the fourth anisotropic conductive paste of the present invention is (I) epoxy resin 30 to 79.8 mass%, (II) phenolic curing agent 10
To 50% by mass, (III) high softening point fine particles 5 to 25% by mass, (IV) conductive particles 0.1 to 25% by mass, (V) defoaming agent 0.1 to 20% by mass, (VI) cup Ring agent 0.1
5% by mass (hereinafter, resin composition 4).

In the present invention, the above resin compositions 1 to 4 are used.
A curing catalyst (VII) can be further added to. Anisotropic conductive paste according to the present invention, by having the above-mentioned configuration, excellent storage stability, dispenser coating workability, anisotropy without resin loss during thermocompression bonding, bubbles and exudation A conductive paste can be obtained, and a cured product thereof has high adhesion reliability and connection reliability even at high temperature and high humidity, and has repairability. The anisotropic conductive paste of the present invention has the following properties (I) to (VII), which have the property of having conductivity in the direction of being hardened by applying pressure and having insulation in the other direction. Will be described in detail.

<Epoxy Resin (I)> The epoxy resin (I) is the anisotropic conductive paste (resin composition) of the present invention.
At 100 mass%, 30 to 80 mass%, preferably 40 to 70 mass%, more preferably 45 to 65 mass%.
It is desirable to use the amount of. When the resin composition contains a defoaming agent (V) described later, the epoxy resin (I) is 30 to 79.9% by mass, preferably 40 to 6% by mass.
9.9% by mass, more preferably 50 to 64.9% by mass
It is desirable to use the amount of. The epoxy resin (I)
When the composition contains the coupling agent (VI), or the defoaming agent (V) and the coupling agent (VI), the epoxy resin (I) is 30 to 79.8% by mass, Preferably 40 to 69.8% by mass, more preferably 50 to 6
It is desirable to use it in an amount of 4.8% by weight.

When the amount of the epoxy resin (I) used is 30% by mass or more in the resin composition (100% by mass), the adhesive reliability and the connection reliability in the cured product of the anisotropic conductive paste of the present invention. Can be secured, and when it is 80% by mass or less, the repairability can be secured in the cured product of the anisotropic conductive paste of the present invention. Here, the repairability, if a problem occurs after bonding the electrodes and the like with an anisotropic conductive paste, the adhesion site may be peeled off, washed, and the electrodes may be bonded again. In this case, the cured product does not remain on the base material such as the glass substrate, and it means the ability to use the base material.

As the epoxy resin (I) used in the present invention, known epoxy resins can be used, but it is preferable that 1 to 6 epoxy groups are contained in one molecule of the epoxy resin (I), preferably the average. It is desirable to use those having 1.2 to 6, and more preferably 1.7 to 6 on average. If the epoxy resin (I) has an average of 1 to 6 epoxy groups in one molecule, it is possible to obtain the adhesive reliability and connection reliability of the anisotropic conductive paste of the present invention at high temperature and high humidity.

The epoxy resin (I) has a molecular weight of gel permeation chromatography (hereinafter referred to as GPC).
The polystyrene-converted average molecular weight is 100 to
It is desirable that it is in the range of 7,000, preferably 150 to 3,000, and more preferably 350 to 2,000. GP
When the polystyrene-reduced average molecular weight by C is in the above range, the anisotropic conductive paste of the present invention is excellent in dispenser coating workability, which is preferable. In the present invention, the epoxy resin (I) may be any combination of the range of the epoxy group contained in one molecule and the range of the polystyrene-converted average molecular weight.

The epoxy resin (I) may be liquid or solid at room temperature. For example, monofunctional epoxy resin (I-1) and polyfunctional epoxy resin (I-
2) can be mentioned, and one selected from these may be used alone or in combination of two or more. As the monofunctional epoxy resin (I-1), an aliphatic monoglycidyl ether compound, an aromatic monoglycidyl ether compound, an aliphatic monoglycidyl ester compound, an aromatic monoglycidyl ester compound, an alicyclic monoglycidyl ester compound, Examples thereof include nitrogen element-containing monoglycidyl ether compounds, monoglycidylpropyl polysiloxane compounds, monoglycidyl alkanes, and the like.

Examples of the aliphatic monoglycidyl ether compounds include those obtained by the reaction of polyalkylene monoalkyl ethers with epichlorohydrin, those obtained by the reaction of aliphatic alcohols with epichlorohydrin, and the like. Examples of the polyalkylene monoalkyl ethers include ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether having an alkyl group or an alkenyl group having 1 to 6 carbon atoms,
Examples thereof include polyethylene glycol monoalkyl ether, pyropyrene glycol monoalkyl ether, dipyropyrene glycol monoalkyl ether, tripyropyrene glycol monoalkyl ether, and polypyropyrene glycol monoalkyl ether. Examples of the fatty acid alcohols include n-butanol, isobutanol, n-octanol, 2-ethylhexyl alcohol, dimethylolpropane monoalkyl ether, methylolpropane dialkyl ether, glycerin dialkyl ether, dimethylolpropane monoalkyl ester, methylolpropane dialkyl ester. , Glycerin dialkyl ester and the like.

Examples of the aromatic monoglycidyl ether compounds include aromatic alcohols or alcohols obtained by modifying them with alkylene glycols such as ethylene glycol and propylene glycol and epichlorohydrin obtained by the reaction of epichlorohydrin. . Examples of the aromatic alcohols include phenol, benzyl alcohol, xylenol, and naphthol.

As the above-mentioned aliphatic monoglycidyl ester compound, a compound obtained by reacting an aliphatic dicarboxylic acid monoalkyl ester with epichlorohydrin,
Examples of the aromatic monoglycidyl ester compound include those obtained by the reaction of aromatic dicarboxylic acid monoalkyl ester and epichlorohydrin. Examples of the polyfunctional epoxy resin (I-2) include aliphatic polyvalent glycidyl ether compounds, aromatic polyvalent glycidyl ether compounds, aliphatic polyvalent glycidyl ester compounds, aromatic polyvalent glycidyl ester compounds, and aliphatic polyvalent glycidyl compounds. Ether ester compound, aromatic polyvalent glycidyl ether ester compound, alicyclic polyvalent glycidyl ether compound, aliphatic polyvalent glycidyl amine compound, aromatic polyvalent glycidyl amine compound, hydantoin type polyvalent glycidyl compound, novolac type polyvalent glycidyl Examples thereof include ether compounds, epoxidized diene polymers, 3,4-epoxy-6-methylcyclohexylmethyl, 3,4-epoxy-6-methylcyclohexane carbonate and bis (2,3-epoxycyclopentyl) ether.

Examples of the aliphatic polyhydric glycidyl ether compounds include those obtained by the reaction of polyalkylene glycols with epichlorohydrin, those obtained by the reaction of polyhydric alcohols with epichlorohydrin, and the like. Examples of the polyalkylene glycols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, pyropyrene glycol, dipyropyrene glycol, tripyropyrene glycol, and polypyropyrene glycol.
Examples of polyhydric alcohols include dimethylolpropane, trimethylolpropane, spiroglycol, and glycerin.

Examples of the aromatic polyvalent glycidyl ether compounds include those obtained by reacting aromatic diols or diols obtained by modifying them with alkylene glycols such as ethylene glycol and propylene glycol, and epichlorohydrin. Examples of the aromatic diols include bisphenol A, bisphenol S, bisphenol F and bisphenol AD.

Examples of the aliphatic polyhydric glycidyl ester compounds include those obtained by the reaction of aliphatic dicarboxylic acids such as adipic acid and itaconic acid with epichlorohydrin. Examples of the aromatic polyvalent glycidyl ester compound include those obtained by the reaction of an aromatic dicarboxylic acid such as isophthalic acid, terephthalic acid, and pyromellitic acid with epichlorohydrin.

Examples of the aliphatic polyvalent glycidyl ether ester compound and the aromatic polyvalent glycidyl ether ester compound include those obtained by the reaction of a hydroxydicarboxylic acid compound and epichlorohydrin.
Examples of the aliphatic polyvalent glycidyl amine compound include those obtained by reacting an aliphatic diamine such as polyethylene diamine with epichlorohydrin.

Examples of the aromatic polyvalent glycidyl amine compounds include those obtained by the reaction of aromatic diamines such as diaminodiphenylmethane, aniline and metaxylylenediamine with epichlorohydrin. Examples of the hydantoin-type polyvalent glycidyl compound include those obtained by reacting hydanin or a derivative thereof with epichlorohydrin.

The novolac-type polyhydric glycidyl ether compound is obtained by reacting a novolak resin derived from phenol or cresol and formaldehyde with epichlorohydrin, polyphenols such as polyalkenylphenol and copolymers thereof, and epichlorohydrin. What was obtained by the reaction of is mentioned.

Examples of the epoxidized diene polymer include epoxidized polybutadiene and epoxidized polyisoprene. <Phenolic curing agent (II)> The phenolic curing agent (II) used in the anisotropic conductive paste (resin composition) of the present invention is 10% in the resin composition (100% by mass).
It is desirable to use in an amount of -50 mass%, preferably 10-40 mass%, more preferably 10-30 mass%. When the amount of the phenolic curing agent (II) used is 10% by mass or more in the resin composition (100% by mass),
The cured product of the resin composition has excellent adhesion reliability and connection reliability at high temperature and high humidity, and is 50% by mass or less,
This is preferable because it is possible to suppress an increase in the viscosity of the resin composition and it is excellent in workability and coatability.

The phenolic curing agent (II) used in the present invention may be liquid or solid at room temperature. One selected from the phenolic curing agents having two or more functional groups may be used alone or in combination of two or more. As such a phenol-based curing agent (II), the phenol-based curing agent described in JP-A-6-100667 is used, and specifically, a phenyl compound or a naphthalene compound and aldehydes, ketones, aromatics Examples thereof include compounds and condensates with alicyclic compounds. Examples of the phenyl compound include phenol, cresol, ethylphenol, and propylphenol. Examples of the naphthalene compound include α-naphthol and β-naphthol. Examples of the aldehydes include formaldehyde (formalin) and paraformaldehyde. Examples thereof include acetone and acetophenone, examples of the aromatic compound include xylylene and divinylbenzene, and examples of the alicyclic compound include dicyclopentadiene.

As the phenol-based curing agent (II), a known one can be used, but it is preferable to use a phenol novolac type curing agent derived from phenol or cresol and formaldehyde. <High softening point fine particles (III)> High softening point fine particles (III) used in the anisotropic conductive paste (resin composition) of the present invention
Can be melted in the anisotropic conductive paste of the present invention at a softening point temperature or higher to increase the viscosity of the paste and suppress its flow. Further, the repairability of the anisotropic conductive paste can be imparted.

The high softening point fine particles (III) are contained in the resin composition (100% by mass) in an amount of 5 to 25% by mass,
Preferably 10 to 20% by mass, more preferably 13 to
It is desirable to use it in an amount of 18% by weight. When the amount of the high softening point fine particles (III) used is 5% by mass or more in the resin composition (100% by mass), it is possible to suppress the occurrence of resin loss and exudation during thermocompression bonding, and 25
It is preferable for the content to be not more than mass% because the viscosity of the anisotropic conductive paste does not rise so much as to hinder the coating work and the workability in dispenser coating and the like is excellent.

The high softening point fine particles (III) have a softening point temperature of 60 to 150 ° C, preferably 70 to 120 ° C.
And the primary particle size is 0.01 to 2 μm, 0.1 to
Any known material may be used as long as it is in the range of 1 μm. High softening point fine particles (III) in the present invention
May be any combination of the softening point temperature range and the primary particle size range. Here, the primary particle size is a particle that cannot be mechanically separated.
A softening point temperature of 60 ° C. or higher is preferable because the anisotropic conductive paste of the present invention has excellent storage stability at room temperature. Further, when the softening point temperature is 150 ° C. or lower, it is 150 to
In the thermocompression bonding process at 200 ° C., the flow of the anisotropic conductive paste can be suppressed and repairability can be imparted. The primary particle diameter of the high softening point fine particles (III) is
From the viewpoint of workability such as dispenser application and connection reliability, the thickness is preferably 0.01 to 2 μm.

The high softening point fine particles (III) can be produced by preparing an emulsion solution of the high softening point fine particles (III) and spray-drying the emulsion solution. Such an emulsion solution is obtained, for example, by copolymerizing 30 to 70% by mass of methyl (meth) acrylate as a monomer and 70 to 30% by mass of another copolymerizable monomer, and preferably another copolymerizable monomer. As, it is desirable to use a polyfunctional monomer. When the above polyfunctional monomer is used, a finely crosslinked structure is formed in the emulsion fine particles.

By using the high softening point fine particles (III) obtained from these emulsion solutions in the anisotropic conductive paste of the present invention, the storage stability of the anisotropic conductive paste at room temperature is further increased, and thermocompression bonding is performed. It is possible to further suppress the occurrence of resin omission and bleeding at the time. Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (acrylate), 2-ethylhexyl (meth) acrylate, amyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl ( Meta)
Acrylate, butoxyethyl (meth) acrylate,
Acrylic acid esters such as phenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, acrylamides, acid monomers such as (meth) acrylic acid, itaconic acid, maleic acid, styrene, Examples thereof include aromatic vinyl compounds such as styrene derivatives.

As the polyfunctional monomer for forming a finely crosslinked structure in the emulsion fine particles, divinylbenzene, diacrylates, 1,3-butadiene,
Conjugated dienes such as 1,3-pentadiene, isoprene, 1,3-hexadiene and chloroprene can be used. Examples of the method for slightly cross-linking the surface of the emulsion fine particles include a method for cross-linking the epoxy group, the carboxyl group, and the amino group of the surface layer of the emulsion fine particles with metal to ionomer cross-link. By forming a fine cross-linking structure in the emulsion fine particles, it becomes difficult for the emulsion fine particles to dissolve in the epoxy resin (I), a solvent, etc. at room temperature, and the storage stability of the anisotropic conductive paste of the present invention can be improved.

<Conductive Particles (IV)> The conductive particles (IV) used in the anisotropic conductive paste (resin composition) of the present invention.
Is 0.1 to 2 in the resin composition (100% by mass).
It is desirable to use 5% by mass, preferably 1 to 20% by mass, more preferably 2 to 15% by mass. When the amount of the conductive particles (IV) used in the resin composition (100% by mass) is 0.1% by mass or more and 25% by mass or less, the anisotropic conductive paste has sufficient conductivity. Can be granted.

As the conductive particles (IV) used in the anisotropic conductive paste of the present invention, known particles can be used. Specifically, gold, nickel, silver, conductive particles of noble metals such as platinum, silver-copper alloy, gold-copper alloy, conductive particles of noble metal alloys such as nickel alloy, organic polymer fine particles such as polystyrene to the noble metal or Examples thereof include conductive particles obtained by forming a film of a noble metal alloy. Preferably, conductive particles of noble metal gold or nickel, conductive particles obtained by forming a noble metal film of gold or nickel on organic polymer fine particles, and the like are desirable. The formation of a noble metal film of gold or nickel on the organic polymer fine particles means that the surface component of the organic polymer fine particles is formed of gold or nickel. Examples of commercially available products include Sekisui Fine Chemical's trade name “Micropearl AU series”. The particle size of these conductive particles is 2 to
It is preferably in the range of 20 μm.

<Defoaming Agent (V)> As the defoaming agent (V) used in the anisotropic conductive paste (resin composition) of the present invention, a known defoaming agent can be used. Specific examples thereof include silicone-based defoaming agents and fluorine-based defoaming agents, preferably silicone-based defoaming agents, and more preferably polysilicone.

Such an antifoaming agent (V) in the resin composition (100% by mass) is 0.1 to 20% by mass, preferably 0.1 to 15% by mass, more preferably 0.5 to
It is desirable to use in an amount of 15% by weight. Defoaming agent (V)
Is used in the resin composition (100% by mass),
When it is 0.1% by mass or more, bubbles are less likely to be generated in the anisotropic conductive paste, and bubbles are not contained even after curing, and when it is 20% by mass or less, dispenser coating workability and The anisotropic conductive paste has excellent adhesiveness, and further, it is possible to suppress deterioration of the gas barrier property after curing.

The polysilicone is preferably a silicone-modified elastomer. Since the silicone is an elastomer, when the anisotropic conductive paste is cured, it is possible to reduce physical shock from the outside, thermal strain during a thermal cycle test, and the like. Further, since the above-mentioned polysilicone is a silicone-modified elastomer, it is possible to further alleviate physical impact from the outside, thermal strain during a thermal cycle test, and the like. Here, the silicone modification is to graft-bond a silicone having a functional group to an elastomer.

As the above-mentioned polysilicone, the epoxy resin (I) which is a component of the anisotropic conductive paste of the present invention is used.
It is preferable to use a silicone-modified elastomer which is grafted to an epoxy resin other than. Generally, epoxy resins and silicones have low compatibility, and thus phase separation easily occurs. Therefore, by using the silicone-modified elastomer grafted to the epoxy resin as the polysilicone, the polysilicone can be uniformly dispersed in the anisotropic conductive paste.

Such a polysilicone has a softening point temperature of -80 ° C to 0 ° C, preferably -80 to -20.
C., more preferably -80 to -40.degree. When the softening point is in the above range, the effect of alleviating physical impact from the outside, thermal strain during a heat cycle test, etc. is improved, and high adhesive strength can be secured. The polysilicone has a primary particle size of 0.05 to 5 μm,
It is desirable that the rubber-like polymer particles have a diameter of preferably 0.1 to 3.5 μm, more preferably 0.1 to 2 μm. When the primary particle diameter of the poly-silicone is 0.05 μm or more, aggregation does not occur in the anisotropic conductive paste, and the viscosity of the paste is stable, and workability such as dispenser application is excellent, which is preferable. . Also,
By setting the primary particle diameter of the polysilicone to 5 μm or less, workability such as dispenser application is excellent, and high adhesive strength can be secured after the anisotropic conductive paste containing the polysilicone is cured. it can. In the present invention, the polysilicone has a softening point range of 1 and above.
Any combination with the range of the secondary particle size may be used.

As a method for forming the above-mentioned polysilicone,
Method using fine particles of silicone rubber, JP-A-60-72
No. 957, a double bond is introduced into an epoxy resin and a hydrogen-containing silicone capable of reacting with the double bond is reacted to form a graft body,
A method of polymerizing a silicone rubber monomer in the presence of a graft body, a method of introducing a double bond into an epoxy resin and reacting a polymerizable vinyl group-containing silicone rubber monomer therewith to form a graft body, in the presence of the graft body And a method of polymerizing the silicone rubber monomer. Preferred is a method in which the silicone rubber particles are formed after forming the graft body and the graft body without using the silicone rubber fine particles, and the viscosity of the polysilicone obtained by these methods is small even when dispersed, which is preferable. Dispenser coating workability can be obtained.

<Coupling Agent (VI)> The coupling agent (VI) used in the anisotropic conductive paste (resin composition) of the present invention improves the adhesive force between the resin composition and the substrate, Furthermore, electrical circuit wiring formed on one of the substrates,
It is used to improve the adhesive force with the electric circuit wiring formed on the other substrate. The amount used is 0.1% by mass to 5% by mass in the resin composition (100% by mass),
Preferably 0.1 to 4% by mass, more preferably 0.1.
It is desirable that the amount be 3% by mass. When the amount of the coupling agent (VI) used is 0.1% by mass or more in the resin composition (100% by mass), the adhesiveness between the anisotropic conductive paste and the base material is high, and the amount is 5% by mass. When it is at most%, the cured product of the paste will have sufficient hardness, and the contamination of peripheral members can be reduced.

As the coupling agent (VI), a known coupling agent can be used. Specific examples include a trialkoxysilane compound and a methyldialkoxysilane compound. More specifically, as the trialkoxysilane compound, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N −
Examples thereof include aminoethyl-γ-iminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane. Further, as the methyl dialkoxy silane compound, γ-glycidoxy propyl methyl dimethoxy silane, γ-glycidoxy propyl methyl diethoxy silane, γ-aminopropyl methyl dimethoxy silane, γ-amino propyl methyl dimethoxy silane, N -Aminoethyl- [gamma] -iminopropylmethyldimethoxysilane, [gamma] -mercaptropylmethyldimethoxysilane, [gamma] -aminopropyltrimethoxysilane, [gamma] -mercaptopyrupylmethyldimethoxysilane, and isocyanate propylmethyldiethoxysila.

<Curing catalyst (VII)> Curing catalyst (VII) used in the anisotropic conductive paste (resin composition) of the present invention
Acts as a catalyst when the epoxy resin (I) reacts with the phenolic curing agent (II), and is specifically added for the purpose of curing the resin composition in a very short time. Such curing catalyst (VII) can be selected from among the already known epoxy curing catalysts. In particular, it is preferable to use a latent epoxy curing catalyst that exhibits thermosetting activity by heating at 40 ° C. or higher. However, the curing catalyst (VII) is a phenolic curing agent (II).
Is not included.

Examples of the latent curing catalyst which exhibits thermosetting activity at a heating temperature of 40 ° C. or higher include dicyandiamide and its derivatives, and dividazid compounds such as adipic acid dihydrazide and isophthalic acid dihydrazide. Further, a derivative of an imidazole compound and a modified product thereof, that is, an imidazole-based curing catalyst may be used. As such an imidazole-based curing catalyst,
Specifically, 2-methylimidazole, 2-ethyl-4
-Methylimidazole, imidazole derivative such as 2-n-pentadecylimidazole, complex of imidazole compound and aromatic acid anhydride, imidazole-modified derivative such as adduct of imidazole compound and epoxy resin,
Examples include modified microcapsules.

The modified microcapsules, that is, microcapsulated imidazole-based curing catalysts include 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-n-pentadecylimidazole-based curing catalysts as core materials. As an example, a microencapsulated product enclosed by a fine shell can be mentioned. The curing catalyst (VII) is 1 in the resin composition (100% by mass).
It is desirable to use it in an amount of 5% by mass or less, preferably 1 to 10% by mass. When the content is 15% by mass or less, the characteristics of the cured epoxy resin are exhibited, and high adhesion reliability can be obtained.

In the present invention, if the phenolic curing agent (II) is not used in the anisotropic conductive paste and only the curing catalyst (VII) is used, in this case, the epoxy resin (I) is The resin composition is cured by an ionic polymerization reaction, but this cured product may have insufficient performance than the curing agent obtained by using the phenolic curing agent (II).

<Other Additive Materials> The anisotropic conductive paste (resin composition) of the present invention may be added with other additive materials such as an inorganic filler and a solvent.
The inorganic filler is added for the purpose of adjusting the viscosity and reducing the thermal stress of the cured product, and can be selected from already known inorganic compounds. Specific examples of such an inorganic filler include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, Examples thereof include potassium titanate, kaolin, talc, asbestos powder, quartz powder, mica and glass fiber.

The particle size of the inorganic filler is not particularly limited as long as it does not affect the conduction characteristics of the anisotropic conductive paste, but is 2 μm or less, preferably 0.01 to 1 μm.
m is preferable. The inorganic filler is not particularly limited as long as it does not affect the conduction characteristics of the anisotropic conductive paste, but is 40% by mass or less, preferably 5 to 30% by mass in the resin composition (100% by mass). % Is preferably used.

A part or all of the inorganic filler is graft-modified with the epoxy resin (I) and / or the coupling agent (VI) in an amount of 1 to 50% by weight, when the amount of the inorganic filler is 100% by weight. Is preferably provided. That is, it is preferable to use an inorganic filler having a grafting ratio of 1 to 50%, which is represented by the weight increase amount obtained by the repeated solvent washing method.

Here, in order to obtain the grafting ratio by the repeated solvent washing method, the following may be carried out. First, the inorganic filler partially or wholly graft-modified,
Wet filtration is repeated 5 to 10 times with 10 to 20 times the mass of the following solvent. By this filtration, the epoxy resin (I) and the coupling agent (VI) which have not been graft-modified are washed away. As the solvent, an epoxy resin (I) is used.
And a good solvent for the coupling agent (VI) is used, and examples thereof include acetone, methyl ethyl ketone, methanol, ethanol, toluene, and xylene. Next, the inorganic filler remaining after the filtration is dried and its mass is measured. That mass is the dry mass of the grafted and modified inorganic filler. From this measured value, the mass increase rate is calculated according to the following formula. The grafting rate may be obtained by a Soxhlet continuous extraction method using the solvent instead of the repeated solvent washing method.

Formula: Grafting ratio (%) = [(dry weight of inorganic filler modified by grafting-dry weight of inorganic filler before grafting modification) / dry weight of inorganic filler before grafting modification] ] × 100 Specific examples of the solvent include methyl ethyl ketone,
Examples thereof include ketone solvents such as methyl isobutyl ketone and cyclohexanone, ether solvents such as diethylene glycol dimethyl ether, methyl carbitol, ethyl carbitol, and butyl carbitol, ethyl acetate, diethylene glycol diacetate, and alkoxydiethylene glycol monoacetate. The amount of the solvent used is
There is no particular limitation, and the solvent is used in an amount such that the solvent does not remain after the anisotropic conductive paste is cured.

The method for preparing the anisotropic conductive paste of the present invention is not particularly limited, but is performed as follows, for example. After the epoxy resin (I), the phenolic curing agent (II), the high softening point fine particles (III), the defoaming agent (V), and the coupling agent (VI) are pre-kneaded in a Dalton mixer at room temperature. Knead with 3 rolls. Next, the anisotropic conductive paste of the present invention can be prepared by adding and mixing the conductive particles (IV) and the curing catalyst (VII), and then kneading and defoaming in a Dalton mixer under vacuum. .

The anisotropic conductive paste of the present invention thus obtained has a viscosity of 30 to 400 Pa.
s, preferably 40 to 200 Pa · s, more preferably 5
It is preferably 0 to 150 Pa · s (EH type viscometer, 2.5 rpm). When the viscosity of the paste is 30 Pa · s or more, it is possible to suppress the flow of resin which causes bubbles during curing by thermocompression bonding, and when it is 400 Pa · s or less, the dispenser coating workability is excellent. Therefore, it is preferable.

<Method of Using Anisotropic Conductive Paste> The method of using the anisotropic conductive paste of the present invention relates to a method of connecting electric circuit wirings. Here, a method of connecting electric circuit wirings in a liquid crystal display is taken as an example. To explain. As shown in FIG. 1, first, in step 1, the anisotropic conductive paste of the present invention is applied to a predetermined position of a liquid crystal display substrate by a dispenser. Next, in step 2, the liquid crystal display substrate and the TCP, which is an IC-mounted circuit substrate, are aligned. Next, in step 3, the anisotropic conductive paste is cured by a heating press fixing method. By these steps 1 to 3, an electric conduction circuit between the liquid crystal display substrate and the TCP is formed.

When the anisotropic conductive paste is applied by the dispenser in step 1, the entire dispenser may be preheated at a temperature of 20 ° C to 50 ° C. The application of the anisotropic conductive paste may be performed by computer control such as application by a dispenser, or may be applied manually to a necessary site. Further, when the anisotropic conductive paste is hardened by the hot press fixing method in step 3, the hot plate for hot pressing is 100 ° C. to 30 ° C.
It is desirable to adjust the temperature within 0 ° C, preferably within the range of 120 to 250 ° C. In addition, the clamping pressure during hot pressing is
The pressure is set to 0.1 to 5 MPa, and uniform heat and pressure is applied to the joint portion between the electrodes. For example, a rubber mat may be placed between the electrode and the pressing surface for pressing.

As described above, when the wiring of the liquid crystal display substrate and the wiring of the TCP are connected by using the anisotropic conductive paste of the present invention, they are connected so as to have conductivity only in the crimping direction. Therefore, insulation between adjacent wirings is maintained, and wirings can be connected with high connection reliability. In the above-mentioned connection method of electric circuit wiring, the liquid crystal display is explained, but it is also applicable to connection of electric circuit wiring in a flat panel display such as an organic electroluminescence display and a plasma display. The anisotropic conductive paste can also be used for connecting wirings of semiconductor devices such as circuit materials, charge-coupled devices, CCDs, and CMOSs.

[0067]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. The tests and measurements carried out in the following examples and comparative examples were carried out by the following methods. <1. Storage stability test> The anisotropic conductive paste was put in a polyethylene container, sealed, and stored in a constant temperature bath kept at -10 ° C. After 30 days, the viscosity at 25 ° C. was measured and judged by the rate of increase. ◯: less than 10% Δ: 10% or more and less than 50% x: 50% or more <2. Applicability test> Anisotropic conductive paste was filled in a 10 cc syringe and then defoamed. A dispenser (Shot Master: manufactured by Musashi Engineering) was applied at a speed of 4 cm per second, and judged according to the following criteria. ◯: No bleeding, no stringing, and good appearance. Δ: No bleeding or stringing, but the appearance was poor. X: Exudation and stringing occur, resulting in extremely poor coatability. <3. Measurement of gelation time> 1 g of anisotropic conductive paste
It was placed on a hot plate at 50 ° C. and stirred with a spatula. The time from when the resin composition was placed on the hot plate until the stringing was eliminated was measured and taken as the gelation time. <4. Measurement of Adhesive Strength> 1 g of anisotropic conductive paste was drawn on a low alkali glass with a dispenser (shot master: manufactured by Musashi Engineering). 230 ° C
The TAB (Tape Automated Bonding) film for test was pressure-bonded with the ceramic tool for 30 seconds at a pressure of 2 MPa to perform bonding. Temperature 25 ℃, humidity 50% R
After being stored in a H (Relative Humidity) thermostat for 24 hours, the peel strength (adhesive strength); g / cm was measured by a tensile tester (manufactured by Intesco). <5. Resin loss confirmation test> 1 g of the anisotropic conductive paste was drawn on a low alkali glass with a dispenser (shot master: manufactured by Musashi Engineering). 230
At a pressure of 2MPa for 30 seconds with a ceramic tool at ℃,
The test TAB film was pressed and bonded. After cooling, the joint portion was observed with a microscope and judged according to the following criteria. ◯: There was no resin omission or bleeding, and the appearance was good. Δ: Some resin was missing between the bumps and the appearance was poor. X: The resin omission and bleeding occurred entirely. <6. Bubble Generation Confirmation Test> Anisotropic conductive paste (1 g) was applied on low-alkali glass with a dispenser (shot master: manufactured by Musashi Engineering). The test TAB film was pressure-bonded with a ceramic tool at 230 ° C. for 30 seconds at a pressure of 2 MPa to bond them together. After cooling, the joint portion was observed with a microscope and judged according to the following criteria. ◯: There were no bubbles and the appearance was good. Δ: Some bubbles were seen between the bumps. X: Bubbles were seen as a whole. <7. Measurement of Conductivity > 1 g of anisotropic conductive paste was applied onto a low alkali glass having ITO (Indium Tin Oxide) wiring by a dispenser (shot master: manufactured by Musashi Engineering). The test TAB film was pressure-bonded with a ceramic tool at 230 ° C. for 30 seconds at a pressure of 2 MPa to bond them together. Immediately after bonding, I
Resistance value (Ω) between TO and electrode on test TAB film
Is measured, and further 600 at 60 ° C. and 95% RH.
After the time storage, the resistance value between the electrodes was measured again. <8. Wiring short confirmation test> Anisotropic conductive paste 1
Drawing of g was performed on a low alkali glass having ITO wiring with a dispenser (shot master: manufactured by Musashi Engineering). 30 with a ceramic tool at 230 ° C
The test TAB film was pressure-bonded at a pressure of 2 MPa for a second and bonded. After cooling, the connection between adjacent ITO electrodes was measured and judged according to the following criteria. ○: Insulation is secured. X: Conducted. <9. Repairability Confirmation Test> 1 g of the anisotropic conductive paste was drawn on a low alkali glass with a dispenser (shot master: manufactured by Musashi Engineering). 30 with a test TAB film and a ceramic tool at 230 ° C
Bonding was performed by pressing under a pressure of 2 MPa for a second.
After cooling, the test TAB film was peeled off by washing with a solvent, and then the surface of the low-alkali glass was observed with a microscope and judged according to the following criteria. ◯: No resin remained and the appearance was good. Δ: The resin partially remained and the appearance was poor. X: The resin remained as a whole.

[0068]

[Synthesis Example 1] Synthesis of high softening point fine particles 10 equipped with a stirrer, nitrogen introducing tube, thermometer, reflux cooling tube
400 g of ion-exchanged water was placed in a 00 ml four-necked flask, 1.0 g of sodium alkyldiphenyl ether disulfonate was charged with stirring, and the temperature was raised to 65 ° C. While maintaining the temperature at 65 ° C. and continuing stirring, 0.4 g of potassium persulfate was added, and then 1.2 g of t-dodecyl mercaptan, 156 g of n-butyl acrylate,
A mixed solution obtained by emulsifying a solution of 4.0 g of divinylbenzene, 3.0 g of sodium alkyldiphenyl ether disulfonate and 200 g of ion-exchanged water with a homogenizer was continuously added dropwise for 4 hours. After the reaction was continued for 2 hours after the dropping, 232 g of methyl methacrylate was added at once and then the reaction was continued for 1 hour, then 8 g of acrylic acid was continuously added in 1 hour, and the reaction was continued at 65 ° C. for 2 hours. After that, it was cooled. It was neutralized to pH = 7 with potassium hydroxide to obtain an emulsion solution having a solid content of 40.6% by mass.

1,000 g of this emulsion solution was spray-dried with a spray dryer to obtain about 400 g of high softening point fine particles having a water content of 0.1% or less. The softening point of the obtained high softening point fine particles was 80 ° C. The high softening point fine particles were analyzed with a submicron particle analyzer (N4PLU).
The particle size was 180 nm as a result of measuring the particle size by S-type; manufactured by Beckman Coulter, Inc.).

[0070]

[Synthesis Example 2] Synthesis of fine particles having a low softening point 10 equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a reflux cooling tube
400 g of ion-exchanged water was placed in a 00 ml four-necked flask, 1.0 g of sodium alkyldiphenyl ether disulfonate was charged with stirring, and the temperature was raised to 65 ° C. After maintaining at 65 ° C. and adding 0.4 g of potassium persulfate while continuing stirring, 1.2 g of t-dodecyl mercaptan, 156 g of n-butyl acrylate, 4.0 g of divinylbenzene, sodium alkyldiphenyl ether disulfonate 3 g 0.0 g and ion-exchanged water 2
A mixed solution obtained by emulsifying a solution of 00 g with a homogenizer was continuously added dropwise over 4 hours. After the reaction was continued for 2 hours after the dropping, 142 g of methyl methacrylate and 90 g of n-butyl acrylate were added at once, and the reaction was continued for 1 hour. Next, 8 g of acrylic acid was continuously added over 1 hour, and the reaction was continued at a constant temperature of 65 ° C. for 2 hours and then cooled. Neutralized to pH = 7 with potassium hydroxide and solid content 4
A 0.6% by mass emulsion solution was obtained.

1,000 g of this emulsion solution was spray-dried to obtain about 400 g of low softening point fine particles having a water content of 0.1% or less. The softening point of the obtained low softening point fine particles was 40 ° C. The particle size of the low softening point fine particles was measured by the submicron particle analyzer used in Synthesis Example 1, and the result was 180 nm.

[0072]

[Synthesis Example 3] Synthesis of silicone elastomer (A) 2000 equipped with a stirrer, gas introduction tube, thermometer, and cooling tube
A bisphenol F type epoxy resin [Epiclon 830S (manufactured by Dainippon Ink and Chemicals, Inc.)] having two epoxy groups in the molecule is prepared in a ml four-necked flask.
g, 12 g of methacrylic acid, 1 g of dimethylethanolamine and 50 g of toluene were added, and 11 were introduced while introducing air.
A double bond was introduced by reacting at 0 ° C. for 5 hours. Next, 5 g of hydroxy acrylate, 10 g of butyl acrylate, and 1 g of azobisisobutyronitrile were added, and the mixture was reacted at 70 ° C. for 3 hours and further at 90 ° C. for 1 hour. Then 11
Detoluene was removed under reduced pressure at 0 ° C. Next, 70 g of a silicone intermediate having a methoxy group in the molecule (manufactured by Toray Dow Corning Silicone Co., Ltd.) and 0.3 g of dibutyltin dilaurate were added, and the reaction was carried out at 150 ° C. for 1 hour,
The reaction was continued for another hour to remove the produced methanol. To the obtained graft body, 300 g of a mixture of room temperature-curing two-component type silicone rubber [KE-1204 (manufactured by Shin-Etsu Silicone Co., Ltd.)] at a ratio of 1/1 was added,
The reaction was carried out for 2 hours to obtain a silicone elastomer (A) in which crosslinked silicone rubber fine particles were uniformly dispersed.

This silicone elastomer (A) was rapidly cured at a low temperature in the presence of a photocuring catalyst, and the fracture surface morphology of the cured product was observed with an electron microscope to measure the dispersed rubber particle size. Particle size value is 1.0
was μm.

[0074]

Example 1 Bisphenol A type epoxy resin as epoxy resin (I), phenol / p-xylylene glycol dimethyl ether polycondensate as phenolic curing agent (II) [Mirex LLL (Mitsui Chemicals, Inc.)],
High softening point fine particles (III) synthesized in Synthesis Example 1 as the high softening point fine particles, silicone elastomer (A) synthesized in Synthesis Example 3 as the defoaming agent (V), and γ-glycidylpropyl as the coupling agent (VI) Trimethoxysilane [KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.)]
Was preliminarily kneaded with a Dalton mixer at room temperature, and then kneaded with three rolls. Then conductive particles (IV)
Micropearl Au-205 (manufactured by Sekisui Chemical Co., Ltd.,
Specific gravity 2.67), imidazole-modified microcapsule type compound [NOVACURE HX374 as a curing catalyst (VII)]
8 (manufactured by Asahi Kasei Epoxy Co., Ltd.)], and kneaded and defoamed under vacuum with a Dalton mixer. The compounding amount of each material is shown in Table 1.

The anisotropic conductive paste thus obtained was evaluated by the following test methods. The results are shown in Table 2.

[0076]

Example 2 An anisotropic conductive paste was prepared and tested in the same manner as in Example 1 except that the curing catalyst in Example 1 was not used and the blending amount was changed as shown in Table 1. . The test results are shown in Table 2.

[0077]

[Example 3] Example 3 was repeated except that the defoaming agent in Example 1 was changed from silicone elastomer A to linear silicone B (DC3037 (manufactured by Shin-Etsu Silicone Co., Ltd.)) and the compounding amount was changed as shown in Table 1. An anisotropic conductive paste was prepared by the same method as in Example 1 and tested. Table 2 shows the test results
Shown in.

[0078]

Example 4 An anisotropic conductive paste was prepared in the same manner as in Example 1 except that the coupling agent (VI) in Example 1 was not used and the blending amount was as shown in Table 1. The test was conducted. The test results are shown in Table 2.

[0079]

Example 5 Coupling agent (VI) in Example 1,
An anisotropic conductive paste was prepared and tested in the same manner as in Example 1 except that the defoaming agent (V) was not used and the blending amount was changed as shown in Table 1. Table 2 shows the test results
Shown in.

[0080]

Example 6 Coupling agent (VI) in Example 1,
The defoaming agent (V) and the curing catalyst were not used, and the blending amount is shown in Table 1.
An anisotropic conductive paste was prepared and tested in the same manner as in Example 1 except that the above procedure was used. The test results are shown in Table 2.

[0081]

Comparative Example 1 An anisotropic conductive paste was prepared and tested in the same manner as in Example 1 except that the high softening point fine particles in Example 1 were not used and the blending amount was changed as shown in Table 1. went. The test results are shown in Table 2.

[0082]

Comparative Example 2 The same method as in Example 1 except that the high softening point fine particles in Example 1 were changed to the low softening point fine particles synthesized in Synthesis Example 2 and the compounding amounts were changed as shown in Table 1. An anisotropic conductive paste was prepared according to to test. The test results are shown in Table 2.

[0083]

Comparative Example 3 An anisotropic conductive paste was prepared and tested in the same manner as in Example 1 except that the compounding amount was changed as shown in Table 1. The test results are shown in Table 2. Table 2
From the results, it was confirmed that the anisotropic conductive pastes of Examples 1 to 6 could obtain good evaluations in all tests.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

According to the present invention, it is possible to provide an anisotropic conductive paste which is excellent in storage stability and workability in dispenser application. In addition, the present invention is anisotropy in which no resin loss, bubbles, or exudation occur even when wiring is connected under severe thermocompression bonding conditions such as a temperature of 200 ° C. and a time of 10 to 30 seconds for maintaining high productivity. The cured product of the conductive paste can provide an anisotropic conductive paste having high adhesion reliability and connection reliability even at high temperature and high humidity, and high repairability.

[Brief description of drawings]

FIG. 1 is a schematic process diagram of a method for connecting electrical circuit wiring according to the present invention.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 63/00 C08L 63/00 C 83/04 83/04 101/00 101/00 C09J 9/02 C09J 9 / 02 161/06 161/06 163/00 163/00 (72) Inventor Tatsushi Murata 580-32 Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals, Inc. (72) Inventor Makoto Nakahara Abeno, Osaka City, Osaka Prefecture 22-22, Nagaike-cho, Chuap Co., Ltd. (72) Inventor Takatoshi Kira 22-22, Nagaike-cho, Abeno-ku, Osaka-shi, Osaka (72) In-house (72) Incorporated Daisuke Ike Sugi, Abeno, Osaka-shi, Osaka 22-22, Nagaike-cho, Chuap Co., Ltd. F-term (reference) 4J002 BC023 BC034 BG013 BG043 BG053 BG063 BG073 BG133 BH003 CC02X CC03X CD00W CD01W CD02W CD03W CD04W CD05W CD06W CD10W CD13W CD18W EQ86ER DA0006 U118 EX037 EX067 EX077 EX087 FA083 FA084 FA086 FB074 FD010 FD114 FD116 FD14X FD148 FD205 GQ02 4J036 AA01 DA02 DA05 FA01 FA13 FB03 FB07 KA16 EC07 EC02 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC2 EC0 KA32 LA09 NA19 5G301 DA01 DA55 DA57 DD01

Claims (16)

[Claims] 1. (I) Epoxy resin 30 to 80% by mass,
(II) Phenolic curing agent 10 to 50% by mass, (III)
High softening point fine particles 5 to 25% by mass, (IV) conductive particles 0.
An anisotropic conductive paste comprising 1 to 25% by mass. 2. (I) Epoxy resin 30 to 79.9% by mass, (II) Phenolic curing agent 10 to 50% by mass, (II
I) High softening point fine particles 5 to 25% by mass, (IV) Conductive particles 0.1 to 25% by mass, (V) Defoaming agent 0.1 to 20% by mass
An anisotropic conductive paste comprising: 3. (I) Epoxy resin 30 to 79.8% by mass, (II) Phenolic curing agent 10 to 50% by mass, (II
I) High softening point fine particles 5 to 25% by mass, (IV) Conductive particles 0.1 to 25% by mass, (VI) Coupling agent 0.1 to 5
An anisotropic conductive paste, characterized by containing mass%. 4. (I) Epoxy resin 30 to 79.8% by mass, (II) Phenolic curing agent 10 to 50% by mass, (II
I) High softening point fine particles 5 to 25% by mass, (IV) Conductive particles 0.1 to 25% by mass, (V) Defoaming agent 0.1 to 20% by mass, (VI) Coupling agent 0.1 to 0.1% An anisotropic conductive paste containing 5% by mass. 5. An anisotropic conductive paste, wherein the anisotropic conductive paste according to any one of claims 1 to 4 further contains a curing catalyst (VII). 6. The epoxy resin (I) has at least 1 to 6 epoxy groups on average in one molecule, and has a polystyrene-converted average molecular weight of 100 to 7,000 by GPC. An anisotropic conductive paste according to any one of items 1 to 5. 7. The anisotropic conductive paste according to claim 1, wherein the phenolic curing agent (II) is a phenol novolac type curing agent. 8. The high softening point fine particles (III) comprise 60 to 1
It has a softening point temperature of 50 ° C. and a primary particle size of 0.01.
It is a range of -2 micrometers, The anisotropic conductive paste in any one of Claims 1-7 characterized by the above-mentioned. 9. The high softening point fine particles (III) are high softening point fine particles obtained by copolymerizing methyl (meth) acrylate and a copolymerizable monomer other than the methyl (meth) acrylate. And 30 to 70% by mass of the methyl (meth) acrylate.
The anisotropic conductive paste according to any one of to 8. 10. The anisotropic conductive paste according to claim 1, wherein the conductive particles (IV) have a surface component made of gold or nickel. 11. The anisotropic conductive paste according to claim 2, wherein the defoaming agent (V) is polysilicone. 12. The polysilicone is a silicone-modified elastomer and has a softening point of -80 to
12. The anisotropic conductive paste according to claim 11, which has a temperature of 0 ° C. and is present as particles in the anisotropic conductive paste and has a primary particle diameter of 0.05 to 5 μm. .. 13. The anisotropic conductive paste according to claim 12, wherein the silicone-modified elastomer is an elastomer in which a silicone-containing group is grafted to an epoxy resin. 14. The viscosity at 25 ° C. is 30 to 400 Pa · s.
The anisotropic conductive paste according to any one of claims 1 to 13, wherein 15. The anisotropic conductive paste according to any one of claims 1 to 14 is used to connect electrical circuit wiring formed on one substrate and electrical circuit wiring formed on the other substrate. A method of using an anisotropic conductive paste, comprising: 16. The anisotropic conductive paste according to claim 1, which is one of a circuit material, a liquid crystal display, an organic electroluminescence display, a plasma display, a charge-coupled device, and a semiconductor device. A method of using an anisotropic conductive paste, which is used for.