KR100673773B1 - Anisotropic conductive film composition using fluoren-based (meth)acrylate - Google Patents

Abstract

Provided is an anisotropic conductive film composition using fluorene-based (meth)acrylate, and thus the prepared anisotropic conductive film prevents a short circuit between circuits and has low initial connection resistance and long-term reliance. The anisotropic conductive film composition comprises (i) 10-80wt% of a thermoplastic resin, (ii) 1-60wt% of a fluorene-based (meth)acrylate oligomer, (iii) 1-50wt% of (meth)acrylate monomer, (iv) 0.1-15wt% of a radical initiator, and (v) 0.01-20wt% of conductive particles. The fluorene-based (meth)acrylate oligomer(ii) is at least one oligomer obtained from fluorene derivatives of the following formula 1, wherein each of Rs is independently an alkyl group, an alkoxy group, an aryl group, or a cycloalkyl group, each of (m)s is independently an integer of 0-4, and each of (n)s is independently an integer of 2-5.

Description

Composition for anisotropic conductive films using fluorene-based (meth) acrylate {ANISOTROPIC CONDUCTIVE FILM COMPOSITION USING FLUOREN-BASED (METH) ACRYLATE}

The present invention relates to a composition for anisotropic conductive films using fluorene-based (meth) acrylate, wherein one component of the cured portion of the fluorene-based (meth) acrylate derivative in which (meth) acrylate is bonded as a functional group to the fluorene derivative Chip on glass mounting (hereinafter referred to as COG mounting) or chip on film mounting used in various display devices including liquid crystal displays (hereinafter referred to as LCDs). The present invention relates to a composition for anisotropic conductive films which improves productivity by preventing short between adjacent circuits for mounting (hereinafter referred to as COF mounting) and having initial low connection resistance and high reliability.

The anisotropic conductive film generally refers to a film 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 pressing processes under a certain condition, the circuit terminals are electrically connected by conductive particles, and an insulating adhesive resin is filled in the pitch between adjacent circuits to form conductive particles. Since they exist independently of each other, high insulation is provided. Such anisotropic conductive films are widely used for LCD panels, tape carrier packages (hereinafter referred to as TCP), or electrical connections such as 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 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, the conventional (i) 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 an inadequate 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. 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, when the reaction rate is quickly adjusted, there is a problem that the conductive particles do not make sufficient contact with the circuit and thus cannot guarantee good connection reliability. .

The present invention is to solve the above problems, by using the fluorene-based (meth) acrylate as one of the components of the hardened portion can prevent short (short) between circuits, the initial low connection resistance and excellent long-term It is an object to provide a resin composition for producing an anisotropic conductive film that can have reliability.

In order to achieve the above object, in the present invention, a fluorene-based (meth) acrylate having a rigid structure as a component of the hardened portion in the existing composition for anisotropic conductive films of the (meth) acrylate type and exhibiting excellent adhesion and insulation It is characterized by the addition of.

That is, the present invention is a binder resin portion made of a thermoplastic resin; Cured part which consists of a fluorene type (meth) acrylate oligomer, a (meth) acrylate oligomer, a fluorene type (meth) acrylate monomer, a (meth) acrylate monomer, and a radical initiator; And it provides the composition for anisotropic conductive films containing electroconductive particle.

In another aspect, the present invention provides an anisotropic conductive film formed of the composition for the anisotropic conductive film.

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

The composition for anisotropic conductive films of the present invention

(Iii) a thermoplastic resin,

(Ii) fluorene-based (meth) acrylate oligomers,

(Iii) a (meth) acrylate monomer,

(Iii) a radical initiator, and

(Iii) It is characterized by including electroconductive particle.

The composition for anisotropic conductive films according to the present invention is preferably

(Iii) 10 to 80 weight percent of thermoplastic resin;

(Ii) 1 to 60% by weight of fluorene-based (meth) acrylate oligomer;

(Iii) 1 to 50% by weight of (meth) acrylate monomer;

(Iii) 0.1 to 15 wt% of a radical initiator; And

(Iii) 0.01 to 20 wt% of conductive particles

It includes.

The composition for anisotropic conductive films according to the present invention comprises (i) at least one member selected from the group consisting of ordinary thermoplastic resins serving as a matrix necessary for forming a film, and (ii) a fluorene-based (meth) acrylate oligomer. A resin composition comprising at least one oligomer selected from the group, (iii) at least one monomer selected from the group consisting of (meth) acrylate monomers, (iii) radical polymerization initiators, and (iii) conductive particles.

Meanwhile, fluorene-based (meth) acrylate oligomers or monomers applied according to the object of the present invention may be obtained from fluorene derivatives represented by the following general formula (1). As a conventional method for obtaining a fluorene derivative, a method of separating and purifying tar has been known. However, the content of fluorene derivative in tar is low, and it is impossible to obtain a large amount of high-purity fluorene derivative by the above method. Therefore, in recent years, a method of synthesizing fluorene derivatives in addition to the separation and purification methods such as the production of aryl radicals through the reaction of aromatic diazoaluminum compounds with copper ions (Pschorr reaction), indenes and butadienes Otto Paul Hermann Diels-Kurt Alder reaction and the like.

[Formula 1]

Where

Each R is independently an alkyl group, an alkoxy group, an aryl group, or a cycloalkyl group,

m is each independently an integer of 0 to 4,

n is independently an integer of 2-5.

The fluorene derivative of Chemical Formula 1 may be obtained by condensation reaction of a phenol compound obtained by air oxidation of fluorene prepared by the above reaction under coexistence of a thiol compound such as mercaptocarboxylic acid and an aqueous hydrochloric acid solution. have.

In the fluorene derivative represented by the formula (1), R represents an alkyl group, an alkoxy group, an aryl group or a cycloalkyl group, and m represents an integer of 0 to 4. In addition, the kind of substituent R may differ with m which shows the number of substituents. Examples of alkyl groups there may be mentioned a C _{1 ~ 4} alkyl group such as methyl, ethyl, propyl, iso- propyl, n- butyl, s- butyl, t- butyl, iso- butyl group. Examples of cycloalkyl groups there may be mentioned a C _{4 ~ 8} cycloalkyl group such as cyclopentyl group, a cyclohexyl group. As the alkoxy group may be mentioned a group C _{1 ~ 4} alkoxy, such as methoxy, ethoxy, propoxy, n- butoxy, iso- butoxy group, t- butoxy group. Examples of the aryl group may be exemplified a phenyl group, 2-methyl-phenyl, 3-methyl-phenyl, 4-methyl-phenyl, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, such as a C _{6 ~ 8} aryl.

Specific examples of the fluorene derivative of Chemical Formula 1 include 9,9-bis- (4-hydroxy phenyl) fluorene; 9,9-bis- (4-hydroxy-2-methyl phenyl) fluorene, 9,9-bis- (4-hydroxy-3-methyl phenyl) fluorene, 9,9-bis- (4-hydroxy Hydroxy-3-ethyl phenyl) fluorene, 9,9-bis- (3-hydroxy-6-methyl phenyl) fluorene, 9,9-bis- (2-hydroxy-4-methyl phenyl) fluorene, 9,9-bis- (alkyl hydroxy phenyl) fluorene such as 9,9-bis- (4-hydroxy-3-t-butyl phenyl) fluorene; 9,9-bis (4-hydroxy-3,5-dimethyl phenyl) fluorene, 9,9-bis (4-hydroxy-2,6-dimethyl phenyl) fluorene, 9,9-bis (4- 9,9-bis (dialkyl hydroxy phenyl) fluorene such as hydroxy-3,5-di-tert-butyl phenyl) fluorene; 9,9-bis (cycloalkyl hydroxy) fluorene such as 9,9-bis (4-hydroxy-3-cyclohexyl phenyl) fluorene; 9,9-bis (arylhydroxy phenyl) fluorene, such as 9, 9-bis (4-hydroxy-3- diphenyl) fluorene, etc. are mentioned.

In the present invention, among these fluorene derivatives, oligomers or monomers belonging to fluorene-based epoxy (meth) acrylates or fluorene-based urethane (meth) acrylates can be used.

In order to synthesize a fluorene-based epoxy (meth) acrylate, for example, a fluorene derivative such as the following Chemical Formula 2 may be used, and by reacting glycidyl (meth) acrylic acid with a fluorene compound represented by the following Chemical Formula 2, A fluorene epoxy (meth) acrylate represented by the formula (3) can be obtained.

[Formula 2]

Where

Each R ₁ is independently a hydrogen atom or a methyl group,

n are each independently an integer of 0 to 15,

m is each independently an integer of 2-4.

[Formula 3]

Where

R ₁ , R ₂ Are each independently a hydrogen atom or a methyl group,

n are each independently an integer of 0 to 15,

m is each independently an integer of 2-4.

The reaction of the fluorene derivative of Formula 2 with glycidyl (meth) acrylate to obtain the fluorene epoxy (meth) acrylate of Formula 3 is a temperature range at 50 to 120 ℃ using an appropriate solvent, if necessary It can be obtained by the reaction for 5 to 30 hours in. Examples of the solvent that can be used above include alkylene monoalkyl ether acetates such as methyl cellosolve acetate, propylene glycol monomethyl ether acetate and 3-methoxy butyl-1-acetate; Methyl ethyl ketone, methyl amyl ketone and the like.

In addition, a method for synthesizing the fluorene-based urethane (meth) acrylate, for example, in the fluorene derivative diol which can be derived from the fluorene derivatives such as the general formula (2) as shown in the following formula (4) By reacting isocyanate and ester with (meth) acrylate having a hydroxyl group, a fluorene urethane (meth) acrylate represented by the following formula (5) can be obtained.

[Formula 4]

Where

Each R ₁ is independently a hydrogen atom or a methyl group,

n is each independently an integer of 1-5.

[Formula 5]

Where

R ₁ and R ₄ are each independently a hydrogen atom or a methyl group,

R ₂ and R ₃ are each independently an aliphatic and alicyclic or aromatic group,

n are each independently an integer of 1 to 5,

m is each independently an integer of 2-5.

As a method for synthesizing the fluorene urethane (meth) acrylate represented by the formula (5), (meth) acrylate having a hydroxyl group in the diisocyanate and ester in the fluorene derivative diol of the formula (4) (hereinafter, A method of reacting all hydroxyl group-containing (meth) acrylates together, a method of reacting a fluorene derivative diol with diisocyanate and then a hydroxyl group-containing (meth) acrylate, a diisocyanate-containing hydroxyl group-containing (meth) acryl Method of reacting fluorene derivative diol after reacting rate, reacting diisocyanate with hydroxyl group-containing (meth) acrylate and then reacting fluorene derivative diol and hydroxyl group-containing (meth) acrylate To react again.

In this case, the fluorene derivative diol (diol) may be exemplified by a compound in which approximately 1 to 10 moles of ethylene oxide or propylene oxide is added to 1 mole of 9,9-bis- (4-hydroxyphenyl) fluorene, Examples of the diisocyanate include 2,4-triylene diisocyanate, 2,6-triylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, m- Phenylene diisocyanate, p-phenylene diisocyanate, 3,3-dimethyl-4,4-diphenyl methane diisocyanate, 4,4-diphenyl methane diisocyanate, 3,3-dimethyl phenylene diisocyanate, 4, 4-biphenylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 4-diphenyl propane diisocyanate, lysine diisocyanate, etc. are mentioned. Examples of the hydroxyl group-containing (meth) acrylate include 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 cyclohexyl (meth) acrylate, 1,6-hexane Diol (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylol-epan di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. are mentioned. Such diisocyanate and hydroxyl-containing (meth) acrylate can be used individually or in combination of 2 or more types.

On the other hand, examples of the aliphatic that may be substituted with R ₂ and R ₃ in Chemical Formula 5 include C1-10 alkylene groups such as methylene, ethylene, propylene, hexamethylene, 2,2,4-trimethyl hexamethylene, and the like. Examples of the alicyclic groups include cyclohexylene, methylene bis cyclohexylene, bicyclo heptane, and the like, and examples of the aromatics include phenylene, triylene, xylene, diphenyl methane, naphthalene, and the like.

As the composition of the composition for anisotropic conductive films of the present invention using the fluorene-based (meth) acrylate derivatives as described above, a thermoplastic resin may be used as the binder resin portion that serves as a matrix for forming the film. The thermoplastic resin may be one or more selected from the group consisting of acrylonitrile, butadiene, acryl, urethane, polyamide, olefin and silicone resins, and the average molecular weight is preferably in the range of 1,000 to 1,000,000. Do. In addition, the thermoplastic resin preferably contains 10 to 80% by weight based on the total composition for the anisotropic conductive film.

In addition, as the composition of the composition for the anisotropic conductive film of the present invention, the curing reaction occurs to ensure the adhesion between the connection layer and the connection reliability as a curing portion fluorene-based (meth) acrylate oligomer, (meth) acrylate monomer, and radical initiator And may further include (meth) acrylate oligomers, fluorene-based (meth) aract monomers.

As the fluorene-based (meth) acrylate oligomer which is one component of the cured part of the present invention and corresponding to the characteristic part of the present invention, one obtained from the fluorene derivative of Formula 1 may be used as described above, and preferably One or more fluorene-based epoxy (meth) acrylate oligomers represented by the formula (3), or fluorene-based urethane (meth) acrylate oligomers represented by the formula (5) may be used.

The excellent insulating properties of the fluorene structure of the fluorene-based (meth) acrylate prevents the occurrence of short circuit between circuits in the anisotropic conductive film using the same, and the rigid structure and excellent adhesiveness of the fluorene structure is anisotropic using By ensuring the initial low connection resistance and high reliability of the conductive film, it minimizes the possibility of defects on the production site, improving productivity and improving the reliability of the final product.

In the case of the fluorene-based (meth) acrylate oligomer is preferably contained in the range of 1 to 60% by weight based on the total composition for the anisotropic conductive film of the present invention, it is a fluorene-based (meth) acrylate oligomer 1 If it is less than% by weight, the rigid structure, excellent adhesion and insulation that can be obtained from the fluorene structure is not obtained, and when it exceeds 60% by weight, the structure itself becomes too rigid and the shrinkage rate is rather severe. This can happen.

In addition, in the composition of the present invention, one or more kinds of oligomers selected from other (meth) acrylate oligomer groups can be used. Other (meth) acrylate oligomers include urethane-based (meth) acrylates, epoxy-based (meth) acrylates, polyester-based (meth) acrylates, fluorine-based (meth) acrylates and silicones with an average molecular weight in the range of about 1,000 to 100,000. (Meth) acrylate, phosphate (meth) acrylate, etc. can be used 1 or more types. It is preferable to use the said other (meth) acrylate oligomer in 1 to 60 weight% with respect to the whole composition for anisotropic conductive films of this invention.

In the present invention, at least one monomer selected from the group of fluorene-based (meth) acrylate monomers can be further used. That is, the use of the fluorene-based (meth) acrylate monomers in the present invention may be optional depending on the case and use. The fluorene-based (meth) acrylate monomer serves as a reactive diluent.

The fluorene-based (meth) acrylate monomer can be used as the oligomer obtained from the fluorene derivative of the formula (1), preferably fluorene-based epoxy (meth) acrylate monomer represented by the formula (3), Alternatively, one or more fluorene-based urethane (meth) acrylate monomers represented by Formula 5 may be used.

In the case of the fluorene-based (meth) acrylate monomer, it is preferable to be contained in the range of 1 to 50% by weight based on the whole composition for anisotropic conductive films of the present invention. In this case, when the fluorene-based (meth) acrylate monomer 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.

Meanwhile, in the present composition, the (meth) acrylate monomer serves as a reactive diluent. 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 -Methacrylo One or more selected from the group consisting of oxyethyl phosphate, dimethylol tricyclo decaine di (meth) acrylate, trimethylolpropanebenzoate acrylate and mixtures thereof can be used, and the composition for anisotropic conductive films of the present invention It is preferable that it is about 1-50 weight% with respect to the whole.

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 combining 1 or more types.

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 isopro 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) dicarbonane , 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) cyclodo Decane, 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-dimethylvaleronitrile). , 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 butyronitrile Reel), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 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, and the like. 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.

The electroconductive particle used by this invention is applied as a filler for giving electroconductive performance as a composition of the composition for anisotropic conductive films of this invention. As said electroconductive particle, Metal particle containing Au, Ag, Ni, Cu, solder, etc .; carbon; A resin containing polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol and the like and a modified resin thereof coated with a metal containing Au, Ag, Ni, etc .; One or more kinds of the insulated conductive particles and the like coated with the insulating particles added thereon may be used. The size of the conductive particles can be selected and used depending on the application in the range of 2 to 30 ㎛ by the pitch of the circuit to be applied, 0.01 to 20% by weight based on the total composition for the anisotropic conductive film, more preferably 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 such as phenolic or hydroxy cinnamate-based substances, which have been 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-ethane Diyl ester, octadecyl 3,5-di-t-butyl-4-hydroxy hydro cinnamate (manufactured by Ciba), 2,6-di-tertiary-p-methylphenol, and the like. Can be used individually or in mixture of 2 or more types, respectively.

No special apparatus or equipment is required to form an anisotropic conductive film using the composition of the present invention, for example, the speed range in which the conductive particles are not pulverized after dissolving the composition of the present invention in an organic solvent such as toluene and liquefying. 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 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 an acrylic resin (SG-280, Nagase Chemtex) dissolved in toluene at 30% by volume; 7% by weight of phenoxy resin (YDCN-500-90P, Kukdo Chemical) dissolved in toluene at 40% by volume; As a hardening part with hardening reaction, 40 weight% of fluorene type epoxy (meth) acrylate monomers (BPEF-A, Osaka gas) represented by General formula (3); 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 Co., Ltd.) having a size of 5 μm were insulated, and then 3 wt% was added to complete the configuration.

Example  2

Fluorene-based epoxy (meth) acryl represented by the formula (3) instead of 40% by weight of the fluorene-based epoxy (meth) acrylate monomer (BPEF-A, Osaka Gas) represented by the formula (3) 20% by weight of acrylate monomer (BPEF-A, Osaka Gas); It carried out by the same method as Example 1 except having used 20 weight% of other epoxy (meth) acrylate oligomers (EB-600, SK-UCB).

Example  3

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 an acrylic resin (SG-280, Nagase Chemtex) dissolved in toluene at 30% by volume; 7% by weight of phenoxy resin (YDCN-500-90P, Kukdo Chemical) dissolved in toluene at 40% by volume; As a hardening part with hardening reaction, a fluorene-type urethane (meth) acrylate oligomer [4,4- (9-fluorenylidene bis 2-phenoxyethanol) (Aldrich) and 2,4- which are represented by General formula (5) Obtained by reacting triylene diisocyanate (Aldrich) under a catalyst followed by 2-hydroxy propyl acrylate] 20% by weight; 20% by weight of other epoxy (meth) acrylate oligomers (EB-600, SK-UCB); 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% benzoyl peroxide as the thermosetting 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 Co., Ltd.) having a size of 5 μm were insulated, and then 3 wt% was added to complete the configuration.

Example  4

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 an acrylic resin (SG-280, Nagase Chemtex) dissolved in toluene at 30% by volume; 7% by weight of phenoxy resin (YDCN-500-90P, Kukdo Chemical) dissolved in toluene at 40% by volume; As a hardening part accompanying hardening reaction, the fluorene type epoxy (meth) acrylate oligomer represented by General formula (3) [fluorene type epoxy (BPF-G, BCF-G, BPEF-G, Osaka gas) and acrylic acid (Aldrich) are used. Obtained by reaction under a catalyst] 20% by weight; Fluorene urethane (meth) acrylate oligomers represented by the formula (5) [4,4- (9-fluorenylidene bis 2-phenoxyethanol) (Aldrich) and 2,4-trilene diisocyanate (Aldrich) Obtained by reacting 2-hydroxy propyl acrylate after reacting under a catalyst] 20% by weight; 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 Co., Ltd.) having a size of 5 μm were insulated, and then 3 wt% was added to complete the configuration.

Example  5

As a binder resin part which acts as a matrix for film formation, 10 weight% of NBR-type resins (N-34, Nippon Xeon) melt | dissolved in toluene / methyl ethyl ketone in 30 volume%; 25% by weight of an acrylic resin (KLS-1025, Fujikura Kasei) dissolved in toluene at 30% by volume; 12% by weight of phenoxy resin (YDCN-500-90P, Kukdo Chemical) dissolved in toluene at 40% by volume; As a hardening part with hardening reaction, 35 weight% of fluorene type epoxy (meth) acrylate oligomers (BPEF-A, Osaka gas) represented by General formula (3); 5% by weight of pentaerythritol hexa (meth) acrylate, which is a radically polymerized (meth) acrylate monomer as the reactive monomer; 2% by weight of 2-methacryloyloxyethyl phosphate; 2% by weight of 2-hydroxyethyl (meth) acrylate; 5% by weight of a fluorene-based epoxy (meth) acrylate monomer (BPEF-A, Osaka Gas) represented by Formula 3; 0.5 wt% of benzoyl peroxide as a thermoset initiator; And 0.5% by weight of lauryl peroxide; Then, in order to impart conductive performance to the anisotropic conductive film, conductive particles (NCI) having a size of 5 μm were insulated, and then 3 wt% was added to complete the configuration.

Example  6

As a binder resin part which acts as a matrix for film formation, 30 weight% of NBR-type resin (N-34, Nippon Xeon) melt | dissolved in toluene / methyl ethyl ketone at 30 volume%; 10% by weight of acrylic resin (KMM-34, Fujikura Kasei) dissolved in toluene at 30% by volume; 7% by weight of phenoxy resin (YDCN-500-90P, Kukdo Chemical) dissolved in toluene at 40% by volume; As a hardening part with hardening reaction, a fluorene-type urethane (meth) acrylate oligomer [4,4- (9-fluorenylidene bis 2-phenoxyethanol) (Aldrich) and 2,4- which are represented by General formula (5) Obtained by reacting triylene diisocyanate (Aldrich) under a catalyst followed by 2-hydroxy propyl acrylate] 22% by weight; 22% by weight of other epoxy (meth) acrylate oligomers (EB-3701, SK-UCB); 2% by weight of 2-methacryloyloxyethyl phosphate which is a radically polymerized (meth) acrylate monomer as a reactive monomer serving as a diluent; Pentaerythritol tri (meth) acrylate 2% by weight; 1% 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 Co., Ltd.) having a size of 5 μm were insulated, and then 3 wt% was added to complete the configuration.

Comparative example  One

As a component of the hardening part accompanied by the curing reaction, an epoxy (meth) acrylate oligomer (EB-600, SK-UCB) was used instead of the fluorene-based epoxy acrylate oligomer represented by the formula (3) (BPEF-A, Osaka Gas). Except that was carried out in the same manner as in Example 1.

Comparative example  2

Epoxy (meth) acrylate oligomer (SP-4010, Showa), which is commercialized in place of the fluorene-based epoxy (meth) acrylate oligomer represented by the formula (3) as a component of the hardening part accompanied by a curing reaction (BPEF-A, Osaka Gas). Polymer) and 5% by weight of pentaerythritol hexa (meth) acrylate instead of 5% by weight of fluorene epoxy (meth) acrylate monomer in the reactive monomer was used in the same manner as in Example 5 Was carried out.

Comparative example  3

Except for using a commercially available urethane (meth) acrylate oligomer (UV-3000B, light) instead of the fluorene-based urethane (meth) acrylate oligomer (JSR) represented by the formula (5) as a component of the curing part accompanied by the curing reaction And the same method as in Example 6.

Said combination liquid was stirred for 60 minutes at normal temperature (25 degreeC) within the speed range in which electroconductive particle does not grind | pulverize. The combination solution formed a film with a thickness of 20 μm on a polyethylene release film treated with a silicone release surface, a casting knife was used for film formation, and the drying time of the film was 10 minutes.

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 6 and Comparative Examples 1 to 3, 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 1000 hours, and thermal shock reliability evaluation was repeated 1000 times of −40 ° C. to 80 ° C. temperature conditions.

The results are shown in Tables 1 and 2 below.

As shown in the 90 ° adhesive strength results of Table 1, it can be seen that the anisotropic conductive film using the fluorene-based (meth) acrylate derivative according to the present invention is excellent in both the initial adhesive strength and the adhesive strength after reliability evaluation.

As shown in the connection resistance measurement results of Table 2, it can be seen that the anisotropic conductive film using the fluorene-based (meth) acrylate derivative according to the present invention has a low resistance value in both the initial connection resistance and the connection resistance after reliability evaluation. According to these results, the anisotropic conductive film using the fluorene-based (meth) acrylate derivative according to the present invention has excellent initial properties and high reliability compared to the anisotropic conductive film using the conventional commercialized (meth) acrylate oligomers It can be seen that.

As described in detail above, the anisotropic conductive film formed from the composition of the present invention using fluorene-based (meth) acrylate, due to the rigid structure, excellent adhesion and insulation of the fluorene structure, the occurrence of short between circuits It can be prevented, has a low initial connection resistance and high reliability, thereby minimizing the possibility of defects in the production site, improving productivity, and improving the reliability of the final product. In addition, fine connection is possible in accordance with the trend of the circuit pattern becoming more and more fine, there is an advantage that can respond to 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 (13)

(Iii) 10 to 80 weight percent of thermoplastic resin; (Ii) 1 to 60% by weight of fluorene-based (meth) acrylate oligomer; (Iii) 1 to 50% by weight of (meth) acrylate monomer; (Iii) 0.1 to 15 wt% of a radical initiator; And (Iii) 0.01 to 20 wt% of conductive particles Composition for anisotropic conductive film comprising a. delete The composition for anisotropic conductive film according to claim 1, wherein the composition further comprises 1 to 60% by weight of at least one oligomer selected from the group of (meth) acrylate oligomers. The composition for anisotropic conductive film according to claim 1 or 3, wherein the composition further comprises 1 to 50% by weight of at least one monomer selected from the group of fluorene-based (meth) acrylate monomers. The composition for anisotropic conductive film according to claim 1, wherein the composition further comprises 0.01 to 10% by weight of at least one additive selected from the group consisting of a polymerization inhibitor, an antioxidant, and a heat stabilizer. The composition for anisotropic conductive films according to claim 1, wherein the (ii) fluorene-based (meth) acrylate oligomer is at least one oligomer obtained from a fluorene derivative represented by the following formula (1). [Formula 1]

Where Each R is independently an alkyl group, an alkoxy group, an aryl group, or a cycloalkyl group, m is each independently an integer of 0 to 4, n is independently an integer of 2-5. The fluorene-based (meth) acrylate oligomer according to claim 1, wherein the fluorene-based (meth) acrylate oligomer is a fluorene-based epoxy (meth) acrylate represented by the following formula (3) and a fluorene-based urethane (meth) acryl represented by the following formula (5). The composition for an anisotropic conductive film, characterized in that at least one oligomer selected from the group consisting of a rate. [Formula 3]

Where R ₁ , R ₂ Are each independently a hydrogen atom or a methyl group, n are each independently an integer of 0 to 15, m is each independently an integer of 2-4. [Formula 5]

Where R ₁ and R ₄ are each independently a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an aliphatic and alicyclic or aromatic group, n are each independently an integer of 1 to 5, m is each independently an integer of 2-5. The fluorene-based epoxy (meth) acrylate represented by Formula 3 is obtained by reacting glycidyl (meth) acrylate with a fluorene compound represented by Formula 2 below, and is represented by Formula 5 Orene-based urethane (meth) acrylate is obtained by reacting (meth) acrylate which has a hydroxyl group with diisocyanate and ester to the fluorene derivative diol of the following general formula (4). [Formula 2]

Where Each R ₁ is independently a hydrogen atom or a methyl group, n are each independently an integer of 0 to 15, m is each independently an integer of 2-4. [Formula 4]

Where Each R ₁ is independently a hydrogen atom or a methyl group, n is each independently an integer of 1-5. The method of claim 1, wherein the (iii) thermoplastic resin is at least one resin selected from the group consisting of acrylonitrile, butadiene, acryl, urethane, polyamide, olefin and silicone resins with an average molecular weight of 1,000 to 1,000,000. Composition for anisotropic conductive film, characterized in that the range. The method according to claim 3, wherein the (meth) acrylate oligomer is a urethane-based (meth) acrylate, epoxy-based (meth) acrylate, polyester-based (meth) acrylate, fluorine-based (meth) acryl having an average molecular weight of 1,000 to 100,000 A composition for an anisotropic conductive film, characterized in that at least one oligomer selected from the group consisting of latex, silicone (meth) acrylate and phosphoric acid (meth) acrylate. The method of claim 1, wherein the (iii) (meth) acrylate monomer is 1,6-hexanediol mono (meth) acrylate, 2-hydroxy ethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylic 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyl oxypropyl (meth) acrylate, 1,4-butanediol (meth) acrylate, 2-hydroxyalkyl (meth) acrylo Monophosphate, 4-hydroxy cyclohexyl (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylol-epan di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri ( Meta) arcrective, 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-phenoxy Cethyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate, ethoxy addition type nonylphenol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene 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-methacryloyl Roxyethyl Phosphate , At least one monomer selected from the group consisting of 2-methacryloyloxy ethyl phosphate, dimethylol tricyclo decane di (meth) acrylate, trimethylolpropanebenzoate acrylate, and mixtures thereof. Composition for anisotropic conductive film. The method of claim 1, wherein the (iii) radical initiator is at least one selected from the group consisting of a photopolymerization initiator and a thermosetting initiator, and the (iii) conductive particles are metals including Au, Ag, Ni, Cu, and solder. particle; carbon; A resin containing polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol, and a modified resin thereof, coated with a metal containing Au, Ag, Ni; And at least one member selected from the group consisting of insulated conductive particles coated by adding insulating particles thereon. Anisotropic conductive film formed of a composition for anisotropic conductive film according to claim 1.