JP2003261852A - Anisotropic conductive adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermally curable anisotropic conductive adhesive especially enabling connection at a low temperature in a short time in the mutual electrical connection of fine circuits such as the connection of an LCD and a TCP, the connection of the TCP and a PCB or the like and also excellent in adhesiveness, connection reliability, storage stability and repairing properties. <P>SOLUTION: The anisotropic conductive adhesive is obtained by dispersing conductive particles in an adhesive resin composition. The adhesive resin composition comprises a urethane acrylate resin, an organic peroxide, a phenoxy resin, a phosphoric ester and a urethane resin elastomer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an LCD (liquid crystal display), a PDP (plasma display) and a TCP.
(Tape carrier package) connection, TCP and P
The present invention relates to an anisotropic conductive adhesive having both low temperature connectivity and storability, which is used for electrical connection between fine circuits such as connection with a CB (printed circuit board).

[0002]

2. Description of the Related Art In recent years, anisotropic conductive adhesives in which conductive particles are dispersed in an adhesive resin have been required for various fine circuit connections such as connection between LCD or PDP and TCP or connection between TCP and PCB. The number has increased dramatically, and anisotropic conductive adhesives have been used as the connection method. In this method, an anisotropic conductive adhesive is sandwiched between the members to be connected and heated and pressed to maintain electrical insulation between adjacent terminals in the plane direction and electrically conduct between the upper and lower terminals. . Anisotropic conductive adhesives have been frequently used for such applications because of the lack of heat resistance of the adherend and electrical shorting between adjacent terminals in fine circuits. The reason is that the conventional connection method cannot be applied.

This anisotropic conductive adhesive is classified into a thermoplastic type and a thermosetting type, but recently, an epoxy resin type thermosetting type which is more reliable than the thermoplastic type. Are being widely used.

Regarding the thermoplastic type anisotropic conductive adhesive, SBS (styrene-butadiene-styrene), SI
Styrene-based copolymers such as S (styrene-isoprene-styrene) and SEBS (styrene-ethylene-butadiene-styrene) have been mainly used. However, these thermoplastic types are basically used by a melt fusion method. It is thought that its workability is generally better than that of thermosetting, if conditions are selected, because it can be applied at a relatively low temperature and for a short time, but it has good moisture resistance and chemical resistance. It was not able to withstand a long-term environmental test due to its low performance and low connection reliability.

On the other hand, thermosetting type anisotropic conductive adhesives, which are currently the mainstream, are generally widely used as epoxy resin type thermosetting types having a good balance between storage stability and curability. However, in practice, these thermosetting types are required to be heated and cured at a temperature of 150 to 200 ° C. for about 30 seconds in order to achieve both storage stability and curability of the resin. For example, at a temperature of less than 150 ° C., it was difficult to cure the resin in a practical connection time.

Further, regarding storage stability, for example, B
F ₃ amine complexes, dicyandiamide, organic acid hydrazides, systems containing latent curing agents such as imidazole compounds have been proposed, but those with excellent storage stability require a long time or high temperature for curing, On the contrary, there is a problem that the one that can be cured at a low temperature in a short time has poor storage stability, and both have advantages and disadvantages.

In addition to the above-mentioned problems, in connection workability of fine circuits using a thermosetting anisotropic conductive adhesive, those which are once connected due to a cause such as a positional deviation,
There is a growing demand for peeling and rejoining (so-called repair) of a member to be connected without damage or damage.
However, while most of them have advantages such as high adhesive strength and high reliability, it is extremely difficult to meet such seemingly contradictory requirements, and satisfactory ones have not been obtained.

In particular, recently, the LCD module has become larger in screen size, higher in definition, and narrower in frame rate.
The connection pitch has become finer and the connection has become narrower. For this reason, for example, in the connection between the LCD and the TCP, the connection pattern is displaced due to the expansion of the TCP at the time of connection, and the members inside the LCD are thermally affected by the temperature at the time of connection due to the narrow width of the connection portion. And other problems have arisen.
Further, in the connection between TCP and PCB, since the PCB has become longer, the PCB and the LCD warp due to the heating at the time of connection, causing a problem that the TCP wiring is disconnected.

Therefore, it has been considered to solve these problems by connecting at a lower temperature. For example, when a conventional thermoplastic type anisotropic conductive adhesive is used for connection, the connection is performed at a relatively low temperature. However, there is a problem that the connection reliability is poor because the resin has low moisture resistance and heat resistance. Also, with thermosetting type epoxy resin type anisotropic conductive adhesive which is the mainstream, when trying to connect at low temperature, it is necessary to lengthen the connection time to cure the resin,
It was not practically applicable.

An anisotropic conductive adhesive capable of low temperature connection, in which conductive particles are dispersed in an adhesive resin containing a cationically polymerizable substance and a sulfonium salt (JP-A-7-90237). Also, a method in which conductive particles are dispersed in an epoxy resin or the like and a 4- (dialkylamino) pyridine derivative (JP-A-4-189883) has been proposed, but the storage stability of the adhesive resin and the connected circuit terminal It has not been put to practical use due to problems such as corrosion.

Also, as a means for enabling low temperature connection,
In a thermosetting anisotropic conductive adhesive in which conductive particles are dispersed in a resin composition containing a radical polymerizable resin, an organic peroxide, a thermoplastic elastomer, and maleimide, the radical polymerizable resin is a phenolic hydroxyl group. Anisotropic conductive adhesive characterized by being a (meth) acryloylated novolak resin, which has an aminosilane coupling agent added for the purpose of improving adhesiveness and connection reliability. In order to have, a substance having a phosphoric acid ester structure having good adhesion to metal,
A combination of a phenoxy resin and a hydroxyl group-containing resin has also been proposed.

However, in the case of using a (meth) acryloylated novolac resin having a phenolic hydroxyl group, the fluidity and the curability of the resin in the low temperature region are insufficient, so that sufficient connection reliability and adhesion are obtained in the low temperature region. It was not possible to obtain strength, and in the case where a substance having a phosphate ester structure and a hydroxyl group-containing resin were used in combination, the adhesive resin had a relatively high hygroscopicity, and thus there was a problem in reliability and storability. As described above, a resin system that satisfies all of curability, workability, adhesiveness after high-temperature / high-humidity treatment, connection reliability, storability, etc. in a well-balanced manner has not yet been obtained. It has not been possible to obtain an anisotropic conductive adhesive which is excellent in heat resistance, adhesiveness, connection reliability, storage stability and repairability.

As a solution to such a problem, there has been proposed one using a urethane acrylate resin as a radically polymerizable resin (Japanese Patent Laid-Open No. 2000-256641). This is because the urethane acrylate resin has excellent adhesiveness due to the flexibility of the cured product due to its ether bond and the urethane bond, and the phosphoric acid ester and urethane acrylate represented by the general formula (3) that are blended at the same time. By copolymerization with a resin, an anisotropic conductive adhesive with excellent heat resistance and especially adhesion to metals can be obtained, and at the same time the hygroscopicity of the resin, which was a drawback when using phosphoric acid ester, was relatively low. As a result, it is possible to achieve both preservation and reliability. Further, the phenoxy resin represented by the general formula (2) is a tough, ductile thermoplastic resin having high cohesive force, has a hydroxyl group that enhances wetting and bonding with a polar adherend, and has a heat resistance. It is also excellent in properties, does not deteriorate even when the adhesive resin is heated and cured, and because it is an amorphous polymer, it does not crystallize even after cooling, and it is possible to obtain a smooth coating film and facilitate film formation. Therefore, it has been considered that an excellent anisotropic conductive adhesive can be obtained by using this in combination with the above.

However, the urethane acrylate resin and the phenoxy resin have a relatively low compatibility, and because they are phase-separated when viewed microscopically, the respective abilities of the respective components cannot be sufficiently exerted, and conversely they are bonded. There was a problem that it led to variations in power and performance degradation.

[0015]

DISCLOSURE OF THE INVENTION The present invention is the result of various investigations in view of the problems of variation in adhesive strength and deterioration of performance based on such low compatibility of phenoxy resin and urethane acrylate resin of the prior art. The purpose of the present invention is to connect LCDs and TCPs, TCP and PCBs, and other electrical circuits such as TCP and PCB. It is also possible to connect at a low temperature for a short time. The present invention aims to provide a heat-curable anisotropic conductive adhesive which is excellent in heat resistance, adhesiveness, connection reliability, storage stability, and repairability.

[0016]

The present invention is directed to a urethane acrylate resin having a structure represented by the general formula (1) as a thermosetting component, a phenoxy resin represented by the general formula (2) as a thermoplastic component, and more generally An anisotropic conductive adhesive obtained by dispersing conductive particles in an adhesive resin composition containing a phosphoric acid ester represented by the formula (3) and an organic peroxide as essential components, and further as a thermoplastic component An anisotropic conductive adhesive containing a urethane resin elastomer having a structure represented by formula (4) in the molecule.

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

As a more preferred embodiment, the urethane resin elastomer having the structure represented by the formula (4) has a number average molecular weight in the range of 10,000 to 100,000, and the urethane resin having the structure represented by the formula (4). The content of the elastomer is 1 with respect to the phenoxy resin represented by the general formula (2).
It is an anisotropic conductive adhesive in the range of 50 parts by weight.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The anisotropic conductive adhesive of the present invention includes a urethane acrylate resin, an organic peroxide, and a thermosetting resin having a structure represented by the general formula (1) as a thermosetting component in a resin composition constituting the anisotropic conductive adhesive. A urethane resin elastomer having the structure of formula (4) is contained in a resin composition comprising a phenoxy resin represented by formula (2) as a plastic component and a phosphoric acid ester represented by formula (3). It is a feature. It has been found that the urethane acrylate resin represented by the general formula (1) and the phenoxy resin represented by the general formula (2) have improved compatibility due to the presence of the urethane resin elastomer having the structure of the formula (4). . This is because the urethane resin elastomer having the structure of formula (4) has good compatibility with both the urethane acrylate resin represented by the general formula (1) and the phenoxy resin represented by the general formula (2). Therefore, it seems that it has become possible to suppress the occurrence of performance variations and performance deterioration due to phase separation, which has been a problem in the past.
As a result, the balance of curability and fluidity during thermocompression bonding, flexibility of the cured product, hygroscopicity, and heat resistance of the cured product is compatible with conventional anisotropic conductive adhesives using urethane acrylate resin or phenoxy resin. It is superior in comparison, and when used for connecting LCD and TCP for LCD applications, connecting TCP and PCB, etc., it obtains higher adhesiveness and higher reliability that cannot be obtained with conventional anisotropic conductive adhesives. be able to.

The urethane acrylate resin used in the present invention is not particularly limited as long as it has a structure represented by the general formula (1), but among them, urethane having a repeating unit number n of 5 to 20 is used. It is more desirable to use an acrylate. From this range, the number of repeating units n
If it is small, the wettability with respect to the adherend is excellent, but the flow of resin at the time of pressure bonding is too large and flows out to the periphery, resulting in a decrease in adhesive strength and reliability. on the other hand,
When the number of repeating units n is larger than this range, the fluidity of the resin decreases, the wettability with respect to the adherend decreases, and the curability also decreases, so that the adhesive strength and reliability also decrease.

These urethane acrylates having different repeating units can be used alone or in admixture of two or more in order to control the fluidity during thermocompression bonding. Further, in order to improve heat resistance, repairability, and fluidity at the time of connection, for example, (meth) acryloylated phenol novolac resin having a phenolic hydroxyl group, vinyl ester resin, unsaturated polyester resin, diallyl phthalate resin, maleimide resin, triimide It is also possible to use a mixture with other radically polymerizable resin such as methylolpropane triacrylate (TMPTA), pentaerythritol diallylate monostearate, tetraethylene glycol diacrylate and pentaerythritol tetraacrylate. Further, it may be diluted with a solvent or the like to facilitate the work of dissolving it in the resin. The blending amount of the urethane acrylate resin used in the present invention is naturally determined in consideration of the adhesiveness to the adherend and workability.

The organic peroxide used in the present invention is not particularly limited, and for example, 1, 1, 3, 3
-Tetramethylbutylperoxy-2-ethylhexanate, t-butylperoxy-2-ethylhexanate, t-hexylperoxy-2-ethylhexanate, 1,1-bis (t-butylperoxy)- 3,3
Examples thereof include 5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, bis (4-t-butylcyclohexyl) peroxydicarbonate and the like. These peroxides may be used alone or as a mixture of two or more kinds of organic peroxides in order to control the curability.
Further, various polymerization inhibitors may be added in advance in order to improve the storage stability. Further, it may be diluted with a solvent or the like and used to facilitate the work of dissolving it in the resin. The type and blending amount of the organic peroxide used in the present invention can be determined in consideration of the curability and storability of the adhesive when each peroxide is blended.

The phenoxy resin used in the present invention is not particularly limited as long as it has the structure of the general formula (2), and phenoxy resins having these various structures may be used alone or in combination of two or more kinds. You may use it. Further, among these phenoxy resins, the number average molecular weight is more preferably in the range of 10,000 to 100,000. If the molecular weight is smaller than this range, the toughness is insufficient and the adhesive strength is reduced. Also, for molecular weights above this range,
The resin fluidity at the time of thermocompression bonding is insufficient, and the connection resistance increases.

Further, as other thermoplastic components, for example, polyimide resin, polybutadiene, polypropylene, styrene-butadiene-styrene copolymer, polyacetal resin, polyvinyl butyral resin, butyl rubber, chloroprene rubber, polyamide resin, acrylonitrile-butadiene copolymer. , Acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl acetate resin, nylon, styrene-isoprene copolymer, styrene-butylene-styrene block copolymer, styrene-ethylene-butylene-
It is also possible to use a styrene block copolymer, a polymethylmethacrylate resin, etc. together.

The phosphoric acid ester in the present invention is not particularly limited as long as it is represented by the general formula (3), and it may be used alone or in combination of two or more kinds. Specific phosphoric acid esters include, for example, (meth) acryloyloxyethyl acid phosphate, (meth) acryloyloxypropyl acid phosphate, (meth) acryloyloxyisopropyl acid phosphate, (meth) acryloyloxypolyoxyethylene glycol acid. Phosphate, (meth) acryloyloxypolyoxypropylene glycol acid phosphate, caprolactone-modified (meth) acryloyloxyethyl acid phosphate, di (meth) acryloyloxypropyl acid phosphate, di [caprolactone-modified (meth) acryloyloxyethyl] acid phosphate, etc. Can be mentioned. With the phosphoric acid esters other than the general formula (3), the coupling effect between the radical polymerizable resin and the metal part of the adherend is low, and only the phosphoric acid ester of the general formula (3) is coupled at a relatively low temperature in a short time. You can get the effect.

The urethane resin elastomer used in the present invention is not particularly limited as long as it contains the structure of formula (4) in the molecule, and various urethane resin elastomers having these structures may be used alone or You may use together 2 or more types. Further, among these urethane resin elastomers, the number average molecular weight is in the range of 10,000 to 100,000, and the content is in the range of 1 to 50 parts by weight with respect to the phenoxy resin represented by the general formula (2). That
More desirable. If the molecular weight is lower than this range,
The toughness of the resin after curing is insufficient and the adhesive force is reduced. If the molecular weight is higher than this range, the fluidity of the resin during thermocompression bonding may be insufficient and the connection resistance may increase. If the content is less than this range, a sufficient compatibility effect cannot be obtained with the urethane acrylate and the phenoxy resin, causing a decrease in adhesive strength and the occurrence of variations. And the phenoxy resin may have poor adhesiveness and connection reliability. Examples of the urethane resin elastomer include reaction products of isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and polyols such as ethylene glycol, 1.4 butanediol, polyethylene glycol, polypropylene glycol. There is.

The conductive particles used in the present invention are not particularly limited as long as they have conductivity, and various metals such as nickel, iron, copper, aluminum, tin, lead, chromium, cobalt, silver and gold are used. Metal alloys, metal oxides, carbon, graphite, glass and ceramics, plastic particles coated with metal, and the like can be applied.
The particle size, material, and compounding amount of these conductive particles can be appropriately selected depending on the pitch and pattern of the circuit to be connected, the thickness and material of the circuit terminal, and the like.

In order to further enhance the adhesiveness, for example,
β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4epoxycyclohexyl) ethyltriethoxysilane, β- (3,4epoxycyclohexyl) ethyldimethoxymethylsilane, β- (3,3
4-epoxycyclohexyl) ethylmethoxydimethylsilane, β- (3,4epoxycyclohexyl) ethyldiethoxyethylsilane, β- (3,4epoxycyclohexyl) ethylethoxydiethylsilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethoxydimethylsilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethoxydiethylsilane, etc. A silane coupling agent can be used together depending on the adherend.

[0028]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples. In addition, Table 1 shows a list of substances used in Examples and Comparative Examples of the present invention.

[0029]

[Table 1]

[0030]

[Chemical 9]

[0031]

[Chemical 10]

<Example 1> As shown in Table 2, a urethane acrylate resin having a structure of the general formula (1) (n =
10) 500 parts by weight, and 1,1,3,3-tetramethylbutylperoxyhexanoate 2 parts by weight, (5)
Urethane resin elastomer represented by the formula (Mn = 30,000)
200 parts by weight of a 20% solution of phenoxy resin dissolved in methyl ethyl ketone, and a phenoxy resin represented by the formula (6) (Mn = 5
10% solution in methyl ethyl ketone
0 parts by weight, 2 parts by weight of caprolactone-modified (meth) acryloyloxyethyl acid phosphate, Ni / A
2.8 parts by weight of u-plated polystyrene particles are mixed and uniformly dispersed, and then cast and dried on a polyethylene terephthalate film that has been subjected to a mold release treatment so that the thickness after drying is 45 μm. A conductive adhesive was obtained.

<Examples 2 to 12> By the formulations shown in Tables 2 and 3, anisotropic conductive adhesives were obtained in the same manner as in Example 1. The formulations in Tables 2 and 3 are shown in parts by weight.

<Comparative Example 1> An anisotropic conductive adhesive was obtained in the same manner as in Example 1 with the ingredients shown in Table 3. The anisotropic conductive adhesives obtained in Examples and Comparative Examples were evaluated by the methods described below.

(Method for evaluating anisotropic conductive adhesive) 1. Preparation of evaluation sample The adherend is 0.5μ in copper foil / polyimide = 25 / 75μm
m tin plated TCP (pitch 0.30 mm, 60 terminals) and 0.8 mm thick 4-layer board (FR-4) inner / outer layer copper foil 18 μm flash gold plated PCB (pitch 0.30 mm, 60 terminals) Book) was used.

2. Adhesive strength measurement method Press-bonded under the conditions of 150 ° C, 30 kg / cm ² , 15 s, and 9
Evaluation was carried out by a 0 ° peel test.

3. Connection Reliability Measurement Method The connection resistance was measured immediately after sample preparation, after a thermal shock test at a temperature of -40 ° C to 150 ° C, and after 100 times of treatment. Those that could not be measured were regarded as poor conduction (OPEN).

4. Storability measuring method After storing the anisotropic conductive film in an atmosphere of 25 ° C for 4 weeks, 1
The connection resistance was measured by pressure bonding under the conditions of 50 ° C., 30 kg / cm ² , and 15 s. A value of 1.5Ω or less was evaluated as ◯, and a value of more than 1.5Ω was evaluated as ×.

The evaluation results are shown in Tables 2 and 3.

[Table 2]

[0040]

[Table 3]

[0041]

By using the anisotropic conductive adhesive of the present invention, fine circuit electrodes can be connected at a low temperature of about 150 ° C., and excellent heat resistance, adhesiveness and connection reliability can be obtained. Also, it is possible to connect at an extremely low temperature in a short time, and an anisotropic conductive adhesive having excellent adhesiveness, connection reliability, storage stability, and repairability can be obtained.

Claims (3)

[Claims] 1. A urethane acrylate resin having a structure represented by the general formula (1) as a thermosetting component, a phenoxy resin represented by the general formula (2) as a thermoplastic component, and further represented by a general formula (3). An anisotropic conductive adhesive obtained by dispersing conductive particles in an adhesive resin composition containing a phosphoric acid ester and an organic peroxide as essential components, further comprising a thermoplastic component represented by the formula (4): An anisotropic conductive adhesive containing a urethane resin elastomer having a structure shown. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] 2. The anisotropic conductive adhesive according to claim 1, wherein the urethane resin elastomer having a structure represented by the formula (4) has a number average molecular weight in the range of 10,000 to 100,000. 3. The content of the urethane resin elastomer having the structure represented by the formula (4) is in the range of 1 to 50 parts by weight with respect to the phenoxy resin represented by the general formula (2). The anisotropic conductive adhesive described.