KR20100077794A - Anisotropic conductive film composition for improvement of adhesion and anisotropic conductive film using it - Google Patents

Abstract

PURPOSE: An anisotropic conductive film composition is provided to obtain excellent mobility and initial adhesive force on various substrates, to prevent a peel-off phenomenon in high temperature/high humidity and a thermal shock condition, and to improve the reliability of various display devices. CONSTITUTION: An anisotropic conductive film comprises: 15-40 parts by weight of a thermoplastic resin binder; 1-10 parts by weight of a radical initiator; 1-10 parts by weight of a silane coupling agent; and 1-20 parts by weight of a conductive particle based on 100.0 parts by weight of a radial curable material. A (poly)silsesquioxane derivative of a chemical formula 1 has obtain by giving reactivity to polyhedral oligomeric silsesquioxane or (poly)silsesquioxane. The (poly)silsesquioxane derivative is used with an amount of 0.5-30 parts by weight based on 100.0 parts by weight of the radial curable material.

Description

Reliability improved composition for anisotropic conductive film and anisotropic conductive film using same {ANISOTROPIC CONDUCTIVE FILM COMPOSITION FOR IMPROVEMENT OF ADHESION AND ANISOTROPIC CONDUCTIVE FILM USING IT}

The present invention relates to a composition for anisotropic conductive films, and more particularly, comprising (poly) silsesquioxane derivatives imparted to POSS (polyhedral oligomeric silsesquioxane) or (poly) silsesquioxane as a component of its composition. It relates to a composition for an anisotropic conductive film and an anisotropic conductive film formed of the composition.

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 a heating and pressing process 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. By being independent of each other, high insulation is provided. Such anisotropic conductive films are generally used for electrical connection of LCD panels and tape carrier packages (hereinafter referred to as TCP) or printed circuit boards and TCP.

However, in accordance with the trend of the display industry, which has recently become larger and thinner, the pitch between electrodes and circuits is gradually becoming finer, and an anisotropic conductive film plays a very important role as one of wiring devices for connecting such 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.

Specifically, among the types of the anisotropic conductive film, (i) the epoxy type anisotropic conductive film is a network structure formed after curing due to the aromatic benzene rings contained in the epoxy resin is very strong, it can express good reliability have. However, in order to form an anisotropic conductive film, at a high temperature and a high pressure due to the part which must use a polymer resin, a high equivalent high molecular weight epoxy resin or a phenoxy resin as a binder part and a large number of aromatic benzene rings, which must be included essentially Since it is not easy to control the flow characteristics of a large amount of bubbles are generated when connected, and thus there is a problem that low adhesion is implemented, there is a problem that the conductive particles are not sufficiently mounted between the circuit to be connected. In addition, due to the very high reaction temperature and long reaction time, maintenance of the process control and the connecting device has been difficult. However, in recent years, the development of a capsule-type latent curing agent or a cationic curing agent lowers the reaction temperature and shortens the reaction time, thereby improving the process problems.

On the other hand, the acrylic type has the advantage that the rapid curing speed of the radical curing reaction can be achieved in a few seconds to achieve fast curing, and significantly reduce the take time (Take Time), the product production rate is greatly improved, but film formation and Due to the polymer resin of low glass transition temperature mainly used for flow control purposes, there is a problem in that long-term reliability is weak in terms of connection and adhesion due to repeated contraction and expansion in the state connected between circuits. On the other hand, if the polymer resin of high glass transition temperature is used, there may be a problem that initial properties such as poor connection and low adhesion due to poor flowability may occur. In addition, when the reaction rate is controlled slowly in order to ensure contact between the conductive particles and the circuit, a difference in flowability occurs due to the difference in rheological properties of the binder resin and the hardened portion, thereby generating a large amount of bubbles in the connection layer, thereby ensuring long-term reliability. On the contrary, when the reaction rate is rapidly adjusted, sufficient contact does not occur between the conductive particles and the circuit, and thus there is a problem in that good connection reliability cannot be guaranteed.

In order to solve the problems of the prior art as described above, the present invention is to solve the problem of adhesion difficult to implement when mounting a display product as described above, the object of the embodiment according to the present invention, polysedral oligomeric silsesquioxane) or (poly) silsesquioxane derivatives with reactivity to (poly) silsesquioxane as a component of the composition, thereby providing excellent fluidity of the entire composition system and excellent initial adhesion to various substrates and high temperature / high humidity and thermal shock conditions It is to maintain the initial appearance by preventing the lifting phenomenon for various adherends such as zinc copper, polyimide during long time driving. In addition, the present invention provides an anisotropic conductive film composition having a broad applicability to various adhesive compositions while improving product reliability for various display devices by having high reliability for other connection resistance, and an anisotropic conductive film by the composition. For the purpose of

In order to achieve the above object, the present invention provides a composition comprising: a) a radical curable material, b) a thermoplastic binder, c) a radical initiator, d) a silane coupling agent, e) conductive particles, and f) a polyhedral oligomeric silsesquioxane (POSS) or ( It provides a composition for an anisotropic conductive film comprising a (poly) silsesquioxane derivative of the general formula (1) to impart reactivity to poly) silsesquioxane.

The present invention also provides a) epoxy compound, b) thermoplastic polymer binder resin, c) epoxy curing agent, d) silane coupling agent, e) inorganic filler, f) conductive particles and g) polyhedral oligomeric silsesquioxane (POSS) or (poly) It provides a composition for an anisotropic conductive film comprising a (poly) silsesquioxane derivative of the general formula (1) given reactivity to the silsesquioxane.

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

[ Formula 1]

Wherein the R groups may be the same or different, one or more R groups are reactive groups, the R reactive groups may be the same or different and are hydrogen, hydroxy, alkoxy, amine, epoxy, isocyanate, methacrylate, acrylate, meta Selected from the group consisting of krillamine, acrylamide, nitrile, norbornenyl, vinyl, styrenyl, and thiol, and the R non-reactive group may be the same or different and selected from the group consisting of C1-30 alkyl and C6-30 aryl do.)

Hereinafter, the configuration and operation of the present invention will be described in detail.

The composition for anisotropic conductive films of the present invention includes (poly) silsesquioxane derivatives that impart reactivity to POSS (polyhedral oligomeric silsesquioxane) or (poly) silsesquioxane as one component of the composition, thereby providing excellent fluidity and various It maintains the initial appearance by preventing the initial phenomenon of adhesion to the substrate and a variety of adhesives such as zinc copper, polyimide during long time operation under high temperature / high humidity and thermal shock conditions, and provides high reliability for other connection resistance.

Therefore, it is possible to provide a composition for anisotropic conductive films having broad applicability to various adhesive compositions while improving product reliability for various display devices. In addition, fine connection is possible according to the tendency of the circuit pattern to be miniaturized, and thus it is possible to cope with the development of high-performance electronic components in the electronic industry.

The present invention is applicable to both the composition for a radically curable anisotropic conductive film and the composition for an epoxy curable anisotropic conductive film, and the present invention will be described in detail below.

A. Composition for radically curable anisotropic conductive film

One embodiment of the present invention, a) 15 to 40 parts by weight of the thermoplastic resin binder a) 100 parts by weight of the radical curable material; c) 1 to 10 parts by weight of radical initiator; d) 1 to 10 parts by weight of the silane coupling agent; And e) 1 to 20 parts by weight of conductive particles, wherein the polysedral oligomeric silsesquioxane (POSS) or (poly) silsesquioxane derivative of the following Chemical Formula 1, which is reactive to (poly) silsesquioxane, is a) a radical curable material. It relates to a composition for an anisotropic conductive film comprising 0.5 to 30 parts by weight relative to 100 parts by weight.

[Formula 1]

Wherein the R groups may be the same or different, one or more R groups are reactive groups, the R reactive groups may be the same or different and are hydrogen, hydroxy, alkoxy, amine, epoxy, isocyanate, methacrylate, acrylate, meta Selected from the group consisting of krillamine, acrylamide, nitrile, norbornenyl, vinyl, styrenyl, and thiol, and the R non-reactive group may be the same or different and selected from the group consisting of C1-30 alkyl and C6-30 aryl do.)

The composition may further comprise additional 0.1 to 10 parts by weight of one or more additives selected from the group consisting of polymerization inhibitors, antioxidants, heat stabilizers, curing accelerators.

Each component is explained in full detail below.

a) radically curable material

  As the radical curable material, a (meth) acrylate oligomer or a (meth) acrylate monomer may be used. Each will be described in detail below.

 (a-1) (meth) acrylate oligomer

On the other hand, in the acrylate-type anisotropic conductive film composition that ensures the adhesion between the connection layer and the connection reliability by generating a radical curing reaction as a component of the hardened portion includes a (meth) acrylate oligomer which is a radical polymerizable material.

As the (meth) acrylate oligomer, one or more oligomers selected from the group of known (meth) acrylate oligomers can be used without limitation, and preferably, urethane-based (meth) acrylates having an average molecular weight in the range of about 1,000 to 100,000, Epoxy-based (meth) acrylate, polyester-based (meth) acrylate, fluorine-based (meth) acrylate, fluorene-based (meth) acrylate, silicone-based (meth) acrylate, phosphoric acid-based (meth) acrylate, maleimide Oligomers, such as a modified (meth) acrylate and an acrylate (methacrylate), can be used individually or in combination of 2 or more types, respectively.

Specifically, the urethane-based (meth) acrylates of the molecular structure of the polyester polyol (polyester polyol), polyether polyol (polyether polyol), polycarbonate polyol (polycarbonate polyol), polycaprolactone polyol (polycarprolactone polyol), ring Ring-opening tetrahydrofurane-propyleneoxide ring opening copolymer, polybutadiene diol, polydimethylsiloxane diol, ethylene glycol, propylene glycol, 1, 4-butanediol (1,4-butanediol), 1,5-pentanediol (1,5-pentanediol), 1,6-hexanediol (1,6-hexanediol), neopentyl glycol, 1 1,4-cyclohexane dimethanol, bisphenol A, hydrogenated bisphenol A, 2,4-toluene diisocyanate, 1,3-character 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexane Synthesized from diisocyanate (1,6-hexan diisocyanate), isophorone diisocyanate,

As said epoxy (meth) acrylate type, the intermediate molecular structure is bisphenol, such as 2-bromohydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, 4,4'- dihydride Consisting of an alkyl group, an aryl group, a methylol group, an allyl group, a cyclic aliphatic group, a halogen (such as tetrabromobisphenol A), a nitro group, or the like having a skeleton such as oxybiphenyl or bis (4-hydroxyphenyl) ether Meta) acrylate oligomer group may be used,

In addition, for example, 1-methyl-2,4-bismaleimidebenzene, N, N'-m-phenylene containing at least two maleimide groups in a molecule as the (meth) acrylate oligomer of the present invention. 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 Mid, N, N'-4, 4- diphenyl ether bismaleimide, N, N'-3,3'- diphenyl thrubis bismaleimide, 2, 2-bis (4- (4-maleimide phenoxy ) Phenyl) propane, 2, 2-bis (3-s-butyl- 4-8 (4-maleimide phenoxy) phenyl) propane, 1, 1-bis (4- (4-maleic) Dephenoxy) phenyl) decane, 4,4'-cyclohexyrylidebis (1- (4 maleimide phenoxyshi) -2-cyclohexyl benzene, 2,2-bis (4- (4 maleimide phenoxy) Phenyl) hexafluoro propane and the like may be used alone or in combination of two or more thereof.

 More preferably, one or more fluorene-based (meth) acrylate oligomers may be used as the (meth) acrylate oligomer, and examples thereof include fluorene-based epoxy (meth) acrylate oligomers and fluorene-based urethanes. (Meth) acrylate oligomers and the like can be used, and the general formula of the fluorene structure is shown in the following formula (2).

[Formula 2]

(Wherein

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 each independently an integer of 2 to 5.)

At this time, the fluorene derivative of the formula (2) is a method of generating an aryl radical by reaction of an aromatic diazoaluminum compound with copper ions (Pschorr reaction), Diels of indenes and butadienes (Otto Paul A phenol compound obtained by air oxidation of fluorene prepared by Hermann Diels) -Kurt Alder reaction or the like can be obtained by condensation reaction in the presence of a thiol compound such as mercaptocarboxylic acid and an aqueous hydrochloric acid solution. A fluorene epoxy (meth) acrylate oligomer having such a fluorene skeleton is reacted with (meth) acrylic acid glycidyl to a fluorene compound using an appropriate solvent in a temperature range at 50 to 120 ° C. for 5 to 30 hours. Fluorene-based urethane (meth) acrylate oligomers can be obtained by reacting fluorene derivative diols with (meth) acrylates having hydroxyl groups on diisocyanates and esters. Examples of the solvent 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.

When using at least one of the above-mentioned fluorene-based (meth) acrylate oligomers as the (meth) acrylate oligomer of the present invention, due to the excellent insulation exhibited by the fluorene structure, the possibility of short circuit between circuits is further increased. And further guarantee the initial low connection resistance and high reliability to improve the productivity and reliability of the final product.

 (a-2) (meth) acrylate monomers

The radical curable type composition according to the embodiment of the present invention includes (meth) acrylate monomer, which is also a radical polymerizable material as another component of the curing part, and the (meth) acrylate monomer serves as a reactive diluent. .

As the (meth) acrylate, one or more monomers selected from the group of known (meth) acrylate monomers can be used without limitation, although not particularly limited, preferably 1,6-hexanediol mono (meth) acryl Latex, 2-hydroxy ethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, 2-hydroxy-3-phenyl oxypropyl (meth) acrylate To 1,4-butanediol (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxy cyclohexyl (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylol Pandi (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerys Tall 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-phenoxy butyl (meth) acrylate, isobornyl (meth) acrylate, Tridecyl (meth) acrylate, ethoxy-added 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 type bisphenol-A di ( Meta) acrylic , Cyclohexanedimethanol di (meth) acrylate, phenoxy-t-glycol (meth) acrylate, 2-methacryloyloxyethyl phosphate, dimethylol tricyclo decane di (meth) acrylate, trimethylol One or more types selected from the group consisting of propanebenzoate acrylate, fluorene-based (meth) acrylate and mixtures thereof can be used.

More preferably, one or more fluorene-based (meth) acrylate monomers may be used as the (meth) acrylate monomer, and such fluorene-based (meth) acrylate monomers are conventionally known and limited ones. Can be used without

Specifically, as the fluorene-based (meth) acrylate monomer, the fluorene-based epoxy (meth) acrylate monomer of the formula (2) or the fluorene-based urethane (meth) acrylate monomer of the formula (2) each alone or 2 Although it can mix and use species, since it is the same as that mentioned above, detailed description is abbreviate | omitted here. On the other hand, examples of commercially available fluorene-based (meth) acrylate monomers include BPEF-A (Osaka Gas).

b) thermoplastic binder

In the anisotropic conductive film, the thermoplastic polymer resin forms a binder portion that serves as a matrix required to form the film, and may be used by selecting one or more from the group consisting of conventional polymer resins.

Examples of the thermoplastic polymer resin include acrylonitrile, styrene-acrylonitrile, methyl methacrylate, butadiene-styrene, butadiene, acryl, urethane, epoxy, phenoxy, polyamide, olefin, and silicone resins. May be used alone or in combination of two or more thereof, and preferably, polyvinyl butyral, polyvinyl formal, polyester, phenol resin, epoxy resin, phenoxy resin, acrylic polymerizable resin, or the like may be used. It is not necessarily limited thereto.

As the thermoplastic polymer resin, it is preferable to use an average molecular weight in the range of 1,000 to 1,000,000, but when using a resin having a molecular weight of less than 1,000, the film properties are excessive due to excessive tack characteristics, which are disadvantageous for film molding, When a resin having a molecular weight of more than 1,000,000 is used, compatibility with (meth) acrylate oligomers and monomers participating in a curing reaction may be deteriorated, and phase separation may occur when preparing a composition mixture.

Among the thermoplastic polymer resins, styrene-acrylonitrile copolymer resin may be used as a resin showing particularly excellent reliability. Generally, styrene-acrylonitrile copolymer resin is a resin having transparency and heat resistance characteristics, Among the polymers, it is particularly used in various electronic materials, constructions, and medical devices because of its excellent performance in electrical, mechanical properties, chemical resistance, dimensional stability, solvent resistance except ketones, and optical transparency. Used for blends. Styrene-acrylonitrile copolymer resins are generally synthesized and manufactured as styrene-acrylonitrile (SAN) copolymers and styrene-acrylonitrile-styrene (ASA) copolymers, and the like. It can be prepared by the method, and in general, as the content of acrylonitrile increases, the physical properties and properties are excellent, but in consideration of the deterioration of workability and thermal stability during processing, SAN resin having a high acrylonitrile content is produced. Except for special cases such as the continuous bulk polymerization method that is superior in transparency and other properties compared to other processes are widely used. The styrene-acrylonitrile copolymer resin is SAN resin, which is AP series of Cheil Industries, SAN resin, which is SAN series of Kumho Petrochemical, SAN resin, which is Lustran series of Bayer, and ASA, Luran S series of BASF. Resin etc. can be purchased and used.

On the other hand, when a large amount of a thermoplastic polymer resin having a high glass transition temperature is used for the purpose of improving reliability, it has a hard structure that is very hard and brittle after curing. When continuous stress is applied from the outside, as the stress cannot be solved inside, cracks may occur and cause deterioration of physical properties. Therefore, in order to solve such a problem, polymer resins such as acrylonitrile, methyl methacrylate-butadiene-styrene, butadiene, acrylic, urethane, etc. having low glass transition temperature and rubber characteristics among the polymer resins Can be used. However, when the rubber-like polymer resin is used, the amount of the polymer resin should be minimized because it may cause the expansion of the cured anisotropic conductive film under conditions such as high temperature / humidity, thereby lowering reliability. Recently, in order to solve these problems, a rubber-like polymer resin having a low glass transition temperature, such as butadiene, is prepared in a core, and then a shell is made using a polymer resin having a relatively high glass transition temperature such as acrylic or styrene. By using a polymer-copolymer resin having a specific structure of the core-shell type in the form of enclosing), it is possible to simultaneously solve the stress problem and the expansion problem related to reliability in the cured anisotropic conductive film. Such core-shell polymer copolymer resins include Gnz AC series and Resinous Kasei's RKB series. It is a product which disperse | distributes the core-shell copolymer resin which consists of methacrylate butadiene styrene.

The thermoplastic polymer resins listed above for the binder portion of the anisotropic conductive film according to the purpose of the present invention are not necessarily limited to the products described. In the case of a composition for a radically curable anisotropic conductive film, the thermoplastic polymer binder resin preferably includes 15 to 40 parts by weight based on 100 parts by weight of the radical curable material. When the content is less than 15 parts by weight, a problem occurs that the film properties are weak, and when the content exceeds 40 parts by weight, a phenomenon occurs that the appearance characteristics and connection resistance are inhibited.

c) radical initiators

The composition for a radically curable anisotropic conductive film according to the embodiment of the present invention may be used in combination of one or more radical initiators as a component for causing a curing reaction of the cured portion.

As the 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 hexa Nonate, 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 per Oxy acetate, dicumyl peroxide, 2,5, -dimethyl-2,5-di (t-butyl peroxy) hexane, t-butyl cumyl peroxide, t-hexyl peroxy neodecanoate, t-hexyl per Oxy-2-ethyl hexanonate, t-butyl peroxy-2-2-ethylhexanoate, t-butyl peroxy isobutylate, 1,1-bis (t-butyl peroxy) cyclohexane, t- Hexyl peroxy isopropyl monocarbo Nate, 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, lauryl peroxide, stearoyl peroxide, succinate 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 noedcanoate, di-n-propyl peroxy dicarbonate, di-iso-propyl peroxy carbonate, bis (4-t-butyl cyclohexyl) peroxy dicarbonate, di-2-ethoxy meth Toxy peroxy dicarbonate, di (2-ethyl hexyl peroxy) Carbonate, 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 Tironitrile), 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. are mentioned. These can be used individually or in mixture of 2 or more types, respectively.

In the case of a composition for radically curable anisotropic conductive film, the radical initiator preferably contains 1 to 10 parts by weight based on 100 parts by weight of the radical curable material. When the content is less than 1 part by weight, the curing reaction is not sufficiently performed. As a result, appearance characteristics and reliability characteristics may be impaired, and when the amount exceeds 10 parts by weight, corrosion and degradation of reliability due to residual radicals may occur.

d) silane coupling agents and other additives

Coupling agents include vinyl trichloro silane, vinyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-methacryloxy propyl trimethoxy silane, 2-aminoethyl-3-aminopropyl methyldimethoxy silane , 3-ureidopropyl triethoxy silane, and the like, and various such silane coupling agents may be used.

The composition for a radically curable anisotropic conductive film of the present invention contains the silane coupling agent in an amount of 1 to 10 parts by weight based on 100 parts by weight of the a) radical curable material.

Meanwhile, in the composition of the composition for each anisotropic conductive film according to the embodiment of the present invention, in order to add additional physical properties without inhibiting basic physical properties, other additives such as polymerization inhibitors, antioxidants, heat stabilizers, curing accelerators, etc. It may be selected from a) 0.1 to 10 parts by weight based on 100 parts by weight of the radical curable material.

As the polymerization inhibitor, one or more selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, phenothiazine and mixtures thereof can be used. In addition, as the antioxidant used for the purpose of preventing oxidation reaction and imparting thermal stability of the composition induced by heat, a branched phenolic or hydroxy cinnamate-based substance 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. As the curing accelerator for improving the reaction rate, at least one of a solid imidazole accelerator, a solid and liquid amine accelerator may be used, etc. The various additives are not limited to the described types.

e) conductive particles

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

As such conductive particles, conventionally known conductive particles can be used without limitation, and preferably, metal particles containing Au, Ag, Ni, Cu, solder, or the like; carbon; Particles coated with a resin containing polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol, and the like, and a metal containing Au, Ag, Ni, etc., using the modified resin thereof as particles; One or more kinds of insulated conductive particles and the like coated with insulating particles thereon may be used, but are not necessarily limited thereto.

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 to be applied, in the case of radical curable adhesive composition 1 to 1 to 100 parts by weight of the radical curable material It may include 20 parts by weight. If the content is less than 1 part by weight, it is easy to cause a poor connection due to the reduction of the connection area when Mis-Align occurs between the terminals during the connection process, and if it exceeds 20 parts by weight, it is easy to cause poor insulation.

f) (poly) silsesquioxane derivatives

The composition of the present invention contains at least one analogous compound selected from the group consisting of polyhedral oligomeric silsesquioxane (POSS) or a group of (poly) silsesquioxane derivatives which is reactive to (poly) silsesquioxane. The general structure of the (poly) silsesquioxane derivatives imparting reactivity to the polyhedral oligomeric silsesquioxane (POSS) or (poly) silsesquioxane is as described in the following general formula (1).

[Formula 1]

Wherein the R groups may be the same or different, one or more R groups are reactive groups, the R reactive groups may be the same or different and are hydrogen, hydroxy, alkoxy, amine, epoxy, isocyanate, methacrylate, acrylate, meta Selected from the group consisting of krillamine, acrylamide, nitrile, norbornenyl, vinyl, styrenyl, and thiol, and the R non-reactive group may be the same or different and selected from the group consisting of C1-30 alkyl and C6-30 aryl do.)

The (poly) silsesquioxane is formed of a siloxane structure such as silica, rather than a hydrocarbon such as an organic polymer, and has excellent heat resistance. (Poly) silsesquioxane has been commercialized under the names 'Glass resin' and 'SST resin' in Owens Illinois and Gelest since it was first synthesized by GE's Brown et al.

There are three kinds of materials having siloxane structural units (Si-O-Si), such as M, D, and Q, and polysiloxanes represented by (RSiO3 / 2) n in general formulas are represented by T unit structure, and (poly) It is called silsesquioxane. Among them, resin materials obtained through high molecular weight reaction through polymerization and the like are Q, T, and D, and show differences in thermal and mechanical properties such as heat resistance depending on the form. (Poly) silsesquioxane possesses basic thermo-mechanical properties, and has excellent thermal stability in the case of heat resistance, and has an initial pyrolysis temperature of 400 ° C or higher, which is lower than the initial pyrolysis temperature of polyimide, which is known as a heat resistant polymer in organic polymers. It is higher than 50 degreeC. On the other hand, unlike silica and silicone resins, it shows excellent compatibility with acrylic resins applied to solubility and other compositions in various solvents. In general, in case of solubility, there is a big difference depending on the type, structure, and molecular weight of the polymer. (Poly) silsesquioxane has high solubility in common organic solvents in the case of high molecular weight, It is soluble in ethyl alcohol and the like.

In addition, the (poly) silsesquioxane is capable of introducing an organic functional group through the remaining linking group that does not have a siloxane bond, thereby giving the characteristics of other organic polymers having a reactive group. (Poly) silsesquioxane-based resins vary in their types, such as hydrogen, alkyl, alkylene, aryl, arylene, and organic functional groups, depending on the substituent R. Polymethylsilsesquioxane, polyphenylsilsesquioxane and polyhydride Rosensilsesquioxane and the like are excellent in thermal and mechanical properties.

The composition of the present invention preferably comprises 0.5 to 30 parts by weight based on 100 parts by weight of the (a) radical curable material by selecting one or more of the (poly) silsesquioxane derivatives. In the composition for radically curable anisotropic conductive films, when the content is less than 0.5 part by weight, there is no effect of improving reliability, and when the content exceeds 30 parts by weight, appearance characteristics are inhibited.

B. Composition for epoxy curable anisotropic conductive film

One embodiment of the present invention, a) 100 weight of the epoxy compound comprising at least one of the epoxy monomer, epoxy oligomer or epoxy resin selected from the group consisting of the bisphenol type, novolak type, glycidyl type, aliphatic and alicyclic B) 80 to 200 parts by weight of the thermoplastic polymer binder resin; c) 8 to 20 parts by weight of an epoxy curing agent; d) 1 to 15 parts by weight of the silane coupling agent; e) 5 to 15 parts by weight of the inorganic filler; And f) 10 to 40 parts by weight of conductive particles, wherein the (poly) silsesquioxane derivative of the following formula (1) imparting reactivity to a polyhedral oligomeric silsesquioxane (POSS) or (poly) silsesquioxane is a) an epoxy compound 100 It relates to a composition for an anisotropic conductive film comprising 1 to 70 parts by weight relative to parts by weight.

[Formula 1]

Wherein the R groups may be the same or different, one or more R groups are reactive groups, the R reactive groups may be the same or different and are hydrogen, hydroxy, alkoxy, amine, epoxy, isocyanate, methacrylate, acrylate, meta Selected from the group consisting of krillamine, acrylamide, nitrile, norbornenyl, vinyl, styrenyl, and thiol, and the R non-reactive group may be the same or different and selected from the group consisting of C1-30 alkyl and C6-30 aryl do.)

The composition may further comprise additional 0.1 to 10 parts by weight of one or more additives selected from the group consisting of polymerization inhibitors, antioxidants, heat stabilizers, curing accelerators.

Each component is explained in full detail below.

a) epoxy

The cured part component of the epoxy type anisotropic conductive film may include at least one of an epoxy resin selected from the group consisting of bisphenol type, novolak type, glycidyl type, aliphatic and alicyclic. Such epoxy resins may be any materials that include at least one bond structure that may be selected from among the known epoxy-based bisphenol, novolak, glycidyl, aliphatic and alicyclic molecular structures. Can be used without

Preferably, the epoxy resin which is solid at normal temperature and the epoxy resin which is liquid at normal temperature can be used together, and a flexible epoxy resin can be used together further here. Examples of the solid epoxy resin include a phenol novolac epoxy resin, a cresol novolac epoxy resin, and an epoxy resin mainly composed of dicyclo pentadiene and bisphenol A. Or an F-type polymer or a modified epoxy resin, but is not necessarily limited thereto. As the liquid epoxy resin at room temperature, bisphenol A or F or mixed epoxy resin may be used. It is not limited to this.

Non-limiting examples of the flexible epoxy resins include dimer acid-modified epoxy resins, epoxy resins based on propylene glycol, urethane (urethane) modified epoxy resins, and the like.

In addition to the general epoxy resins described above, the excellent insulation properties inherent in the molecular structure can reduce the possibility of short circuits, especially between circuits, and ensure low initial connection resistance and excellent reliability, thereby improving productivity and reliability of the final product. A fluorene-based epoxy resin may be used, and the fluorene base structure is as shown in Chemical Formula 2 above. It is preferable to use the fluorene-based epoxy resin in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the composition for epoxy curable anisotropic conductive film, which is relatively insufficient when the content of the epoxy resin is less than 1 part by weight. This is because the appearance and the connection properties are hindered, and when used in excess of 30 parts by weight, a problem may occur in that the structure itself becomes too rigid after curing.

Examples of commercially available epoxy-based materials include DER-331 (DOW Chemical), YDCN-500-80P (Kukdo Chemical), YDCN-500-90P (Kukdo Chemical), YP-50 (Dongdo Chemical), and PKFE. Examples of general resins such as (INCHEMREZ) and fluorene-based epoxy resins include BPFG and BPEGF (Osaka Gas), but are not necessarily limited to the described products.

b) thermoplastic polymer binder resin

The description of the thermoplastic polymer binder resin is the same as that described in the composition for the A radical curable anisotropic conductive film. However, in the case of the composition for epoxy curable films, the content of the thermoplastic polymer binder resin preferably includes 80 to 200 parts by weight based on 100 parts by weight of the a) epoxy compound.

c) epoxy curing agent

On the other hand, the composition for epoxy curable anisotropic conductive films of the present invention is used in combination of one or more kinds of thermosetting agents for epoxy as other components of the curing portion.

The thermosetting agent for epoxy may be used without limitation as long as the thermosetting agent of the epoxy curing type known in the prior art, specific examples thereof include an acid anhydride, amine, imidazole, hydrazide, cationic, etc. Among the curing agents may be used alone or in combination of two or more to meet the purpose, but is not particularly limited thereto.

Such a thermosetting agent for epoxy is preferably included in the range of 8 to 20 parts by weight based on 100 parts by weight of the a) epoxy compound. When the content is less than 8 parts by weight, the curing reaction may not be sufficiently carried out, which may hinder the appearance characteristics and the reliability characteristics. When the content is more than 20 parts by weight, the stability and the reliability may be reduced due to the residual curing agent. .

d) silane coupling agents and other additives

The description of the silane coupling agent and the other additives is the same as those described in the composition for the A radical curable anisotropic conductive film and the kind and content thereof.

e) inorganic fillers

Adhesive composition for epoxy curable anisotropic conductive film comprises an inorganic filler in the range of 25 to 70 parts by weight based on 100 parts by weight of the a) epoxy compound. As the inorganic filler, it is preferable to include hydrophobic nano silica particles having a size of about 5 to 20 nanometers (nm) surface-treated with an organic silane. Inorganic fillers provide proper flow and robust hardening structure in the adhesive bonding and curing process to suppress thermal expansion at high temperatures to provide excellent initial adhesion and low connection resistance.

Hydrophobic nano silica particles having a size of about 5 to 20 nanometers (nm) surface-treated with such organic silanes include Aerosil R-972, Aerosil R-202, Aerosil R-805, Aerosil R-812, Aerosil R-8200 ( Degussa) and the like, and may be used, but is not necessarily limited thereto.

f) conductive particles

The base material for the conductive particles is the same as that described in the composition for the A radical curable anisotropic conductive film, except that the epoxy curable anisotropic conductive film composition includes the conductive particles in the range of 10 to 40 parts by weight based on 100 parts by weight of the a) epoxy compound. do.

g) (poly) silsesquioxane derivatives

The description of the (poly) silsesquioxane derivative is the same as that described in the composition for the A radical curable anisotropic conductive film. However, in the case of the composition for epoxy curable films, the content of the poly) silsesquioxane derivative is preferably 1 to 70 parts by weight based on 100 parts by weight of the a) epoxy compound. When the content is less than 1 part by weight, there is no effect of improving reliability, and when the content exceeds 70 parts by weight, a phenomenon in which appearance characteristics are inhibited appears.

The method for forming an anisotropic conductive film using the composition according to each embodiment of the present invention does not require any special apparatus or equipment, and after dissolving one or more resins selected from thermoplastic resins constituting the binder part in an organic solvent to liquefy it Stirring for a certain time within the speed range that the other binder portion resin and the cured portion and the conductive particles are not pulverized, it is applied to a thickness of 10 to 50 ㎛ on a release film and then dried for a certain time to have a single layer structure An anisotropic conductive film can be obtained. In this case, a conventional organic solvent can be used as the organic solvent without limitation, and in the present invention, an anisotropic conductive film having a multilayer structure of two or more layers may be obtained by repeating the above procedure two or more times.

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

< Example  1>

The binder resin part serving as a matrix for forming a film is 20 g of NBR-based resin (N-21, Nipon Xeon) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 30% by weight, and acrylic compound dissolved in methyl ethyl ketone at 25% by weight. Urethane (meth) acrylate oligomer (UV-3000B, Nippon Synthetic Chemical Co., Ltd.) dissolved in methyl ethyl ketone at 20 g, 60 wt% of copolymer resin (KLS-1040, Fujikura Chemical) 9 g; toluene / methyl ethyl at 50 wt% 1 g of a (poly) silsesquioxane derivative having an acrylic group dissolved in a ketone azeotropic mixed solvent; As a hardening part with hardening reaction, 30 g of urethane (meth) acrylate oligomers (Miramer PU-330, Miwon Corporation), 3 g of 2-methacryloyloxyethyl phosphate which is a radical polymerization type (meth) acrylate monomer as a reactive monomer, 10 g of pentaerythritol tri (meth) acrylate, 2 g of benzoyl peroxide as a thermosetting radical initiator; As a filler for imparting conductive performance to the anisotropic conductive film, conductive particles (23GNR5.0-MX, NCI Co., Ltd.) having a size of 5 µm were insulated, and 5 g was added to complete the configuration.

< Example  2>

As a binder resin part serving as a matrix for forming a film, 20 g of NBR-based resin (N-21, Nipon Xeon) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 30% by weight, and acrylic compound dissolved in methyl ethyl ketone at 25% by weight 10 g of a (poly) silsesquioxane derivative having an acrylic group dissolved in a toluene / methyl ethyl ketone azeotrope mixed solvent at 20 g, 50 wt% of a copolymer resin (KLS-1040, Fujikura Kasei); As a hardening part with hardening reaction, 30 g of urethane (meth) acrylate oligomers (Miramer PU-330, Miwon Corporation), 3 g of 2-methacryloyloxyethyl phosphate which is a radical polymerization type (meth) acrylate monomer as a reactive monomer, 10 g of pentaerythritol tri (meth) acrylate, 2 g of benzoyl peroxide as a thermosetting radical initiator; Then, as a filler for imparting conductive performance to the anisotropic conductive film, the conductive particles (23GNR5.0-MX, NCI Co., Ltd.) having a size of 5 µm were insulated, and then 5 g was added to complete the configuration.

< Example  3>

The binder resin part serving as a matrix for forming a film is 20 g of NBR-based resin (N-21, Nipon Xeon) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 30% by weight, and acrylic compound dissolved in methyl ethyl ketone at 25% by weight. 20 g of a (poly) silsesquioxane derivative having an acrylic group dissolved in a toluene / methyl ethyl ketone azeotrope mixed solvent at 20 g, 50 wt% of a copolymer resin (KLS-1040, Fujikura Kasei); As a hardening part with hardening reaction, 20 g of urethane (meth) acrylate oligomers (Miramer PU-330, Unwon Corporation), 3 g of 2-methacryloyl oxyethyl phosphate which are radical polymerization type (meth) acrylate monomers as a reactive monomer, 10 g of pentaerythritol tri (meth) acrylate, 2 g of benzoyl peroxide as a thermosetting radical initiator; Then, as a filler for imparting conductive performance to the anisotropic conductive film, the conductive particles (23GNR5.0-MX, NCI Co., Ltd.) having a size of 5 µm were insulated, and 5 g was added to complete the configuration.

< Example  4>

As the binder resin portion serving as the matrix for forming the film, bisphenol-A type epoxy resin / reactive epoxy diluent / methyl methacrylate-butadiene-styrene core-shell copolymer resin was used in a weight ratio of 30/30/40. 25 g of mixed resin (RKB-2023, Reginous Kasei), 25 g of phenoxy resin (PKHH, INCHEMREZ) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 40% by weight; As a hardening part with hardening reaction, 1 weight of (poly) silsesquioxane derivatives which have an epoxy group melt | dissolved in the propylene glycol methyl ethyl acetate solvent by 50 weight%, an epoxy resin (Epikote-154, JER company, Japan) 9g, fluorene 20 g of an epoxy resin (BPEFG, Osaka Gas); 10 g of hydrophobic nano silica particles (Aerosil R-805, Degussa) surface-treated with octylsilane; 3 g of an aromatic sulfonium hexafluoro antimonate (San aid SI-60L, SANSHIN chemical) which induces a cation curing reaction as a thermosetting epoxy curing agent; 2 g of γ-glycidoxy propyl trimethoxy silane (KBM-403, ShinEtsu) as coupling agent; Then, as a filler for imparting conductive performance to the anisotropic conductive film, conductive particles (AULEB-004A, Sekisui Co., Ltd.) having a size of 5 µm were insulated, and then 5 g was added to complete the configuration.

< Example  5>

As the binder resin portion serving as the matrix for forming the film, bisphenol-A type epoxy resin / reactive epoxy diluent / methyl methacrylate-butadiene-styrene core-shell copolymer resin has a weight ratio of 30/30/40. 25 g of mixed resin (RKB-2023, Reginous Kasei), 25 g of phenoxy resin (PKHH, INCHEMREZ) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 40% by weight; As a hardening part with hardening reaction, 10 weights of (poly) silsesquioxane derivatives which have an epoxy group melt | dissolved in the propylene glycol methyl ethyl acetate solvent by 50 weight%, 20g of fluorene type epoxy resins (BPEFG, Osaka gas); 10 g of hydrophobic nano silica particles (Aerosil R-805, Degussa) surface-treated with octylsilane; 3 g of an aromatic sulfonium hexafluoro antimonate (San aid SI-60L, SANSHIN chemical) which induces a cation curing reaction as a thermosetting epoxy curing agent; 2 g of γ-glycidoxy propyl trimethoxy silane (KBM-403, ShinEtsu) as coupling agent; Then, as a filler for imparting conductive performance to the anisotropic conductive film, conductive particles (AULEB-004A, Sekisui Co., Ltd.) having a size of 5 µm were insulated, and then 5 g was added to complete the configuration.

< Example  6>

As the binder resin portion serving as the matrix for forming the film, bisphenol-A type epoxy resin / reactive epoxy diluent / methyl methacrylate-butadiene-styrene core-shell copolymer resin was used in a weight ratio of 30/30/40. 25 g of mixed resin (RKB-2023, Reginous Kasei), 25 g of phenoxy resin (PKHH, INCHEMREZ) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 40% by weight; As a hardening part with hardening reaction, 20 weights of (poly) silsesquioxane derivatives which have an epoxy group melt | dissolved in the propylene glycol methyl ethyl acetate solvent by 50 weight%, 10 g of fluorene type epoxy resins (BPEFG, Osaka gas); 10 g of hydrophobic nano silica particles (Aerosil R-805, Degussa) surface-treated with octylsilane; 3 g of an aromatic sulfonium hexafluoro antimonate (San aid SI-60L, SANSHIN chemical) which induces a cation curing reaction as a thermosetting epoxy curing agent; 2 g of γ-glycidoxy propyl trimethoxy silane (KBM-403, ShinEtsu) as coupling agent; Then, as a filler for imparting conductive performance to the anisotropic conductive film, conductive particles (AULEB-004A, Sekisui Co., Ltd.) having a size of 5 µm were insulated, and then 5 g was added to complete the configuration.

< Comparative example  1>

The binder resin part serving as a matrix for forming a film is 20 g of NBR-based resin (N-21, Nipon Xeon) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 30% by weight, and acrylic compound dissolved in methyl ethyl ketone at 25% by weight. 10 g of urethane (meth) acrylate oligomer (UV-3000B, Nippon Synthetic Chemical Co., Ltd.) dissolved in methyl ethyl ketone at 20 g of copolymer resin (KLS-1040, Fujikura Kasei), 60 wt%; As a hardening part with hardening reaction, 30 g of urethane (meth) acrylate oligomers (Miramer PU-330, Miwon Corporation), 3 g of 2-methacryloyloxyethyl phosphate which is a radical polymerization type (meth) acrylate monomer as a reactive monomer, 10 g of pentaerythritol tri (meth) acrylate, 2 g of benzoyl peroxide as a thermosetting radical initiator; As a filler for imparting conductive performance to the anisotropic conductive film, conductive particles (23GNR5.0-MX, NCI Co., Ltd.) having a size of 5 µm were insulated, and 5 g was added to complete the configuration.

< Comparative example  2>

As a binder resin part serving as a matrix for forming a film, 20 g of NBR-based resin (N-21, Nipon Xeon) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 30% by weight and 25% by weight in methyl ethyl ketone 25 g of a (poly) silsesquioxane derivative having an acrylic group dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 20 g and 50 wt% of an acrylic copolymer resin (KLS-1040, Fujikura Kasei); As a hardening part with hardening reaction, 15 g of urethane (meth) acrylate oligomers (Miramer PU-330, Miwon Corporation), 3 g of 2-methacryloyloxyethyl phosphate which are radical polymerization type (meth) acrylate monomers as a reactive monomer, 10 g of pentaerythritol tri (meth) acrylate, 2 g of benzoyl peroxide as a thermosetting radical initiator; As a filler for imparting conductive performance to the anisotropic conductive film, conductive particles (23GNR5.0-MX, NCI Co., Ltd.) having a size of 5 µm were insulated, and 5 g was added to complete the configuration.

< Comparative example  3>

As the binder resin portion serving as the matrix for forming the film, bisphenol-A type epoxy resin / reactive epoxy diluent / methyl methacrylate-butadiene-styrene core-shell copolymer resin was used in a weight ratio of 30/30/40. 25 g of mixed resin (RKB-2023, Reginous Kasei), 25 g of phenoxy resin (PKHH, INCHEMREZ) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 40% by weight; As a hardening part with hardening reaction, 10 g of epoxy resins (Epikote-154, JER Corporation, Japan), 20 g of fluorene-type epoxy resins (BPEFG, Osaka Gas); 10 g of hydrophobic nano silica particles (Aerosil R-805, Degussa) surface-treated with octylsilane; 3 g of an aromatic sulfonium hexafluoro antimonate (San aid SI-60L, SANSHIN chemical) which induces a cation curing reaction as a thermosetting epoxy curing agent; 2 g of γ-glycidoxy propyl trimethoxy silane (KBM-403, ShinEtsu) as coupling agent; Then, as a filler for imparting conductive performance to the anisotropic conductive film, conductive particles (AULEB-004A, Sekisui Co., Ltd.) having a size of 5 µm were insulated, and then 5 g was added to complete the configuration.

< Comparative example  4>

As the binder resin portion serving as the matrix for forming the film, bisphenol-A type epoxy resin / reactive epoxy diluent / methyl methacrylate-butadiene-styrene core-shell copolymer resin was used in a weight ratio of 30/30/40. 25 g of mixed resin (RKB-2023, Reginous Kasei), 25 g of phenoxy resin (PKHH, INCHEMREZ) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 40% by weight; As a hardening part with hardening reaction, 25 weights of (poly) silsesquioxane derivatives which have an epoxy group melt | dissolved in the propylene glycol methyl ethyl acetate solvent by 50 weight%, 5g of fluorene type epoxy resins (BPEFG, Osaka gas); 10 g of hydrophobic nano silica particles (Aerosil R-805, Degussa) surface-treated with octylsilane; 3 g of an aromatic sulfonium hexafluoro antimonate (San aid SI-60L, SANSHIN chemical) which induces a cation curing reaction as a thermosetting epoxy curing agent; 2 g of γ-glycidoxy propyl trimethoxy silane (KBM-403, ShinEtsu) as coupling agent; Then, as a filler for imparting conductive performance to the anisotropic conductive film, conductive particles (AULEB-004A, Sekisui Co., Ltd.) having a size of 5 µm were insulated, and then 5 g was added to complete the configuration.

Each said combination liquid was stirred for 60 minutes at normal temperature (25 degreeC) within the speed range in which electroconductive particle is not pulverized. The combination solution formed a film having a thickness of 20 μm on a polyethylene release film treated with a silicone release surface, and a casting knife was used to form the film. The drying time of the film was 10 minutes at 50 ° C. It was.

Evaluation of Properties and Reliability of Anisotropic Conductive Films

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 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. and 1 second and a main compression condition of 180 ° C., 5 seconds, and 3 MPa. Each specimen was prepared 7 pieces, 90 ° adhesive force was measured (ASTM D3330 / D3330M-04) using the specimen prepared as described above, and the connection resistance (ASTM F43-64T) was measured by a four-terminal (probe) measuring method It was. In addition, the high temperature / high humidity reliability evaluation (ASTM D117) was performed at a temperature of 85 ° C. and a relative humidity of 85% for 1000 hours, and the thermal shock reliability evaluation (ASTM D1183) was repeated 1000 times of a temperature condition of −40 ° C. to 80 ° C. The results are shown in Tables 1 and 2 below.

(Initial and Reliable Adhesion Results)

As shown in the 90 ° adhesive strength measurement results after the initial and reliability evaluation of Table 1, the (poly) siles that gave reactivity to the polyhedral oligomeric silsesquioxane (PSOS) -containing compound and (poly) silsesquioxane according to an embodiment of the present invention The anisotropic conductive film using the quoxane derivative as a component of the composition, the anisotropic conductive film of Comparative Example 1, Comparative Example 3 not using the resin and the content of the (poly) silsesquioxane derivatives according to the embodiment of the present invention It can be seen that compared to Comparative Examples 2 and 4, the excellent results in both the initial adhesive strength and the adhesive strength after the reliability evaluation.

(Initial connection resistance and reliability connection resistance measurement results)

As shown in the connection resistance measurement results of Table 2, one of the compositions of the polyhedral oligomeric silsesquioxane (POSS) -containing compound and the (poly) silsesquioxane derivative imparted with reactivity to the (poly) silsesquioxane according to an embodiment of the present invention It can be seen that the anisotropic conductive film used as a component has a low resistance value at both the initial connection resistance and the connection resistance after the reliability evaluation, and according to these results, a polyhedral oligomeric silsesquioxane (PSOS) -containing compound and a (poly) Anisotropic conductive films made of conventional thermoplastic resins, acrylic or phenoxy resins, and the like, in which an anisotropic conductive film using a (poly) silsesquioxane derivative which imparts reactivity to silsesquioxane as a component is conventionally commercialized It can be seen that it has excellent initial properties and high reliability compared to.

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. In addition, the present invention includes both a polyhedral oligomeric silsesquioxane (POSS) -containing compound and a (poly) silsesquioxane derivative imparted with reactivity to (poly) silsesquioxane. Without being limited to the kind described in the appended claims, the appended claims cover such modifications and variations as fall within the spirit of the invention.

Claims (11)

a) relative to 100 parts by weight of a radical curable material b) 15 to 40 parts by weight of the thermoplastic resin binder; c) 1 to 10 parts by weight of radical initiator; d) 1 to 10 parts by weight of the silane coupling agent; And e) 1 to 20 parts by weight of conductive particles, (S) containing 0.5 to 30 parts by weight of polysedral oligomeric silsesquioxane (POSS) or (poly) silsesquioxane derivative of the following Chemical Formula 1 to which reactivity is imparted to (a) 100 parts by weight of the radical curable material Composition for anisotropic conductive films to be. [Formula 1]

Wherein the R groups may be the same or different, one or more R groups are reactive groups, the R reactive groups may be the same or different and are hydrogen, hydroxy, alkoxy, amine, epoxy, isocyanate, methacrylate, acrylate, meta Selected from the group consisting of krillamine, acrylamide, nitrile, norbornenyl, vinyl, styrenyl, and thiol, and the R non-reactive group may be the same or different and selected from the group consisting of C1-30 alkyl and C6-30 aryl do.) a) to 100 parts by weight of an epoxy compound comprising at least one of an epoxy monomer, an epoxy oligomer or an epoxy resin selected from the group consisting of bisphenol, novolac, glycidyl, aliphatic and alicyclic b) 80 to 200 parts by weight of the thermoplastic polymer binder resin; c) 8 to 20 parts by weight of an epoxy curing agent; d) 1 to 15 parts by weight of the silane coupling agent; e) 5 to 15 parts by weight of the inorganic filler; And f) 10 to 40 parts by weight of conductive particles, Characterized in that it comprises 1 to 70 parts by weight of the polysedral oligomeric silsesquioxane (POSS) or (poly) silsesquioxane derivative of the formula (1) to give a reactivity to (poly) silsesquioxane (a) 100 parts by weight of the epoxy compound Composition for anisotropic conductive film. [Formula 1]

Wherein the R groups may be the same or different, one or more R groups are reactive groups, the R reactive groups may be the same or different and are hydrogen, hydroxy, alkoxy, amine, epoxy, isocyanate, methacrylate, acrylate, meta Selected from the group consisting of krillamine, acrylamide, nitrile, norbornenyl, vinyl, styrenyl, and thiol, and the R non-reactive group may be the same or different and selected from the group consisting of C1-30 alkyl and C6-30 aryl do.) The method according to claim 1 or 2, The composition is an anisotropic conductive film composition further comprises 0.1 to 10 parts by weight of at least one additive selected from the group consisting of a polymerization inhibitor, an antioxidant, a heat stabilizer, a curing accelerator. The method according to claim 1 or 2, The thermoplastic polymer resin is acrylonitrile-based, styrene-acrylonitrile-based, methyl methacrylate-butadiene-styrene-based, butadiene-based, acryl-based, urethane-based, epoxy-based, phenoxy, polyamide-based, olefin-based, silicone-based, poly-based At least one resin selected from the group consisting of vinyl butyral series, polyvinyl formal series, and polyester series, wherein the composition has an average molecular weight of 1,000 to 1,000,000. The method of claim 1, The radical curable material, Urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, fluorine (meth) acrylate, fluorene (meth) acrylate, silicone (meth) acrylate, phosphoric acid ( At least one oligomer selected from the group consisting of meta) acrylate, maleimide modified (meth) acrylate and acrylate (methacrylate), wherein the (meth) acrylate oligomer has an average molecular weight in the range of 1,000 to 100,000; 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 cyclohexyl (meth) acrylate, neopentyl Glycol 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-hydroperfuryl (meth) acrylate, iso-decyl (meth) acrylate, 2- (2 -on Ethoxy) ethyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (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 ( Meta) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethoxy addition type bisphenol-A di (meth) acrylate Cyclohexanedimethanol di (meth) acrylate, phenoxy-t-glycol (meth) acrylate, 2-methacryloyloxyethyl phosphate, dimethylol tricyclo decane di (meth) acrylate, At least one (meth) acrylate monomer selected from the group consisting of trimethylolpropanebenzoate acrylate, fluorene-based (meth) acrylate and mixtures thereof, or It is a mixture of the said (meth) acrylate oligomer and a (meth) acrylate monomer, The composition for anisotropic conductive films characterized by the above-mentioned. The method of claim 1, The radically curable material includes one or more oligomers or monomers selected from the group consisting of fluorene-based epoxy (meth) acrylates and fluorene-based urethane (meth) acrylates having a fluorene skeleton of the formula (2). Composition for anisotropic conductive film. [Formula 2]

In Chemical Formula 2, 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. 3. The method of claim 2, At least one of the epoxy monomers, epoxy oligomers or epoxy resins selected from the group consisting of bisphenol, novolac, glycidyl, aliphatic and alicyclic compounds is selected from the group consisting of solid epoxy, liquid epoxy and soluble epoxy resins. 1 or more types of composition for anisotropic conductive films. The method of claim 1, The radical initiator is a composition for an anisotropic conductive film, characterized in that at least one selected from the group consisting of a photopolymerization initiator and a thermosetting initiator. 3. The method of claim 2, The curing agent is a composition for anisotropic conductive films, characterized in that at least one selected from the group consisting of acid anhydride, amine, imidazole and hydrazide as a thermosetting agent for epoxy. The method according to claim 1 or 2, The electroconductive particle is a metal particle containing 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 member selected from the group consisting of insulated conductive particles coated by adding insulating particles thereon. Anisotropic conductive film formed of the composition according to claim 1.