KR100787740B1 - Anisotropic conductive film composition for high reliability - Google Patents

Abstract

An anisotropic conductive film composition, and an anisotropic conductive film prepared by using the composition are provided to improve strength, hydrolysis stability, heat resistance and water fastness and to enhance the adhesion stability for a long time, thereby improving reliance. An anisotropic conductive film composition comprises 5-50 wt% of a thermoplastic resin; 1-30 wt% of a carbodiimide compound represented by R1-X-(R2-NCN)n-R2-X-R3; 1-50 wt% of a (meth)acrylate oligomer; 1-30 wt% of a (meth)acrylate monomer; 0.1-15 wt% of a radical initiator; and 0.01-20 wt% of a conductive particle, wherein R1 and R3 are identical or different each other, have at least one olefin double bond, and represent a C3-C40 organic residue formed by removing the functional group from a compound having a functional group capable of reacting with isocyanate; R2 are identical or different each other and are a diisocyanate group; X represents a bond formed by the reaction of an isocyanate group and a functional group capable of reacting with an isocyanate group; and n is an integer of 1-40.

Description

Composition for high reliability anisotropic conductive film {ANISOTROPIC CONDUCTIVE FILM COMPOSITION FOR HIGH RELIABILITY}

The present invention relates to a composition for anisotropic conductive films, and more particularly, by including a carbodiimide compound having an olefinic double bond as a component of the hardened portion, various types including liquid crystal display (hereinafter referred to as LCD) Prevents short circuits between adjacent circuits during chip on glass mounting (hereinafter referred to as COG mounting) or chip on film mounting (hereinafter referred to as COF mounting) used in display devices. The present invention relates to a composition for anisotropic conductive films having initial low connection resistance, excellent adhesive strength and high reliability.

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 circuits and subjected to heating and pressurization under certain conditions, the circuit terminals are electrically connected by conductive particles, and the 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 given.

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 COG mounting or COF mounting.

As a conventional anisotropic conductive film, an epoxy type in which an epoxy- or phenol-based resin and a hardened portion made of a curing agent are mixed with a binder resin portion which generally serves as a matrix for film formation (i), and (ii) a binder resin portion (meta (Meth) acrylate type which mixed the hardening part which consists of an acryl-type oligomer, a monomer, and a radical initiator.

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 can not guarantee long-term connection and adhesion reliability.

On the other hand, the epoxy-type anisotropic conductive film is difficult to temporarily fix to the connection layer because it is not sticky and thus has poor workability, and has a high reaction temperature, making it difficult to maintain the process control and the connection device. there is a problem. In addition, the conventional (ii) (meth) acrylate type anisotropic conductive film has a flowability difference due to the difference in rheological 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. Since a large amount of bubbles are generated in the connection layer, the reliability cannot be guaranteed. On the contrary, when the reaction rate is rapidly adjusted, the conductive particles do not have sufficient contact with the circuit, and thus there is a problem in that good connection reliability cannot be guaranteed.

Accordingly, many researchers have been trying to solve the above problems.

The present invention is to solve the problems of the above-described anisotropic conductive film, and to provide a composition for anisotropic conductive film that can maintain excellent initial adhesion and excellent long-term reliability.

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

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) carbodiimide compound, (C) (meth) acrylate oligomer, (D) (meth) acrylate monomer, (E ) Radical initiator, and (F) conductive particles.

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

The composition for the anisotropic conductive film of the present invention is one of a hardened portion containing a carbodiimide compound which is excellent in initial adhesiveness and hydrolysis stability and can maintain long-term reliability in a radical polymerizable material used as a binder portion and a hardened portion made of a conventional thermoplastic resin. It is used as a component.

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

(A) thermoplastic resin

The thermoplastic resin of the present invention is a film-forming binder resin, which serves as a matrix for forming a film, and the thermoplastic resin may be acrylonitrile-based, butadiene-based, acrylic-based, urethane-based, polyamide-based, olefin-based, silicone-based resins, and the like. In detail, polyvinyl butyral, polyvinyl formal, polyester, phenol resin, epoxy resin, phenoxy resin, acrylic polymerizable resin, and the like may be commonly used.

The average molecular weight of the thermoplastic resin is used in the range of 1,000 to 5,000,000 and is preferably used in 5 to 50% by weight. If it is less than 5% by weight, there is a problem in film formation, and if it is more than 50% by weight, overall physical properties such as initial connection resistance and reliability may be degraded.

When using an acrylic polymer type resin as the thermoplastic resin for forming the film, it is preferable to use a resin having a high glass transition temperature (Tg) of 30 to 120 ° C., and the acrylic polymer type resin is in the range of 30 to 120 ° C. One or more acrylic monomers having a glass transition temperature of can be obtained by polymerizing at a high molecular weight of 10,000 or more.

Specifically, the acrylic polymer-based resin is ethyl, methyl, propyl, butyl, hexyl, oxyl, dodecyl, lauryl acrylate and methacrylate and its acrylate, acrylic acid, meta acrylate, methyl methacrylate It is a rubber-like polymer acrylic resin made by polymerizing at least one acrylic monomer selected from vinyl acetate and acrylic monomer modified therefrom.

In addition, the acrylic polymer-based resin essentially includes a hydroxyl group or a carboxyl group, may optionally further include an epoxy group or an alkyl group, wherein the acid value is preferably 10 to 150 mgKOH / g. This is because when an acrylic resin having an acid value of less than 10 mgKOH / g is used, there is a problem in that sufficient adhesive strength is not expressed, and when an acid value of more than 150 mgKOH / g is used, a problem of corrosion of the surface of the connection substrate occurs.

When the acrylic polymerizable resin is used as the thermoplastic resin (film forming binder resin), those having an average molecular weight of 50,000 to 2,000,000 can be used. If the molecular weight is too low, the film properties are not good due to excessive tack characteristics for film forming, and if the molecular weight is too high, compatibility with acrylate oligomers participating in other curing reactions is required. This is because deterioration may cause phase separation in the preparation of the composition mixture.

(B) Carbodiimide  compound

The carbodiimide compound of the present invention has a structure of the following formula and is used as a hydrolysis stabilizer of a compound containing an ester group by using the high reactivity of the carbodiimide group, or by crosslinking with a resin having a carboxyl group such as an acrylic resin. The strength of the resin can be improved. As a result, long-term connection and adhesion reliability can be expressed even after repeated shrinkage and expansion in the connection structure under hydrolysis stability, heat resistance, water resistance, and high temperature and high humidity, and can maintain excellent adhesion with various types of adherends such as zinc and copper polyimide. have.

Carbodiimide compounds having the structure of Formula 1 are used as stabilizers for hydrolytic degradation of polyaddition and polycondensation products, such as compounds containing ester groups, for example polyurethanes.

Carbodiimide compounds can be prepared by, for example, carbon dioxide by reacting mono- or polyisocyanates with catalysts such as compounds containing bound phosphorus, metal carbonyls, phospholines, phosphenes, phospholidines, oxides and sulfides thereof It can manufacture by removing.

The carbodiimide compound of the present invention is a compound represented by the following formula (2).

(Wherein R ₁ and R ₃ , which are the same or different, each have at least one olefinic double bond, and have an organic moiety having 3 to 40 carbon atoms formed by removing the functional group from a compound having a functional group capable of reacting with an isocyanate group) And a plurality of R ₂ groups may be different from each other, and X represents a bond formed by a reaction between an isocyanate group and a functional group capable of reacting with an isocyanate group, and n represents an integer of 1 to 40.

As a compound having at least one olefinic double bond for imparting R ₁ and R _{3 and} having a functional group capable of reacting with an isocyanate group, specifically, 2-hydroxy ethyl acrylate, 2-hydroxy propyl methacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, glycidyl acrylate, glycidyl methacrylate, allyl alcohol, 3-1 butene-1-ol, 4-penten-1-ol, allyl Amine, N-methylallylamine, N-ethyl-2-methylallylamine, diallylamine, allylcyclohexylamine, butadiene monooxide, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene , Allylglycidyl ether, 2-allylphenol, 2-allyloxyethanol, pentaerythritol triallyl ether, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monoacrylate, 2-sulfo Ethyl meta Acrylate, 2-hydroxy-3-dimethacryloxypropane or polypropylene glycol monoacrylate and the like.

In addition, as the diisocyanate used as R ₂ in the formula (2), aliphatic isocyanates such as 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylene diisocyanate or isophorone diisocyanate, or 4,4'- Aromatic diisocyanates, such as diphenylmethane diisocyanate, triylene diisocyanate, or triisopropylladenphenyl diisocyanate, can be used.

Such a carbodiimide compound may be polymerized together with an unsaturated polyester resin to improve the strength and hydrolysis resistance of the unsaturated polyester resin and to add to the resin having a functional group capable of reacting with a carbodiimide group to polymerize. If it is, the water resistance and chemical resistance of the resin can be improved.

It is preferable that the said carbodiimide compound is about 1 to 30 weight% with respect to the whole composition for anisotropic conductive films. This is because if it is less than 1% by weight, there is a problem that the initial adhesive strength and long-term reliability is lowered, and if it is more than 30% by weight, the film properties are degraded.

(C) ( Meta ) Acrylate Oligomer

 Examples of the (meth) acrylate oligomer of the present invention include urethane-based (meth) acrylates, epoxy-based (meth) acrylates, polyester-based (meth) acrylates, fluorine-based (meth) acrylates having an average molecular weight of about 1,000 to 100,000, Silicone type (meth) acrylate, phosphoric acid type (meth) acrylate, etc. can be used 1 or more types.

It is preferable to use the said (meth) acrylate oligomer in 1-50 weight% with respect to the whole composition for anisotropic conductive films of this invention, As a specific example of the said acrylate (methacrylate), methyl acrylate and ethyl Acrylate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimetholpropane triacrylate, tetra methylol methane tetra acrylate, 2-hydroxy-1,3 -Diacryloxy propane, 2, 2-bis [4- (acryloxy polymethoxy) phenyl] propane, 2, 2-bis [4- (acryloxy polyethoxy) phenyl] propane, dicyclopentenyl acrylate , Tricyclodecanyl acrylate, tris (acryloyloxyethyl) isocyanate, and the like, which are used alone or in combination There.

As the (meth) acrylate oligomer (C), one obtained from a fluorene derivative can be used, and preferably a fluorene-based epoxy (meth) acrylate oligomer, a fluorene-based urethane (meth) acrylate oligomer, or the like can be used. 1 or more types can be used. The excellent insulating properties of the fluorene structure of the fluorene-based (meth) acrylate excellently prevents the possibility of short circuit between circuits in the anisotropic conductive film using the same, and the rigid structure and excellent adhesion properties of the fluorene structure By ensuring the initial low connection resistance and high reliability of the anisotropic conductive film, it minimizes the possibility of defects in the production site, thereby improving productivity and improving the reliability of the final product.

In the case of the fluorene-based (meth) acrylate oligomer is preferably used in the range of 1 to 50% by weight. In this case, when the fluorene-based (meth) acrylate oligomer is used in excess of 50% by weight, the crosslinking degree is excessively formed after curing, so that the structure itself is too rigid and the shrinkage may be somewhat severe. If it is less than% by weight, the curing density is lowered, which may cause problems such as lowering of reliability.

(D) ( Meta ) Acrylate Monomer

The (meth) acrylate monomers of the present invention serve as reactive diluents. Examples of the (meth) acrylate monomers include 1,6-hexanediol mono (meth) acrylate, 2-hydroxy ethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, and 2-hydroxy butyl ( Meta) acrylate, 2-hydroxy-3-phenyl oxypropyl (meth) acrylate, 1,4-butanediol (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxy cyclo Hexyl (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylol-epan di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin di (meth) acrylate, t-hydrofurfuryl (meth) acrylate, Iso-decyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) Acrylate, isobonyl (meth) acrylate, tridecyl (meth) acrylate, ethoxyaddition nonylphenol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tri Ethylene glycol di (meth) acrylate, t-ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, tripropylene glycol di (meth) Acrylate, ethoxy addition bisphenol-A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, phenoxy-t-glycol (meth) acrylate, 2-methacryloyloxyethyl phosphate, 2 Methacryl One or more selected from the group consisting of hydroxyethyl phosphate, dimethylol tricyclo decaine di (meth) acrylate, trimethylolpropanebenzoate acrylate and mixtures thereof can be used, and for the anisotropic conductive film of the present invention It is preferable that it is about 1-50 weight% with respect to the whole composition.

(E) Radical Initiator

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

Examples of the photopolymerization initiator include benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4-methyl diphenyl sulfide, iso-propyl thioxanthone, diethyl thioxanthone, 4-diethyl ethyl benzoate, benzoin ether, Benzoyl propyl ether, 2-hydroxy-2-methyl-1-phenyl propane-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-iso-propyl benzene hydroperoxide, cumene hydroperoxide , Iso-butyl 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 furnace Edecanoate, di-n-propyl peroxy dicarbonate, di-iso-propyl peroxy carbonate, bis (4-t-butyl cyclohexyl) peroxy dicarbonate, di-2-ethoxy methoxy peroxy di Carbonate, di (2-ethylhexyl peroxy) dica Nate, 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) cyclo Dodecane, 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, and examples of the azo initiator include 2,2'-azobis (4-methoxy-2,4-dimethyl valeronitrile). ), 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-methyl butyl Nitrile), 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.

It is preferable that the said radical initiator contains 0.1-15 weight% with respect to the whole composition for anisotropic conductive films of this invention.

(F) conductive particles

 The conductive particles used in the present invention is applied as a filler (filler) for imparting electrical conductivity to 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 depending on the use in the range of 2 to 30 ㎛ by the pitch of the circuit applied, 0.01 to 20% by weight, more preferably based on the total composition for the anisotropic conductive film It may comprise 3 to 10% by weight.

Meanwhile, the composition of the composition for anisotropic conductive films of the present invention may additionally include 0.01 to 10% by weight of other additives such as polymerization inhibitors, antioxidants, and heat stabilizers to add additional physical properties without inhibiting basic physical properties. .

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

In addition, antioxidants or heat stabilizers, such as phenolic or hydroxy cinnamate-based substances, which have been prepared for the purpose of preventing oxidation reactions and imparting thermal stability to the composition induced by heat, may be added. (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 (above manufactured by Ciba), 2,6-di-tertiary-p-methylphenol, and the like. The other additives may be used alone or in combination of two or more thereof.

 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 on a release film to a thickness of 10 to 50 ㎛ and then dried for a certain time to obtain an anisotropic conductive film having a single layer structure by volatilizing toluene and 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  One

As a binder resin part which acts as a matrix for film formation, 20 weight% of NBR-type resins (N-34, Nipon Xeon) melt | dissolved in toluene / methyl ethyl ketone in 30 volume%; 20% by weight of urethane rubber (KUB2001, Gangnam Chemical) dissolved in a solvent of methyl ethyl ketone at 30% by volume; As a hardening part with hardening reaction, 30 weight% of an epoxy acrylate oligomer (SP1509, a shohwa polymer); 10% by weight of carbodiimide compound (P-200, Rein Chemie); 3% by weight of 2-methacryloyloxyethyl phosphate which is a radically polymerized (meth) acrylate monomer as the reactive monomer; Pentaerythritol tri (meth) acrylate 8% by weight; 3% by weight of 2-hydroxyethyl (meth) acrylate; 0.5 wt% of benzoyl peroxide as a thermoset initiator; And 0.5% by weight of lauryl peroxide; Then, as a filler for imparting conductive performance to the anisotropic conductive film, the conductive particles (NCI) having a size of 5 μm were insulated and then 5 wt% was added to complete the configuration.

Example  2

The binder resin part serving as a matrix for forming a film is the same as that of Example 1, and the curing part accompanying the curing reaction includes 30 wt% of a urethane acrylate oligomer (EA270, SK UCB); 10% by weight of carbodiimide compound (P-200, Rein Chemie); 3% by weight of 2-methacryloyloxyethyl phosphate which is a radically polymerized (meth) acrylate monomer as the reactive monomer; Pentaerythritol tri (meth) acrylate 8% by weight; 3% by weight of 2-hydroxyethyl (meth) acrylate; 0.5 wt% of benzoyl peroxide as a thermoset initiator; And 0.5% by weight of lauryl peroxide; Then, as a filler for imparting conductive performance to the anisotropic conductive film, the conductive particles (NCI) having a size of 5 μm were insulated and then 5 wt% was added to complete the configuration.

Example  3

The binder resin part serving as a matrix for forming a film is the same as in Example 1, and the curing part accompanying the curing reaction includes 15 wt% of an epoxy acrylate oligomer (SP1509, show oligomer); 15 wt% urethane acrylate oligomer (EA270, SK UCB); 10% by weight of carbodiimide compound (P-200, Rein Chemie); 3% by weight of 2-methacryloyloxyethyl phosphate which is a radically polymerized (meth) acrylate monomer as the reactive monomer; Pentaerythritol tri (meth) acrylate 8% by weight; 3% by weight of 2-hydroxyethyl (meth) acrylate; 0.5 wt% of benzoyl peroxide as a thermoset initiator; And 0.5% by weight of lauryl peroxide; Then, as a filler for imparting conductive performance to the anisotropic conductive film, the conductive particles (NCI) having a size of 5 μm were insulated and then 5 wt% was added to complete the configuration.

Comparative example  One

As a binder resin part which acts as a matrix for film formation, 20 weight% of NBR-type resins (N-34, Nipon Xeon) melt | dissolved in toluene / methyl ethyl ketone in 30 volume%; 20% by weight of urethane rubber (KUB2001, Gangnam Chemical) dissolved in a solvent of methyl ethyl ketone at 30% by volume; As a hardening part with hardening reaction, 40 weight% of epoxy acrylate oligomers (SP1509, a shohwa polymer); 3% by weight of 2-methacryloyloxyethyl phosphate which is a radically polymerized (meth) acrylate monomer as the reactive monomer; Pentaerythritol tri (meth) acrylate 8% by weight; 3% by weight of 2-hydroxyethyl (meth) acrylate; 0.5 wt% of benzoyl peroxide as a thermoset initiator; And 0.5% by weight of lauryl peroxide; Then, as a filler for imparting conductive performance to the anisotropic conductive film, the conductive particles (NCI) having a size of 5 μm were insulated and then 5 wt% was added to complete the configuration.

Comparative example  2

The binder resin part serving as a matrix for forming a film is the same as that of Comparative Example 1, and the curing part accompanying the curing reaction includes 40 wt% of a urethane acrylate oligomer (EA270, SK UCB); 3% by weight of 2-methacryloyloxyethyl phosphate which is a radically polymerized (meth) acrylate monomer as the reactive monomer; Pentaerythritol tri (meth) acrylate 8% by weight; 3% by weight of 2-hydroxyethyl (meth) acrylate; 0.5 wt% of benzoyl peroxide as a thermoset initiator; And 0.5% by weight of lauryl peroxide; Then, as a filler for imparting conductive performance to the anisotropic conductive film, the conductive particles (NCI) having a size of 5 μm were insulated and then 5 wt% was added to complete the configuration.

Comparative example  3

The binder resin part serving as a matrix for forming a film is the same as that of Comparative Example 1, and the curing part accompanying the curing reaction includes 20 wt% of an epoxy acrylate oligomer (SP1509, show polymerized polymer); 20 wt% urethane acrylate oligomer (EA270, SK UCB); 3% by weight of 2-methacryloyloxyethyl phosphate which is a radically polymerized (meth) acrylate monomer as the reactive monomer; Pentaerythritol tri (meth) acrylate 8% by weight; 3% by weight of 2-hydroxyethyl (meth) acrylate; 0.5 wt% of benzoyl peroxide as a thermoset initiator; And 0.5% by weight of lauryl peroxide; Then, as a filler for imparting conductive performance to the anisotropic conductive film, the conductive particles (NCI) having a size of 5 μm were insulated and then 5 wt% was added to complete the configuration.

Comparative example  4

The binder resin part serving as a matrix for forming a film is the same as that of Comparative Example 1, and the curing part accompanying the curing reaction includes 10% by weight of an epoxy acrylate oligomer (SP1509, show polymerized polymer); Carbodiimide compound (P-200, Rein Chemie) 35 wt%; 3% by weight of 2-methacryloyloxyethyl phosphate which is a radically polymerized (meth) acrylate monomer as the reactive monomer; 3 wt% pentaerythritol tri (meth) acrylate; 3% by weight of 2-hydroxyethyl (meth) acrylate; 0.5 wt% of benzoyl peroxide as a thermoset initiator; And 0.5% by weight of lauryl peroxide; Then, as a filler for imparting conductive performance to the anisotropic conductive film, the conductive particles (NCI) having a size of 5 μm were insulated and then 5 wt% was added to complete the configuration.

Examples and comparative examples are summarized in Table 1 below.

Anisotropy  Evaluation of Properties and Reliability of Conductive Film

In order to evaluate the initial physical properties and reliability of the anisotropic conductive films prepared from Examples 1 to 4 and Comparative Examples 1 to 4, each film was left at room temperature for 1 hour, and then ITO glass (indium tin oxide glass) and COF, Using a TCP (Tape Carrier Package), the connection was carried out under a pressure bonding condition of 160 ° C. for 1 second and a main compression condition of 180 ° C. for 5 seconds and 3 MPa.

Each specimen was prepared by seven, using the specimen prepared as described above was measured for 90 ° adhesive force, and the connection resistance was measured by the four probe (probe) method. In addition, high temperature and high humidity reliability evaluation was performed at a temperature of 85 ° C. and a relative humidity of 85% for 500 hours, and thermal shock reliability evaluation was repeated 500 times at −40 ° C. to 80 ° C., and the results are shown in Table 2 and Table. 3 is shown.

As shown in the results of Table 2, it can be seen that the anisotropic conductive film using the carbodiimide compound according to the present invention in the hardened portion is excellent in both the initial adhesive strength and the adhesive strength after reliability evaluation.

As shown in the results of Table 3, it can be seen that the anisotropic conductive film using the carbodiimide compound according to the present invention has a low resistance value at both the initial connection resistance and the connection resistance after the reliability evaluation. The anisotropic conductive film using the carbodiimide compound according to the present invention has excellent initial properties and high reliability as compared to the anisotropic conductive film composed only of other radically curable resins such as epoxy and urethane acrylate, which are commercially available. Able to know.

As described in detail above, the present invention comprises a carbodiimide compound having a molecular weight (Mw) of about 100 to 100,000 and having an olefinic double bond useful as a hydrolysis stabilizer and a crosslinking agent for resins, thereby providing The anisotropic conductive film formed from the composition of the resin is excellent in initial bond strength improvement and hydrolysis stability, heat resistance, water resistance, and maintains the bonding structure to various adhesives such as zinc copper, polyimide and the like especially under high temperature and high humidity conditions. Not only adhesion but also high long-term reliability under high temperature and high humidity conditions.

Therefore, it is possible to improve productivity by minimizing the possibility of defects in the field, and there is a big advantage to improve the reliability of the final product. In addition, since fine connection is possible in accordance with the trend of circuit patterns becoming more and more fine, there is an advantage that it is possible to cope with the development of high-performance electronic components in the electronic industry.

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) 5-50 weight percent of thermoplastic resin; (B) 1-30 wt% of the carbodiimide compound represented by the following formula (2); (C) 1-50% by weight of (meth) acrylate oligomer; (D) 1-30 weight percent of the (meth) acrylate monomer; A composition for anisotropic conductive films comprising 0.1 to 15% by weight of (E) radical initiator and 0.01 to 20% by weight of (F) conductive particles. [Formula 2]

(Wherein R ₁ and R ₃ , which are the same or different, each have at least one olefinic double bond, and have an organic moiety having 3 to 40 carbon atoms formed by removing the functional group from a compound having a functional group capable of reacting with an isocyanate group) Indicates, R ₂ is diisocyanate and the plurality of R ₂ groups may be different from each other, X represents a bond formed by a reaction between an isocyanate group and a functional group capable of reacting with an isocyanate group, and n represents an integer of 1 to 40.) delete The method of claim 1, The thermoplastic resin (A) has an average molecular weight of 1,000 to 5,000,000, an anisotropic conductivity, characterized in that at least one selected from the group consisting of acrylonitrile-based, butadiene-based, acrylic, urethane-based, polyamide-based, olefin-based and silicone-based resins Composition for film The method of claim 3, wherein The thermoplastic resin (A) has a high glass transition temperature (Tg) of 30 to 120 ℃, an acrylic polymerizable resin having an acid value of 10 to 150 mgKOH / g composition for anisotropic conductive film. The method of claim 1, The carbodiimide compound (B) has a molecular weight of 100 to 100,000, a composition for an anisotropic conductive film produced by reacting a catalyst to monoisocyanate or polyisocyanate to remove carbon dioxide. The method of claim 1, The (meth) acrylate oligomers (C) are urethane-based (meth) acrylates, epoxy-based (meth) acrylates, polyester-based (meth) acrylates, fluorine-based (meth) acrylates and silicones having an average molecular weight in the range of 1,000 to 100,000. A composition for anisotropic conductive films, characterized in that at least one oligomer selected from the group consisting of (meth) acrylate, phosphoric acid (meth) acrylate, and fluorene (meth) acrylate. The method of claim 1, The (meth) acrylate monomer (D) is 1,6-hexanediol mono (meth) acrylate, 2-hydroxy ethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, 2-hydroxy-3-phenyl oxypropyl (meth) acrylate, 1,4-butanediol (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxy Roxy cyclohexyl (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylol-epan di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin di (meth) acrylate, t-hydroperfuryl (meth) acrylate, Iso-decyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) Acrylate, isobonyl (meth) acrylate, tridecyl (meth) acrylate, ethoxyaddition nonylphenol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tri Ethylene glycol di (meth) acrylate, t-ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, tripropylene glycol di (meth) Acrylate, ethoxy addition bisphenol-A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, phenoxy-t-glycol (meth) acrylate, 2-methacryloyloxyethyl phosphate, 2 Methacryl Ilrok when ethyl phosphate, dimethylol-tricyclo decane di (meth) acrylate, trimethylolpropane benzoate acrylate and one composition for the anisotropic conductive film, characterized in that at least one kind monomer selected from the group consisting of a mixture thereof. The method of claim 1, The radical initiator (E) is an anisotropic conductive film composition, characterized in that at least one member selected from the group consisting of a photopolymerization initiator and a thermosetting initiator. The method of claim 1, The conductive particles (F) are metal particles including Au, Ag, Ni, Cu, solder; carbon; A resin comprising polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol and a modified resin thereof coated with a metal containing Au, Ag, Ni; And at least one selected from the group consisting of insulated conductive particles coated by adding insulating particles thereon. An anisotropic conductive film made of the composition for anisotropic conductive films according to any one of claims 1 and 3 to 9.