KR20100077793A - 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 to various substrates, to maintain an initial exterior by preventing the composition from being lifted in high temperature/high humidity and a thermal impact condition, and to have high reliability to other contact resistances. CONSTITUTION: An anisotropic conductive film comprises: 100-300 parts by weight of a radical curable material; 5-15 parts by weight of a radical initiator; 10-40 parts by weight of a conductive particles; and 3-8 parts by weight of a coupling agent based on 100.0 parts by weight of a thermoplastic polymer binder resin. The thermoplastic polymer binder resin includes 5-75 parts by weight of a polyester-polysiloxane copolymer which is marked as a chemical formula 1 based on 100.0 parts by weight of a binder resin. The chemical formula 1 is (A)_aB. In the chemical formula 1, a is integer more than 1 and (A) shows a polyester unit having a structure of H-[O-(CR^1_2)n-CO-]m-X-R^2-.

Description

Composition for anisotropic conductive films with improved reliability and anisotropic conductive films using same {ANISOTROPIC CONDUCTIVE FILM COMPOSITION FOR IMPROVEMENT OF ADHESION AND ANISOTROPIC CONDUCTIVE FILM USING IT}

The present invention relates to a composition for an anisotropic conductive film, and more particularly to a composition for an anisotropic conductive film comprising a polyester-polysiloxane copolymer as a component of the composition 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 widely used for LCD panels and tape carrier packages (hereinafter referred to as TCP) or electrical connections such as 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, the maintenance of the process control and the connecting device was 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 the display product as described above, the object of the embodiment according to the present invention, polyester-polysiloxane By including the copolymer as a component of the composition, it has excellent fluidity of the entire composition system, excellent initial adhesion to various substrates, and prevents the floating phenomenon of various adhesives such as zinc copper and polyimide during long-term operation under high temperature / high humidity and thermal shock conditions. Maintaining the initial appearance and having high reliability for other connection resistance, thereby improving the product reliability for a variety of display devices while having a wide range of applications for various adhesive compositions and compositions By anisotropic conductive film The purpose is to provide.

In order to achieve the above object, the present invention, a) thermoplastic polymer binder resin, b) radical curable material, c) radical initiator, d) conductive particles and e) coupling agent, a) thermoplastic polymer binder resin It provides a composition for an anisotropic conductive film comprising a polyester-polysiloxane copolymer.

In addition, the present invention, a) thermoplastic polymer binder resin, b) at least one epoxy monomer selected from bisphenol type, novolak type, glycidyl type, aliphatic and alicyclic, epoxy oligomer or epoxy resin, c) epoxy curing agent, d) conductivity Particles, e) a coupling agent, f) an inorganic filler, wherein a) the thermoplastic polymer binder resin provides a composition for an anisotropic conductive film, characterized in that it comprises a polyester-polysiloxane copolymer.

As described in detail above, by including a polyester-polysiloxane copolymer as a component of the composition, excellent flowability of the entire composition system, excellent initial adhesion to various substrates and zinc copper, polyimide when driven for a long time under high temperature / high humidity and thermal shock conditions Maintains the initial appearance by preventing the lifting phenomenon for a variety of adherends, such as, and has a 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.

Hereinafter, the present invention will be described in detail.

A. Radical  Adhesive composition for curable anisotropic conductive film

One embodiment of the present invention, as the adhesive composition for radically curable anisotropic conductive film,

a) with respect to 100 parts by weight of the thermoplastic polymer binder resin

b) 100 to 300 parts by weight of a radical curable material,

c) 5 to 15 parts by weight of radical initiator,

d) 10-40 weight part of electroconductive particle; And

e) 3 to 8 parts by weight of coupling agent,

The a) thermoplastic polymer binder resin relates to a composition for an anisotropic conductive film, characterized in that it comprises 5 to 75 parts by weight of the polyester-polysiloxane copolymer represented by the formula (1) relative to 100 parts by weight of the binder resin.

[Formula 1]

(A) _a B

(Wherein a is an integer ≥ 1, (A) means a polyester unit having a structure of H- [O- (CR ¹ ₂ ) _n -CO-] _m -XR ^2- , and B is (R _{^{3 2 SiO 2/2) P}} (r 3 3 SiO 1/2) q [O 1/2 H] r [O 1/2 SiR 4 2] means a polysiloxane unit with the structure of _t. in addition, in the formula, X means oxygen or NR ^x , R ¹ means the same or different monovalent substituted or unsubstituted hydrocarbon radicals or hydrogen, R ² has 1 to 40 carbon atoms and individual carbon atoms can be substituted with oxygen atoms. Divalent substituted or unsubstituted valuable hydrocarbon radical, R ^x means a monovalent substituted or unsubstituted hydrocarbon radical having 1 to 20 carbon atoms and wherein individual carbon atoms can be substituted with oxygen atoms, hydrogen or- SiR 'means ^₂ -R ₂ -NR ^x, and, where R' is the same or different and means a monovalent substituted or unsubstituted hydrocarbon radical , N is the mean of 3-10 integers, m means an integer of 1 to 1000. In addition, the formula, R ³ may be the same or different, a substituted or unsubstituted, aliphatic, saturated or unsaturated, linear, cyclic, Or a branched hydrocarbon or hydrocarbon-oxy radical having 1 to 20 carbon atoms, or a substituted or unsubstituted hydrocarbon or hydrocarbon-oxy radical having 6 to 20 carbon atoms, and R ⁴ is the same or different, Substituted or unsubstituted, aliphatic saturated, linear, cyclic, or branched hydrocarbon or hydrocarbon-oxy radical, or substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms, or Meaning a hydrocarbon-oxy radical, P is an integer from 0 to 3000, q is an integer from 0 to 50, r is an integer ≧ 0 and t is an integer ≧ 1.)

The composition may further include 0.1 to 5 parts by weight of at least one additive selected from the group consisting of an polymerization inhibitor, an antioxidant, a heat stabilizer, and a curing accelerator, based on 100 parts by weight of the thermoplastic binder resin.

Hereinafter, each component constituting the composition according to the embodiment of the present invention will be described in detail.

a) thermoplastic polymer binder resin

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. It can be manufactured by a general method, and in general, as the content of acrylonitrile increases, the physical properties and properties are excellent, but SAN resin having a high acrylonitrile content in consideration of deterioration in processability and thermal stability during processing. Except for special cases such as manufacturing, continuous bulk polymerization has been widely used, which is superior in transparency and other physical properties to other processes. 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-based 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 / high 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 with respect to the binder portion of the anisotropic conductive film according to the object of the present invention are not necessarily limited to the products described, 5 to 50% by weight based on 100% by weight of the composition selected from at least one It is preferable to include. If the content is less than 5% by weight, there is a problem that the film properties are weakened. If the content is more than 50% by weight, appearance characteristics and connection resistance are inhibited.

(a-1) Polyester-Polysiloxane Copolymer

At least one analogous compound selected from polyester-polysiloxane copolymers is included in the binder as an essential inclusion component of the anisotropic conductive film for achieving the object of the present invention. The general structure of the polyester-polysiloxane copolymer is as described in part in the following formula (1).

[Formula 1]

(A) _a B

(Where a is an integer ≥ 1, (A) means a polyester unit having a structure of H- [O- (CR ¹ ₂ ) _n -CO-] _m -XR ^2- , and B is (R _{^{3 2 SiO 2/2) P}} (r 3 3 SiO 1/2) q [O 1/2 H] r [O 1/2 SiR 4 2] means a polysiloxane unit with the structure of _t. in addition, in the formula, X means oxygen or NR ^x , R ¹ means the same or different monovalent substituted or unsubstituted hydrocarbon radicals or hydrogen, R ² has 1 to 40 carbon atoms and individual carbon atoms can be substituted with oxygen atoms. Divalent substituted or unsubstituted valuable hydrocarbon radical, R ^x means a monovalent substituted or unsubstituted hydrocarbon radical having 1 to 20 carbon atoms and wherein individual carbon atoms can be substituted with oxygen atoms, hydrogen or- SiR 'means ^₂ -R ₂ -NR ^x, in which R' is the same or different and means a monovalent substituted or unsubstituted hydrocarbon radical , N is the mean of 3-10 integers, m means an integer of 1 to 1000. In addition, the formula, R ³ may be the same or different, a substituted or unsubstituted, aliphatic, saturated or unsaturated, linear, cyclic, Or a branched hydrocarbon or hydrocarbon-oxy radical having 1 to 20 carbon atoms, or a substituted or unsubstituted hydrocarbon or hydrocarbon-oxy radical having 6 to 20 carbon atoms, and R ⁴ is the same or different , Substituted or unsubstituted, aliphatic saturated, linear, cyclic, or branched hydrocarbon having 1 to 20 carbon atoms or hydrocarbon-oxy radical, or substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms Or a hydrocarbon-oxy radical, P is an integer from 0 to 3000, q is an integer from 0 to 50, r is an integer ≧ 0 and t is an integer ≧ 1.)

The polyester-polysiloxane copolymers of the present invention show a number of excellent properties as the degree of polymerization and the polysiloxane component to polyester content ratio are controlled. The copolymers of the present invention show a wide range of applications as such or as components in various resins. By chemical bonding of polysiloxanes and aliphatic polyesters, the copolymers of the present invention show superior improved physical properties compared to the parent polymer or simple mixtures. There is also a characteristic that does not exhibit any bleeding effect. Polyester-polysiloxane copolymers can be widely used throughout mechanical or electronic materials that require the effects of adhesives, coatings, cosmetics, waxes, plastics, antiwear, antislip, and the like.

Polysiloxanes tend to show a high affinity for basic substances, and also have a lower compatibility with other organic compounds. However, as a result of copolymerizing an aliphatic polyester to polysiloxane, it has superior advantages in physical properties such as solubility, flowability, adhesion to various substrates, heat resistance, impact resistance, weather resistance, and coating properties, compared to conventional polysiloxane compounds.

The polyester-polysiloxane copolymer can implement various physical properties depending on the main component. When the main component of the copolymer is an aliphatic polyester, it can be used as a binder or an additive of a surface coating material and various coating compositions, which is moisture / waterproof and weather resistant. , Anti-wear effect, anti-block, anti slip, etc. can be improved. In addition, the main components of polysiloxanes include electrical and electronic components, laminated circuit boards, composite materials, paints, adhesives, structural materials, and anticorrosive applications and modifications of mechanical properties, which have improved properties over the addition of conventional polysiloxanes. see.

Furthermore, the polyester-polysiloxane copolymers of the present invention can improve the properties of various thermosetting / thermoplastic resins as one component of the composition. Examples of thermosetting resins to which the polyester-polysiloxane copolymer may be added include epoxy resins, polyurethanes, polyureas, polyamides, epoxy resins, unsaturated polyester resins, polyester-polyether copolymers, polyimides, melamine resins, Phenolic resins, diallyl phthalate resins and derivatives thereof, and examples of thermoplastic resins include polyacrylonitrile, polymethacrylonitrile, polymethyl acrylate, polyacrylamide, polymethacrylate and polymethacryl. Latex esters, and other acrylic resins, polystyrenes, polyesters, polyamides, polyesteramides, thermoplastic polyurethanes, polyvinyl chlorides, polycarbonates, polyacetals, polyvinylidene chlorides, polyvinyl alcohols and cellulose derivatives.

It is preferable to include 5 to 75 parts by weight relative to 100 parts by weight of the binder resin by selecting one or more of the polyester-polysiloxane copolymers listed above as a factor for improving the reliability for the anisotropic conductive film according to the object of the present invention. In the case of a radically curable adhesive composition, when the content is less than 5 parts by weight, there is no effect of improving reliability, and when it exceeds 75 parts by weight, a phenomenon in which appearance characteristics are inhibited appears.

b) Radical  Curable material

As the radical curable material, a (meth) acrylate oligomer or a (meth) acrylate monomer may be used, and it is preferable to include 100 to 300 parts by weight based on 100 parts by weight of the binder. If the content is less than 100 parts by weight, the appearance and curing properties are lowered, and if it exceeds 300 parts by weight, the adhesion and reliability with the substrate, film properties and the like may be inhibited. Each will be described in detail below.

(b-1) ( Meta ) 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, 1,4 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-bromohydro quinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, 4,4'-di Composed of a skeleton such as hydroxybiphenyl, bis (4-hydroxyphenyl) ether, and 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, etc. What is chosen from the (meth) acrylate oligomer group can 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 , 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-maleimidephenoxy) 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 one or more of the above-mentioned fluorene-based (meth) acrylate oligomers are used as the (meth) acrylate oligomer of the present invention, due to the excellent insulation exhibited in the fluorene structure, the possibility of short circuit between circuits can be further increased. And further ensure the initial low connection resistance and high reliability to improve the productivity and reliability of the final product.

(b-2) ( Meta ) Acrylate Monomer

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 Lithol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin di (meth) acrylate, t-hydroperfuryl (meth) acrylate, iso-decyl (meth) acrylate, 2- ( 2-ethoxyethoxy) ethyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tri Decyl (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 type bisphenol-A di (meth) Acryl , 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).

c) Radical Initiator

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 monocar 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.

It is preferable that the said radical initiator contains 5-15 weight part with respect to 100 weight part of binder resin of this invention. If the content is less than 5 parts by weight, the curing reaction may not be sufficiently performed, the appearance characteristics and reliability characteristics may be inhibited. If the content exceeds 15 parts by weight, corrosion and deterioration of reliability due to residual radicals may occur.

d) 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 in the range of 2 to 30 ㎛ by the pitch of the circuit to be applied, and in the case of a radical curable adhesive composition includes 10 to 40 parts by weight relative to 100 parts by weight of the binder resin can do. If the content is less than 10 parts 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 the content exceeds 40 parts by weight, it is easy to cause poor insulation.

e) Coupling agent  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.

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 0.1 to 5 parts by weight based on 100 parts by weight of the binder resin is selected.

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. Kis- (methylene- (3,5-di-t-butyl-4-hydro cinnamate) methane, 3,5-bis (1,1-dimethylethyl) -4-hydroxy benzene propanoic acid thiol di -2,1-ethanediyl ester, octadecyl 3,5-di-t-butyl-4-hydroxy hydrocinnamate (above manufactured by Ciba), 2,6-di-tertiary-p-methylphenol, and the like In addition, the curing accelerator for improving the reaction rate may be used at least one of a solid imidazole accelerator, a solid and a liquid amine curing accelerator, etc. The various additives are not limited to the types described.

B. Adhesive Composition for Epoxy Type Anisotropic Conductive Film

Composition for the epoxy type anisotropic conductive film according to another embodiment of the present invention,

a) 100 parts by weight of a thermoplastic polymer binder resin,

b) 25 to 60 parts by weight of at least one epoxy monomer, epoxy oligomer or epoxy resin selected from bisphenol type, novolac type, glycidyl type, aliphatic and alicyclic,

c) 5 to 20 parts by weight of an epoxy curing agent,

d) 5 to 25 parts by weight of conductive particles,

e) 1 to 8 parts by weight of the coupling agent and

f) 10 to 50 parts by weight of an inorganic filler,

The a) thermoplastic polymer binder resin relates to a composition for an anisotropic conductive film, comprising 3 to 60 parts by weight of the polyester-polysiloxane copolymer represented by the formula (1) relative to 100 parts by weight of the binder resin.

The composition may further include 0.1 to 5 parts by weight of at least one additive selected from the group consisting of an polymerization inhibitor, an antioxidant, a heat stabilizer, and a curing accelerator, based on 100 parts by weight of the thermoplastic binder resin.

Hereinafter, each component constituting the composition according to the embodiment of the present invention will be described in detail.

a) thermoplastic polymer binder resin

The thermoplastic polymer binder resin is the same as that described for the composition for radically curable anisotropic conductive films. However, in the case of epoxy curable adhesive composition, it is preferable that the content of polyester polysiloxane copolymer contains 3 to 60 weight part with respect to 100 weight part of binder solid content.

b) 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. As such an epoxy resin, any material containing at least one bond structure that can be selected from among the known epoxy-based molecular structures such as bisphenol type, novolak type, glycidyl type, aliphatic, alicyclic, etc. is not limited. Can be used

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.

In the present invention, it is preferable to use the epoxy resin composed of bisphenol type, novolak type, glycidyl type, aliphatic and alicyclic in the range of 25 to 60 parts by weight relative to 100 parts by weight of the thermoplastic binder resin solid content. When the content is less than 25 parts by weight, the hardened part is relatively insufficient, and the appearance and connection properties are inhibited. When the content is more than 60 parts by weight, the film properties are insufficient and the reliability deterioration characteristics are inhibited.

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.

c) epoxy curing agent

The composition for epoxy curable anisotropic conductive films of this invention uses a combination of 1 or more types of epoxy thermosetting agents as another component of a hardening part.

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 5 to 20 parts by weight based on 100 parts by weight of the thermoplastic binder resin solid content. When the content is less than 5 parts by weight, the curing reaction may not be sufficiently carried out, the appearance characteristics and reliability characteristics may be inhibited. When the content is more than 20 parts by weight, stability degradation and reliability degradation due to the residual curing agent may occur.

d) conductive particles

      It is the same as the kind described about the composition for radically curable anisotropic conductive films. However, in the case of the epoxy curable adhesive, the content of the conductive particles is preferably included 5 to 25 parts by weight relative to 100 parts by weight of the binder resin.

e) Coupling agent  And other additives

      The same kind as the described coupling agent and additive for the composition for radically curable anisotropic conductive films can be used. In the adhesive composition for an epoxy curable anisotropic conductive film, the coupling agent is preferably used in an amount of 1 to 8 parts by weight based on 100 parts by weight of the binder resin, and other additives may be added in an amount of 0.1 to 10 parts by weight.

f) weapons filler

The adhesive composition for epoxy curable anisotropic conductive films includes 20 to 50 parts by weight of the inorganic filler relative to 100 parts by weight of the binder. 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.

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 The other binder part resin and the hardened part and the conductive particles are stirred for a predetermined time within the range of the pulverization, and applied to a thickness of 10 to 50 ㎛ on a release film and then dried for a certain time to volatilize the organic solvent to form a single layer structure Branches can obtain an anisotropic conductive film. 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. 20 g of copolymer resin (KLS-1040, Fujikura Kasei), 9 g of urethane resin (KUB2001, Gangnam), dissolved in methyl ethyl ketone at 40% by weight, 1 g of polyester-polysiloxane copolymer; 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, 5 g of the conductive particles (23GNR5.0-MX, NCI Co., Ltd.) having a size of 5 µm was insulated and then 5 g was added to complete the configuration.

< Example  2>

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 copolymer resin (KLS-1040, Fujikura Kasei), 10 g of polyester-polysiloxane copolymer; 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, 5 g of the conductive particles (23GNR5.0-MX, NCI Co., Ltd.) having a size of 5 µm was insulated and then 5 g was added to complete the configuration.

< Example  3>

The binder resin portion serving as a matrix for forming a film is 15 g of NBR-based resin (N-21, Nipon Xeon) dissolved in toluene / methyl ethyl ketone azeotropic mixed solvent at 30% by weight, and acrylic compound dissolved in methyl ethyl ketone at 25% by weight. 15 g of copolymer resin (KLS-1040, Fujikura Kasei), 20 g of polyester-polysiloxane copolymer; 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  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), 19 g of phenoxy resin (PKHH, Inchemrez, USA) dissolved in toluene at 30% by weight, 1 g of polyester-polysiloxane copolymer; As the hardening part accompanied by the curing reaction, 23 g of an epoxy resin (JER-834, Japan epoxy resin) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 30% by weight and 30% by weight in a toluene / methyl ethyl ketone azeotropic mixed solvent 14 g of fluorene-based 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; 1 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 4 g was added to complete the configuration.

< Example  5>

As the binder resin portion serving as the matrix for film formation, bisphenol-A epoxy resin / reactive epoxy diluent / methyl methacrylate-butadiene-styrene core-shell copolymer resin has a weight ratio of 30/30/40. 25 g of resin mixed with (RKB-2023, Reginous Kasei), 10 g of phenoxy resin (PKHH, Inchemrez, USA) dissolved in toluene at 30% by weight, 10 g of polyester-polysiloxane copolymer; As the hardening part accompanied by the curing reaction, 23 g of an epoxy resin (JER-834, Japan epoxy resin) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 30% by weight and 30% by weight in a toluene / methyl ethyl ketone azeotropic mixed solvent 14 g of fluorine-based 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; 1 g of γ-glycidoxy propyl trimethoxy silane (KBM-403, ShinEtsu) as coupling agent; 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 4 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), 20 g of polyester-polysiloxane copolymer; As the hardening part accompanied with the curing reaction, 23 g of an epoxy resin (JER-834, Japan epoxy resin) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 30% by weight and 30% by weight in a toluene / methyl ethyl ketone azeotropic mixed solvent was used. 14 g of dissolved fluorene-based 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; 1 g of γ-glycidoxy propyl trimethoxy silane (KBM-403, ShinEtsu) as coupling agent; 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 4 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. 20 g of copolymer resin (KLS-1040, Fujikura Chemical), 10 g of urethane resin (KUB2001, Kangnam Chemical) dissolved in methyl ethyl ketone at 40 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, 15 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 copolymer resins (KLS-1040, Fujikura Kasei), 25 g of polyester-polysiloxane copolymer; 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  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), 20 g of phenoxy resin (PKHH, Inchemrez, USA) dissolved in toluene at 30% by weight; As a hardening part accompanied with a curing reaction, 23 g of an epoxy resin (JER-834, Japan epoxy resin) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 30 g, and a flu dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 30 wt% Oren epoxy resin (BPEFG, Osaka Gas) 14g; 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; 1 g of γ-glycidoxy propyl trimethoxy silane (KBM-403, ShinEtsu) as coupling agent; 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 4 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. 20 g of mixed resin (RKB-2023, Reginous Kasei), 25 g of polyester-polysiloxane copolymer; As the hardening part accompanied by the curing reaction, 23 g of an epoxy resin (JER-834, Japan epoxy resin) dissolved in a toluene / methyl ethyl ketone azeotropic mixed solvent at 30% by weight and 30% by weight in a toluene / methyl ethyl ketone azeotropic mixed solvent 14 g of fluorene-based 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; 1 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 4 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 the silicon release surface-treated polyethylene base film, using a casting knife to form a film, the drying time of the film was 10 at 50 ℃ Minutes.

Evaluation of Physical 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 2 and Comparative Examples 1 to 2, 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, compared to the anisotropic conductive film using a polyester-polysiloxane copolymer according to an embodiment of the present invention as a component of the composition, the resin is not used Compared with the anisotropic conductive film of Example 1, Comparative Example 3 and the polyester-polysiloxane copolymer according to the embodiment of the present invention, Comparative Example 2, Comparative Example 4 showed excellent results in both the initial adhesive strength and the adhesive strength after the reliability evaluation It can be seen.

(Initial connection resistance and reliability connection resistance measurement results)

As shown in the connection resistance measurement results of Table 2, the anisotropic conductive film using the polyester-polysiloxane copolymer according to the embodiment of the present invention as a component of the composition had low resistance values at both the initial connection resistance and the connection resistance after the reliability evaluation. It can be seen that the anisotropic conductive film using the polyester-polysiloxane copolymer according to the embodiment of the present invention as a component of the composition according to the results of the conventional commercially available thermoplastic resin and acrylic or phenoxy resin, etc. It can be seen that it has excellent initial properties and high reliability compared to the anisotropic conductive film consisting of only.

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 all of the polyester-polysiloxane copolymer represented by the general formula (1), and is not limited to the kind described in the above general formula in the claims, the appended claims belong to the gist of the present invention. Includes modifications and variations.

Claims (11)

a) with respect to 100 parts by weight of the thermoplastic polymer binder resin b) 100 to 300 parts by weight of a radical curable material, c) 5 to 15 parts by weight of radical initiator, d) 10-40 weight part of electroconductive particle; And e) 3 to 8 parts by weight of coupling agent, The a) thermoplastic polymer binder resin is a composition for an anisotropic conductive film, characterized in that it comprises 5 to 75 parts by weight of the polyester-polysiloxane copolymer represented by the formula (1) relative to 100 parts by weight of the binder resin. [Formula 1] (A) _a B (Wherein a is an integer ≥ 1, (A) means a polyester unit having a structure of H- [O- (CR ¹ ₂ ) _n -CO-] _m -XR ^2- , and B is (R ^{_{3 2 SiO 2/2) P}} (R 3 3 SiO 1/2) q [O 1/2 H] r [O 1/2 SiR 4 2] means a polysiloxane unit with the structure of _t. in addition, in the formula, X means oxygen or NR ^x , R ¹ means the same or different monovalent substituted or unsubstituted hydrocarbon radicals or hydrogen, R ² has 1 to 40 carbon atoms and individual carbon atoms can be substituted with oxygen atoms. Divalent substituted or unsubstituted valuable hydrocarbon radical, R ^x means a monovalent substituted or unsubstituted hydrocarbon radical having 1 to 20 carbon atoms and wherein individual carbon atoms can be substituted with oxygen atoms, hydrogen or- SiR 'means ^₂ -R ₂ -NR ^x, in which R' is the same or different and means a monovalent substituted or unsubstituted hydrocarbon radical , N is the mean of 3-10 integers, m means an integer of 1 to 1000. In addition, the formula, R ³ may be the same or different, a substituted or unsubstituted, aliphatic, saturated or unsaturated, linear, cyclic, Or a branched hydrocarbon or hydrocarbon-oxy radical having 1 to 20 carbon atoms, or a substituted or unsubstituted hydrocarbon or hydrocarbon-oxy radical having 6 to 20 carbon atoms, and R ⁴ is the same or different, Substituted or unsubstituted, aliphatic saturated, linear, cyclic, or branched hydrocarbon or hydrocarbon-oxy radical, or substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms, or Meaning a hydrocarbon-oxy radical, P is an integer from 0 to 3000, q is an integer from 0 to 50, r is an integer ≧ 0 and t is an integer ≧ 1.) a) with respect to 100 parts by weight of the thermoplastic polymer binder resin b) 25 to 60 parts by weight of at least one epoxy monomer, epoxy oligomer or epoxy resin selected from bisphenol type, novolac type, glycidyl type, aliphatic and alicyclic, c) 5 to 20 parts by weight of an epoxy curing agent, d) 5 to 25 parts by weight of conductive particles, e) 1 to 8 parts by weight of the coupling agent and f) 10 to 50 parts by weight of an inorganic filler, The a) thermoplastic polymer binder resin is an anisotropic conductive film composition, characterized in that it comprises a polyester-polysiloxane copolymer represented by the formula (1) 3 to 60 parts by weight relative to 100 parts by weight of the binder resin. [Formula 1] (A) _a B (Wherein a is an integer ≥ 1, (A) means a polyester unit having a structure of H- [O- (CR ¹ ₂ ) _n -CO-] _m -XR ^2- , and B is (R ^{_{3 2 SiO 2/2) P}} (r 3 3 SiO 1/2) q [O 1/2 H] r [O 1/2 SiR 4 2] means a polysiloxane unit with the structure of _t. in addition, in the formula, X means oxygen or NR ^x , R ¹ means the same or different monovalent substituted or unsubstituted hydrocarbon radicals or hydrogen, R ² has 1 to 40 carbon atoms and individual carbon atoms can be substituted with oxygen atoms. Divalent substituted or unsubstituted valuable hydrocarbon radical, R ^x means a monovalent substituted or unsubstituted hydrocarbon radical having 1 to 20 carbon atoms and wherein individual carbon atoms can be substituted with oxygen atoms, hydrogen or- SiR 'means ^₂ -R ₂ -NR ^x, in which R' is the same or different and means a monovalent substituted or unsubstituted hydrocarbon radical , N is the mean of 3-10 integers, m means an integer of 1 to 1000. In addition, the formula, R ³ may be the same or different, a substituted or unsubstituted, aliphatic, saturated or unsaturated, linear, cyclic, Or a branched hydrocarbon or hydrocarbon-oxy radical having 1 to 20 carbon atoms, or a substituted or unsubstituted hydrocarbon or hydrocarbon-oxy radical having 6 to 20 carbon atoms, and R ⁴ is the same or different, Substituted or unsubstituted, aliphatic saturated, linear, cyclic, or branched hydrocarbon or hydrocarbon-oxy radical, or substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms, or Meaning a hydrocarbon-oxy radical, P is an integer from 0 to 3000, q is an integer from 0 to 50, r is an integer ≧ 0 and t is an integer ≧ 1.) The method according to claim 1 or 2, The composition may further comprise 0.1 to 5 parts by weight of at least one additive selected from the group consisting of a polymerization inhibitor, an antioxidant, a heat stabilizer and a curing accelerator, based on 100 parts by weight of the thermoplastic binder resin. The method according to claim 1 or 2, The thermoplastic polymer binder resin may be 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, At least one resin selected from the group consisting of polyvinyl 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 radically curable materials include urethane-based (meth) acrylates, epoxy-based (meth) acrylates, polyester-based (meth) acrylates, fluorine-based (meth) acrylates, fluorene-based (meth) acrylates, and silicone-based (meth) acrylates. At least one oligomer selected from oligomers consisting of latex, phosphate (meth) acrylates, maleimide modified (meth) acrylates and acrylates (methacrylates), or mixtures thereof, wherein the average molecular weight is in the range of 1,000 to 100,000 ( Meta) acrylate oligomers; 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, penta Erythritol 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; It is a mixture of the said (meth) acrylate oligomer and the said (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 monomer, epoxy oligomer or epoxy resin selected from the group consisting of the bisphenol type, novolak type, glycidyl type, aliphatic and cycloaliphatic is selected from the group consisting of solid phase epoxy, liquid epoxy and soluble epoxy resin 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.