KR100841193B1 - Anisotropic conductive adhesive composition using carboxyl modified polyacetal resin and the adhesive flim using thereof - Google Patents

Abstract

An anisotropic conductive adhesive composition, and an anisotropic conductive adhesive film prepared from the composition are provided to improve adhesive strength, moisture resistance, heat resistance and mechanical properties. An anisotropic conductive adhesive composition comprises 100 parts by weight of a thermoplastic resin which is at least one selected from the group consisting of an olefin resin, a butadiene resin, an acrylonitrile-butadiene copolymer, a carboxyl-terminated acrylonitrile-butadiene copolymer and a phenoxy resin; 40-100 parts by weight of a carboxyl modified polyacetal resin having a weight average molecular weight of 10,000-500,000; 80-150 parts by weight of a radical polymerizable material; a radical initiator; and a conductive particle.

Description

Anisotropic conductive adhesive composition using a carboxyl modified polyacetal resin and an adhesive film using the same {ANISOTROPIC CONDUCTIVE ADHESIVE COMPOSITION USING CARBOXYL MODIFIED POLYACETAL RESIN AND THE ADHESIVE FLIM USING THEREOF}

The present invention relates to an anisotropic conductive adhesive composition and an adhesive film using the same, comprising a carboxyl modified polyacetal resin having excellent adhesive properties and reliability as a component of the binder portion, and more particularly, to a carboxyl modified polyacetal resin. Is incorporated as a component of the binder portion, and chip on glass (COG) is used for various display devices including liquid crystal display (hereinafter referred to as LCD) or chip on film mounting ( Chip On Film (hereinafter referred to as COF mounting) relates to an anisotropic conductive adhesive composition which prevents short between adjacent circuits and maintains initial low connection resistance, excellent adhesive strength and high reliability, and an adhesive film using the same will be.

In general, an anisotropic conductive film refers to a film-like adhesive in which conductive particles such as metal particles such as nickel (Ni) and gold (Au) or polymer particles coated with such metals are dispersed. When placed between the circuits and subjected to heating and pressing processes under a certain condition, the circuit terminals are electrically connected by conductive particles, and a pitch between the adjacent circuits is filled with an insulating adhesive resin to form conductive particles. Since they exist independently of each other, high insulation is provided. Such anisotropic conductive films are widely used for electrical connection of LCD panels, tape carrier packages (hereinafter referred to as TCP), or printed circuit boards and TCP.

On the other hand, with the trend of the display industry, which has recently become larger and thinner, the pitch between electrodes and circuits is gradually miniaturized, and anisotropic conductive film plays a very important role as one of wiring devices for connecting these fine circuit terminals. . As a result, the anisotropic conductive film has attracted much attention as a connection material such as chip on glass mounting or chip on film mounting.

As a conventional anisotropic conductive film, (i) an epoxy type in which a cured portion composed of an epoxy or phenolic resin and a curing agent is mixed in a binder resin portion which acts as a matrix for film formation, and (ii) a (meth) acrylic type in a binder resin portion. There is a (meth) acrylate type in which a cured portion composed of an oligomer, a monomer and a radical initiator is mixed.

However, since the binder portion of the conventional anisotropic conductive film only serves as a film forming agent, it does not contribute significantly to the initial adhesive strength or the connection reliability, and the shrinkage and expansion are repeated in the connection structure due to the polymer resin of low glass transition temperature, which is mainly used. There is a problem that cannot guarantee long-term connection and adhesion reliability.

On the other hand, the conventional epoxy type anisotropic conductive film has poor adhesiveness and is difficult to temporarily fix to the connection layer, resulting in poor workability, very high reaction temperature, making process control and maintenance of the connection device difficult, and long-term reliability. There is a problem falling.

In addition, (ii) the (meth) acrylate type anisotropic conductive film also has a flowability difference due to the difference in rheology properties of the binder resin part and the hardened part when the reaction rate is slowly adjusted to ensure contact between the conductive particles and the circuit. There is a problem that can not guarantee long-term reliability by generating a large amount of bubbles in the connection layer, on the contrary, if the reaction rate is controlled quickly, the conductive particles do not come into sufficient contact with the circuit, and thus cannot guarantee good connection reliability. Even during manufacture, there is a problem that the stability of the liquid solution is not sufficiently secured.

(Iii) The carboxyl modified polyacetal resin has a high glass transition temperature, and can exhibit long-term connection and adhesion reliability even after repeated shrinkage and expansion in the connection structure under high temperature and high humidity, and maintain excellent adhesion with various kinds of adhesives. It has the characteristics to be able. With these characteristics in mind, our researchers have tried to solve the above problems by applying the carboxyl modified polyacetal resin as a component of the vaander portion.

An object of the present invention is to solve the problems of the anisotropic conductive film described above as a component of the binder portion of a carboxyl modified polyacetal resin having excellent heat resistance, moisture resistance, and mechanical properties, and exhibiting high adhesive properties under high temperature and high humidity. It is an object of the present invention to provide an anisotropic conductive adhesive composition capable of improving not only high adhesion and moisture resistance, heat resistance and mechanical properties, but also excellent long-term reliability.

Another object of the present invention is to provide an anisotropic conductive adhesive film prepared using the anisotropic conductive adhesive composition.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention for achieving the above object is (A) thermoplastic resin, (B) carboxyl modified polyacetal resin having an average molecular weight of 10,000 to 500,000, (B) radically polymerizable material, (D) radical initiator And (E) conductive particles.

Another aspect of the present invention for achieving the above object relates to an anisotropic conductive adhesive film made of the anisotropic conductive adhesive composition.

The anisotropic conductive adhesive composition of the present invention and the adhesive film using the same are characterized in that they include carboxyl modified polyacetal resin having excellent heat resistance, moisture resistance, and mechanical properties, and exhibiting high adhesive properties under high temperature and high humidity as one component of the binder part. .

Hereinafter, the present invention will be described in more detail.

(A) thermoplastic resin

The thermoplastic resin of the present invention is applicable as long as it is at least one component selected from the group consisting of olefin resins, butadiene resins, acrylonitrile butadiene copolymers, carboxyl terminal acrylonitrile butadiene copolymers and phenoxy resins.

 Since such a thermoplastic resin exhibits high pressure adhesiveness, it is possible to express excellent adhesive force and adhesiveness by a heat press circuit connection step of an anisotropic conductive film and to obtain good connection of a circuit terminal. The thermoplastic resin is suitably 15 to 50% by weight in the anisotropic conductive film composition. This is because if less than 15% by weight, the adhesion is insufficient, and if more than 50% by weight, the curing performance is lowered due to the lack of radical curing reaction.

In addition, in the present invention, it is preferable to use a thermoplastic resin having a weight average molecular weight in the range of 10,000 to 1,000,000. If the molecular weight is too low, the film strength is not expressed, the adhesiveness is excessive, the film is not formed properly, if the molecular weight is too high, the miscibility deteriorates and phase separation may occur in the preparation of the anisotropic conductive film composition. Because there is.

(B) an average molecular weight of 10,000 to 500,000 Carboxyl  denaturalization Poly  Acetal resin

The carboxyl modified polyacetal resin of the present invention is a film-forming polymer resin, which is a carboxyl-modified polyvinyl butyral resin or polyvinyl formal resin through an esterification reaction.

Since the carboxyl-modified polyacetal resin is applied to the present invention, not only it can contribute to the improvement of adhesion compared to the case of using the conventional polyacetal resin, but also the toughness is increased, which is advantageous for film formation, and also various raw materials. Compatibility with is improved, and high liquid stability can be secured.

It is preferable to use the thing of the range whose average molecular weights are 10,000-500,000 as polyacetal resin for the said carboxyl modification. This is because when the molecular weight is less than 10,000, it does not contribute to film formation, and when the molecular weight is greater than 500,000, the flowability of the composition is poor at the time of heat compression due to excessive increase in toughness.

The polyacetal resin to be subjected to the carboxyl modification is a copolymer-type polyacetal resin, in which a polyacetal resin obtained by acetal polyvinyl alcohol and an aliphatic unsaturated group or polyester unsaturated compound are introduced into the side chain of the polyacetal resin. Modified polyacetal resins are suitable.

The polyacetal resin preferably has acetal group ratio of 50 mole% or more, because acetal group ratio of less than 50 mole% may cause deterioration in moisture resistance.

The composition ratio of the carboxyl-modified polyacetal resin is 40 to 100 parts by weight relative to 100 parts by weight of the thermoplastic resin content, which is lowered in the film strength of the anisotropic conductive film when the content of the carboxyl-modified polyacetal resin is less than 40 parts by weight. This is because not only the mechanical properties are poor, but it does not help to exhibit the adhesive force, and if it is more than 100 parts by weight, the stability of the adhesive composition is deteriorated, and thus film formation is difficult.

(C) Radical Polymerizable  matter

In the present invention, a radical polymerizable resin was used as a hardening part to cause a curing reaction to ensure adhesion and connection reliability between the connection layers. The radically polymerizable material used in the present invention is not particularly limited, and any radical polymerizable material may be used. The radically polymerizable substance includes an acrylate (methacrylate), a maleimide compound, and the like, and it is also possible to use the monomer or the oligomer in any state or to use the monomer and the oligomer in combination.

Specific examples of the acrylate (methacrylate) include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimetholpropane triacrylate , Tetramethylol methane tetra acrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis [4- (acryloxypolymethoxy) phenyl] propane, 2,2-bis [4- (Acryloxypolyethoxy) phenyl] propane, dicyclopentenyl acrylate, tricyclodecanyl acrylate, tris (acryloyloxyethyl) isocyanate, and the like, which may be used alone or in combination. Can be.

As said maleimide compound, it should have at least 2 or more maleimide groups in a molecule | numerator, For example, 1-methyl- 2, 4-bismaleimide benzene, N, N'-m- phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m-toylene bismaleimide, N, N'-4,4- biphenylene bismaleimide, N, N'-4,4- ( 3,3'- dimethyl biphenylene) bismaleimide, N, N'-4,4- (3,3'- dimethyl diphenyl methane) bismaleimide, N, N'-4,4- (3, 3'-diethyl diphenyl methane) bismaleimide, N, N'-4,4- diphenylmethane bismaleimide, N, N'-4,4- diphenyl propane bismaleimide, N, N'- 4,4-diphenyl etherbismaleimide, N, N'-3,3'- diphenyl sulfone bismaleimide, 2,2-bis (4- (4-maleimide phenoxy) phenyl) propane, 2, 2-bis (3-s-butyl-4-8 (4-maleimidephenoxy) phenyl) propane, 1,1-bis (4- (4-maleimidephenoxy) phenyl) , 4,4'- cyclohexylidenebis (1- (4 maleimide phenoxyshi) -2-cyclohexyl benzene, 2,2-bis (4- (4 maleimide phenoxy) phenyl) hexafluoro propane And these may be used alone or in combination.

In the present invention, the content of the radically polymerizable material is 80 to 150 parts by weight based on 100 parts by weight of the thermoplastic resin (A) content, which means that if the content of the radically polymerizable material is less than 80 parts by weight, trust due to the lowering of the curing density after the pressing process Deterioration of the properties and overall flowability is deteriorated, the contact between the conductive particles and the circuit substrate at the time of adhesion is poor, the connection resistance is increased or the connection reliability is lowered. This is because film formation is difficult and there is a problem that the adhesive properties are degraded.

As described above, a monomer or oligomer may be used for the radical polymerizable material, or a combination of the monomer and the oligomer may be applied. Accordingly, the present invention provides a sum of the radical polymerizable material and the initiator content for improving curability, fluidity during heating, and workability. It may further include 0.8 to 20 parts by weight of the monomer or oligomer relative to 100 parts by weight. If the content of the monomer or oligomer is less than 0.8 parts by weight, the curing reaction rate is lowered and the curing density is lowered. If the content of the monomer or oligomer is more than 20 parts by weight, the process characteristics are deteriorated due to an increase in the initial tack. .

In addition, the present invention may include a radically polymerizable material having a phosphate ester structure to improve the adhesion strength and room temperature stability to the radically polymerizable material, the content of which is 100 parts by weight of the total of the radically polymerizable material and the initiator content 0.3 to 9 parts by weight may be added. The radically polymerizable substance which has the said phosphate ester structure can be obtained as a reactant of phosphoric anhydride and 2-hydroxyethyl (meth) acrylate.

(D) Radical Initiator

As a radical initiator which is another component of the hardening part used by this invention, a photoinitiator or a thermosetting initiator can be used in combination of 1 or more types.

Examples of the photopolymerization initiator include benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4-methyl diphenyl sulfide, isopropyl thioxanthone, diethyl thioxanthone, 4-diethyl benzoate, benzoin ether, and benzoyl. Propyl ether, 2-hydroxy-2-methyl-1-phenyl propan-1-one, diethoxy acetophenone and the like can be used.

As the thermosetting initiator, peroxide-based and azo-based may be used. Examples of the peroxide-based initiator include t-butyl peroxylaurate, 1,1,3,3-t-methylbutylperoxy-2- Ethyl hexanonate, 2,5-dimethyl-2,5-di (2-ethylhexanoyl peroxy) hexane, 1-cyclohexyl-1-methylethyl peroxy-2-ethyl hexanonate, 2,5- Dimethyl-2,5-di (m-toluoyl peroxy) hexane, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxy benzoate, t- Butyl peroxy acetate, dicumyl peroxide, 2,5, -dimethyl-2,5-di (t-butyl peroxy) hexane, t-butyl cumyl peroxide, t-hexyl peroxy neodecanoate, t- Hexyl peroxy-2-ethyl hexanonate, t-butyl peroxy-2-2-ethylhexanoate, t-butyl peroxy isobutylate, 1,1-bis (t-butyl peroxy) cyclohexane, t-hexyl peroxy isopropyl Monocarbonate, t-butyl peroxy-3,5,5-trimethyl hexanonate, t-butyl peroxy pivalate, cumyl peroxy neodecanoate, di-isopropyl benzene hydroperoxide, cumene hydroperoxide, Isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethyl hexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxide , 3,5,5-trimethyl hexanoyl peroxide, benzoyl peroxy toluene, 1,1,3,3-tetramethyl butyl peroxy neodecanoate, 1-cyclohexyl-1-methyl ethyl peroxy noede Decanoate, di-n-propyl peroxy dicarbonate, di-isopropyl peroxy carbonate, bis (4-t-butyl cyclohexyl) peroxy dicarbonate, di-2-ethoxy methoxy peroxy dicarbonate, di (2-ethylhexyl peroxy) dicarbo Yit, dimethoxy butyl peroxy dicarbonate, di (3-methyl-3-methoxy butyl peroxy) dicarbonate, 1,1-bis (t-hexyl peroxy) -3,3,5-trimethyl cyclohexane , 1,1-bis (t-hexyl peroxy) cyclohexane, 1,1-bis (t-butyl peroxy) -3,3,5-trimethyl cyclohexane, 1,1- (t-butyl peroxy) Cyclododecane, 2,2-bis (t-butyl peroxy) decane, t-butyl trimethyl silyl peroxide, bis (t-butyl) dimethyl silyl peroxide, t-butyl triallyl silyl peroxide, bis (t- Butyl) diallyl silyl peroxide, tris (t-butyl) aryl silyl peroxide, and the like. Examples of the azo initiator include 2,2'-azobis (4-methoxy-2,4-dimethyl valero. Nitrile), dimethyl 2,2'-azobis (2-methyl propionate), 2,2'-azobis (N-cyclohexyl-2-methyl propionide), 2,2-azobis (2, 4-dimethyl valeronitrile), 2,2'-azobis (2-methylbutyl) Tril), 2,2'-azobis [N- (2-propenyl) -2-methylpropionide], 2,2'-azobis (N-butyl-2-methyl propionide), 2, 2'-azobis [N- (2-propenyl) -2-methyl propionide], 1,1'-azobis (cyclohexane-1-carbonitrile), 1-[(cyano-1-methyl Ethyl) azo] formamide, etc., and these can be used in mixture of 1 or more types.

The content of the radical initiator is determined in a range that can achieve a balance between the properties to be cured in the adhesive and the retention of the adhesive, in the present invention, the thermoplastic resin (A), the average molecular weight of 10,000 to 500,000 carboxyl modified poly It is preferable that it is 0.3-10 weight part with respect to a total of 100 weight part of acetal resin (B) and the said radically polymerizable substance (C) content. When the content of the radical initiator is less than 0.3 parts by weight, the compression property is lowered due to the lowering of the curing reaction rate, and when the content of the radical initiator is more than 10 parts by weight, the film is cured by heating and then the brittle property of the anisotropic conductive film is increased. The problem is that the anisotropic conductive film is not completely removed upon rework, which is undesirable.

(E) conductive particles

The conductive particles used in the present invention is applied as a filler for imparting conductivity of the composition for anisotropic conductive films of the present invention.

Examples of the conductive particles include metal particles including Au, Ag, Ni, Cu, solder, and the like; carbon; Resins containing polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol and the like, and modified resins thereof as particles to be coated with metals such as Au, Ag and Ni; One or more kinds of the insulated conductive particles coated with the insulating particles added thereon may be used.

The size of the conductive particles may be selected and used in the range of 1 to 30 μm by the pitch of the circuit to be applied, and may be used by mixing particles of different sizes.

The conductive particles are preferably 0.2 to 30 parts by weight based on 100 parts by weight of the total content of the carboxyl-modified polyacetal resin and the radical polymerizable material having a molecular weight of 10,000 or more. If the content of the conductive particles is less than 0.2 parts by weight, it is not easy to cause poor connection, and if it exceeds 30 parts by weight, it is not preferable because the insulation is likely to occur.

The present invention may further include a silane coupling agent as a coupling agent, wherein the coupling agent promotes adhesion between the surface of an inorganic material such as copper and glass and the resin of the anisotropic conductive film and improves heat resistance and moisture resistance when blended. It improves connection reliability.

The coupling agent may be added in the range of 0.2 to 10 parts by weight based on 100 parts by weight of the total amount of the radically polymerizable material (C) and the radical initiator (D), which serves as a coupling agent when the content is less than 0.2 part by weight. It is difficult to do it, and when it exceeds 10 weight part, the cohesion force of resin falls, and as a result, the problem of adhesive force and inferior reliability arises.

On the other hand, the composition for anisotropic conductive films of the present invention is 100 parts by weight of the total amount of the radical polymerizable material and the initiator content of other inhibitors such as polymerization inhibitors, antioxidants, heat stabilizers in order to add additional properties without inhibiting the basic physical properties It may further comprise in the range of 0.03 to 0.3 parts by weight relative.

The polymerization inhibitor may be selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, phenothiazine and mixtures thereof.

In addition, a phenolic or hydroxy cinnamate-based substance prepared for the purpose of preventing oxidation reaction and imparting thermal stability to the composition induced by heat may be added. For example, tetrakis- (methylene- (3, 5-di-t-butyl-4-hydro cinnamate) methane, 3,5-bis (1,1-dimethylethyl) -4-hydroxy benzene propanoic acid thiol di-2,1-ethanediyl ester, Octadecyl 3,5-di-t-butyl-4-hydroxy hydrocinnamate (manufactured by Ciba), 2,6-di-tertiary-p-methylphenol, and the like. Or it can mix and use 2 or more types.

No particular apparatus or equipment is required to form an anisotropic conductive film using the composition of the present invention, for example, the rate range at which the conductive particles are not pulverized after dissolving the composition of the present invention in an organic solvent such as toluene. After stirring for a certain period of time, it is applied to a thickness of 10 to 50 ㎛ on a release film and then dried for a period of time to obtain an anisotropic conductive film by volatilizing toluene or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for illustrative purposes only and are not intended to limit the protection scope of the present invention.

Example

Example 1

As a binder resin part which acts as a matrix for film formation, 30 weight% of acrylonitrile butadiene copolymers (1072CGX, Zeon Chemical) melt | dissolved in toluene / methyl ethyl ketone at 25 volume%; 20 weight% of polyvinyl butyral resins which were carboxyl-modified polyvinyl butyral resin (B-76, Solusa) and dissolved in methyl ethyl ketone at 30% by volume; As a hardening part, 38 weight% of epoxy acrylate polymers (SP1509, Showa polymer); 2.5 weight% of TMPTMA which is a (meth) acrylate monomer as an acrylate monomer; 2.5 weight% of 2-methacryloyloxyethyl phosphate which is a (meth) acrylate monomer as an epoxy acrylate monomo; 2.5 wt% of benzoyl peroxide as a thermosetting initiator; 0.49% by weight of 3-methacyloxypropyltrimethoxysilane as a coupling agent; 0.01 weight% of hydroquinone monomethyl ether as an inhibitor; Then, 4.00 wt% of conductive particles (Ni) having a size of 5 μm was added as a filler for imparting conductive performance to the anisotropic conductive film, thereby obtaining a film forming composition.

Comparative Example 1

As a binder resin part which acts as a matrix for film formation, 30 weight% of acrylonitrile butadiene copolymers (1072CGX, Zeon Chemical) melt | dissolved in toluene / methyl ethyl ketone at 25 volume%; 20% by weight of polyvinyl butyral resin (B-76, Solusa) dissolved in methyl ethyl ketone at 30% by volume; The other hardening part and the additive were carried out similarly to Example 1, and obtained the composition for film formation.

Comparative Example 2

As a binder resin part which acts as a matrix for film formation, 30 weight% of acrylonitrile butadiene copolymers (1072CGX, Zeon Chemical) melt | dissolved in toluene / methyl ethyl ketone at 25 volume%; 20% by weight of acrylic resin (SG-280, Nagase Chemtex) dissolved in toluene at 20% by volume; The other hardening part and the additive were carried out similarly to Example 1, and obtained the composition for film formation.

The composition was stirred for 60 minutes at room temperature (25 ° C.) within a rate range in which the conductive particles were not crushed. The composition was formed into a film having a thickness of 45 μm on a silicone release surface treated polyethylene base film, a casting knife was used for film formation, and the drying time of the film was 5 minutes at 80 ° C.

Evaluation of Physical Properties, Reliability and Flowability of Anisotropic Conductive Films

In order to evaluate the initial physical properties, reliability, and flowability of the anisotropic conductive films prepared from Example 1, Comparative Examples 1 and 2 above, each film was used at 80 ° C., 2 using PCB, COF, and TCP (Tape Carrier Package). First, the pressure bonding conditions of 1.0 MPa and 160 ° C., 5 seconds, and the main pressing conditions of 3.0 MPa were connected.

Sample preparation has a significant variation in the adhesion force depending on the presence or absence of SR contact between the PCB and the COF. In order to secure the pure adhesion of the film, the ACF width was 1.0mm for sample preparation and the variation caused by the SR contact was removed in advance.

Ⅰ) Each specimen was prepared by five, 90 ° adhesive strength was measured using the specimen prepared as described above, and the connection resistance was measured by 4 probe method.

Ii) The high temperature and high humidity reliability evaluation was performed at a temperature of 85 ° C. and a relative humidity of 85% for 250 hours and 500 hours, and iii) after 250 to 500 cycles at −40 ° C. to 100 ° C. and one cycle / hr. Thermal shock reliability evaluation was performed.

The physical properties of the anisotropic conductive film according to the present invention shown in the experimental results of Tables 1 to 2 can be interpreted as follows.

접착) adhesion

In general, the anisotropic conductive film requires an adhesive force of 600gf / cm or more, although it depends on the TEG and the conditions used by the company. Both the Example and the comparative example of this invention ensure the initial 600gf / cm adhesive force. However, the adhesive strength after high temperature, high humidity and thermal shock progressed to 600gf / cm or less in Comparative Examples 1 and 2, and in particular, in Comparative Example 2, not only the initial adhesive strength was low but also a large decrease after the reliability, which was reliable. It can be seen that the stability is lowered. In addition, compared to Comparative Example 1 using a polyvinyl butyral resin, Example 1 using a carboxyl-modified polyvinyl butyral resin can be seen that the initial adhesion is higher, high temperature, high humidity 500 hours (hr), thermal shock 500 times ( In the cycle), it shows the same level as the initial adhesive strength, it can be seen that the high adhesion required for the anisotropic conductive film.

Ii) connection resistance

In order to ensure sufficient conductivity of the anisotropic conductive film should have an electrical resistance of 2Ω or less under the same conditions as the above experiment, as shown in the connection resistance measurement results of Table 2, anisotropic using a carboxyl modified polyacetal resin according to the present invention It can be seen that the conductive film (Example 1) has a low resistance value in both the initial connection resistance and the connection resistance after the reliability evaluation. On the other hand, Comparative Example 1 shows an unstable connection state due to the increase in the electrical resistance of about 2Ω after the progress of reliability, and particularly in Comparative Example 2, it can be seen that much more than 2Ω, which is a usable area as 3.05Ω to 4.92Ω. . Considering the fact that this crimping time is gradually decreasing according to the recent process conditions, in particular, in order to perform the crimping in a short time of 4 seconds or less, it is necessary to maintain high reliability and current carrying capacity even under conditions of high temperature, high humidity and thermal shock. Examples 1 and 2 cannot satisfy this condition. On the contrary, Example 1 according to the present invention is continuously maintained under 2Ω even under adverse conditions such as high temperature, high humidity and thermal shock, so that anisotropic conductive film can be used in various devices and devices stably to solve problems of energization that may actually occur after long time use. Shows that it can be secured.

As described in detail above, incorporating a carboxyl-modified polyacetal resin having excellent adhesive properties and reliability into the radical polymerizable material as a curing agent as one component of the binder part improves high adhesive strength and heat resistance and moisture resistance, thereby providing excellent long-term reliability. A composition and an anisotropic conductive film can be obtained.

Although the present invention has been described as the preferred embodiment mentioned above, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Accordingly, the appended claims include such modifications and variations as fall within the spirit of the invention.

Claims (10)

(A) a thermoplastic resin, (B) a carboxyl modified polyacetal resin having a weight average molecular weight of 10,000 to 500,000, (C) a radical polymerizable material, (D) a radical initiator, and (E) conductive particles, The thermoplastic resin (A) is an anisotropic conductive adhesive, characterized in that at least one component selected from the group consisting of olefin resin, butadiene resin, acrylonitrile butadiene copolymer, carboxyl terminal acrylonitrile butadiene copolymer and phenoxy resin Composition. The method of claim 1, 40 to 100 parts by weight of the carboxyl-modified polyacetal resin (B) having a weight average molecular weight of 10,000 to 500,000 relative to 100 parts by weight of the thermoplastic resin (A) content and 80 to 150 parts by weight of the radically polymerizable material (C); , 0.3 to 10 parts by weight of the radical initiator (D) relative to a total of 100 parts by weight of the thermoplastic resin (A), a carboxyl-modified polyacetal resin (B) and a radical polymerizable material (C) having a weight average molecular weight of 10,000 to 500,000. Include, 0.2 to 30 parts by weight of the conductive particles (E) relative to a total of 100 parts by weight of the content of the carboxyl-modified polyacetal resin (B) and the radical polymerizable material (C) having a weight average molecular weight of 10,000 to 500,000. Anisotropic Conductive Adhesive Composition. delete The method of claim 1, The carboxyl-modified polyacetal resin (B) having a weight average molecular weight of 10,000 to 500,000 is selected from at least one of polyvinyl butyral resin or polyvinyl formal resin, and anisotropically characterized by carboxyl modification through an esterification reaction. Conductive adhesive composition. The method of claim 1, The radically polymerizable material (C) is an anisotropic conductive adhesive composition, characterized in that the epoxy acrylate. The method of claim 1, An anisotropic conductive adhesive composition further comprises 0.8 to 20 parts by weight of the monomer or oligomer of the radical polymerizable material to 100 parts by weight of the total amount of the radical polymerizable material (C) and the radical initiator (D). The method of claim 1, Anisotropically conductive adhesive composition further comprises 0.3 to 9 parts by weight of the radically polymerizable material having a phosphate ester structure relative to the total of 100 parts by weight of the radically polymerizable material (C) and the radical initiator (D) content. The method of claim 1, Anisotropically conductive adhesive composition, characterized in that it further comprises 0.2 to 10 parts by weight of the coupling agent based on 100 parts by weight of the total amount of the radically polymerizable material (C) and the radical initiator (D). The method of claim 1, Anisotropically conductive adhesive composition further comprises 0.03 to 0.3 parts by weight of inhibitor based on 100 parts by weight of the total amount of the radically polymerizable material (C) and the radical initiator (D). Anisotropically conductive adhesive film made of the anisotropically conductive adhesive composition according to any one of claims 1, 2 and 4 to 9.