KR101355854B1 - Anisotropic conductive film - Google Patents

Abstract

The present invention relates to an anisotropic conductive film containing a polyester urethane resin and tricyclodecane dimethanol diacrylate together.
More specifically, the present invention contains a polyester urethane resin and tricyclodecane dimethanol diacrylate together, high storage elastic modulus, strong resistance to shrinkage and expansion, less bubble generation, even if left for a long time under high temperature and high humidity The present invention relates to an anisotropic conductive film excellent in reliability of adhesive strength and reliability of connection.

Description

Anisotropic conductive film < RTI ID = 0.0 >

The present invention contains polyester urethane resin and tricyclodecane dimethanol diacrylate together, and thus has high storage elastic modulus, resists shrinkage and expansion, has low bubble generation, reliable adhesion even when left for a long time under high temperature and high humidity. The anisotropic conductive film excellent in the reliability connection property.

Anisotropic conductive film (ACF) is a film obtained by dispersing conductive particles such as metal particles such as nickel (Ni) and gold (Au), or polymer particles coated with such metals in a resin such as epoxy Means a polymeric film having electric anisotropy and adhesiveness which has conductivity in the film thickness direction of the film and has insulating property in the plane direction. When the film is placed between the circuit to be connected with the anisotropic conductive film and subjected to a heating and pressing process under a certain condition, the circuit terminals are electrically connected by the conductive particles, and an insulating adhesive resin And the conductive particles are filled independently of each other, thereby providing high insulating properties.

In recent years, there has been a tendency that panels are becoming larger and wirings are widening. As a result, the space between the electrode and the electrode is widened. As a result, the connecting substrate is expanded by the compression due to heat and pressure at the time of bonding, and after the bonding, the connecting substrate shrinks again and the degree of expansion and contraction of the bonding composition is seriously generated, There is a problem that the filling effect of the adhesive composition is deteriorated.

Conventionally, in order to solve such a problem, there is a method using a binder resin having a high glass transition temperature (Tg) (Japanese Patent Laid-Open No. 2011-0159486, etc.). However, in the case of using a binder resin having a high glass transition temperature, although the physical properties are hard and the resistance to shrinkage and expansion is improved, the flowability of the resin is reduced and the indentation is weakened, resulting in a decrease in the contact area of the conductive particles. By doing so, there is a problem of lowering connection reliability.

On the other hand, as a prior art related to the present invention, there is Republic of Korea Patent Publication No. 10-2011-0095127. The above prior art is a film containing a phenoxy resin and a radical polymerizable material, and relates to a low temperature fast curing type anisotropic conductive film excellent in connectivity.

The prior art discloses the use of tricyclodecane dimethanol diacrylate as a radical polymerizable material, but it is disclosed to use it with a phenoxy resin, which is a problem. Specifically, phenoxy resin is a compound having a very high acid value, and when used with a radically polymerizable material, has a tendency to promote metal corrosion, and when the semiconductor device is connected by using an anisotropic conductive film utilizing the same, the reliability of the device is lowered. there is a problem. Therefore, the phenoxy resin and tricyclodecane dimethanol diacrylate have a problem of compatibility, and it is difficult to expect high reliability properties with the above-described prior art using them together, and hard properties and withstand resistance to shrinkage / expansion can also be expected. none.

Japanese Laid-Open Patent Publication No. 2011-0159486 (August 08, 2011) Republic of Korea Patent Publication A No. 10-2011-0095127 (August 24, 2011)

In order to solve the above problems, the present inventors have a polyester urethane resin and tricyclodecane dimethanol diacrylate together, so that the storage elastic modulus is high, so it is resistant to shrinkage and expansion, there is little bubble generation, and high temperature and high humidity. Even if it was left for a long time under the condition, the anisotropic conductive film excellent in reliable adhesive force and reliable connection property was developed.

An object of the present invention is to provide an anisotropic conductive film containing polyester urethane resin and tricyclodecane dimethanol diacrylate, exhibiting rigid physical properties and suppressing volume change due to heat.

In addition, the present invention has a strong resistance to heat shrinkage and expansion to provide an anisotropic conductive film that not only suppresses the initial bubble generation of the film bonding site, but also suppresses the increase in the bubble area after a long time under high temperature and high humidity. The purpose.

In addition, an object of the present invention is to provide an anisotropic conductive film having rigid properties and excellent in excellent adhesive strength.

The present invention relates to an anisotropic conductive film containing a polyester urethane resin and tricyclodecane dimethanol diacrylate together.

According to one aspect of the present invention,

a) a binder portion comprising a polyester urethane resin;

b) radically polymerizable materials including tricyclodecane dimethanol diacrylate;

c) a curing initiator; And

d) conductive particles

It provides the anisotropic conductive film containing.

According to another aspect of the present invention,

To 100 parts by weight of solids of the anisotropic conductive film,

a) 40 to 80 parts by weight of a binder part comprising a polyester urethane resin;

b) 5 to 50 parts by weight of a radically polymerizable material comprising tricyclodecane dimethanol diacrylate;

c) 0.1 to 10 parts by weight of a curing initiator; And

d) 0.1 to 10 parts by weight of conductive particles

It provides the anisotropic conductive film containing.

According to another aspect of the present invention, there is provided an anisotropic conductive film containing 5 to 40 parts by weight of the polyester urethane resin based on 100 parts by weight of the solid content of the anisotropic conductive film.

According to still another aspect of the present invention, there is provided an anisotropic conductive film containing 5 to 30 parts by weight of the tricyclodecane dimethanol diacrylate, based on 100 parts by weight of the solid content of the anisotropic conductive film.

According to still another aspect of the present invention, in the anisotropic conductive film, an anisotropic conductive film further containing organic or inorganic particles is provided.

According to another aspect of the present invention, the organic particles may be an acrylic resin such as an acrylate resin, an ethylene acrylate copolymer, an ethylene acrylic acid copolymer, an olefin resin such as an ethylene resin, an ethylene propylene copolymer, butadiene resin, or acryl. Ronitrile butadiene copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, carboxylated styrene-ethylenebutadiene-styrene block copolymer, ethylene styrene butylene block copolymer, Rubbers such as butadiene rubber, nitrile-butadiene rubber, styrene butadiene rubber, chloroprene rubber, vinyl resins such as vinylbutylal resin and vinylform resin, ester resins such as polyester and cyanate ester resin, phenoxy resin, silicone And particles made of rubber or urethane resin. These may be used singly or in combination of two or more.

According to another embodiment of the present invention, the inorganic particles may be silica, but is not limited thereto.

According to still another aspect of the present invention, there is provided an anisotropic conductive film containing 1 to 20 parts by weight of the organic or inorganic particles, based on 100 parts by weight of the solid content of the anisotropic conductive film.

According to still another aspect of the present invention, there is provided an anisotropic conductive film having a storage modulus at 40 ° C of 100 MPa or more after 90% or more of curing.

According to still another aspect of the present invention, an anisotropic conductive film having a bubble area of 20% or less based on the inter-electrode space area after 500 hours at a temperature of 85 ° C. and a relative humidity of 85% after main compression. to provide.

According to still another aspect of the present invention, an anisotropic conductive film having an adhesive strength of 500 gf / cm or more after being left for 500 hours at 85 ° C. and 85% relative humidity after main compression is provided.

According to another aspect of the present invention, as an anisotropic conductive film containing a polyester urethane resin and tricyclodecane dimethanol diacrylate,

a) the storage modulus at 40 ° C. is at least 100 MPa;

b) After the main compression, an anisotropic conductive film is provided in which the bubble area after being left for 500 hours at a temperature of 85 ° C. and a relative humidity of 85% is 20% or less based on the inter-electrode space area.

According to still another aspect of the present invention, there is provided a semiconductor device including a wiring board and a semiconductor chip and connected with the anisotropic conductive film.

Since the anisotropic conductive film of the present invention contains a polyester urethane resin and tricyclodecane dimethanol diacrylate together, it has a high storage elastic modulus, resists shrinkage and expansion, has little resistance to bubbles, and is left for a long time under high temperature and high humidity. Even if it is, it has the effect which was excellent in reliable adhesive force and reliable connection property.

More specifically, the present invention has an effect of providing an anisotropic conductive film containing polyester urethane resin and tricyclodecane dimethanol diacrylate, exhibiting rigid physical properties and suppressing volume change due to heat.

In addition, the present invention has a strong resistance to shrinkage and expansion due to heat not only to suppress the initial bubble generation of the film bonding site, but also to provide an anisotropic conductive film that suppresses the increase in the bubble area after a long time standing under high temperature and high humidity Has

In addition, the present invention has the effect of providing an anisotropic conductive film having a solid physical properties but excellent in excellent adhesion.

Hereinafter, the present invention will be described in more detail. Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

According to one aspect of the present invention,

a) a binder portion comprising a polyester urethane resin;

b) radically polymerizable materials including tricyclodecane dimethanol diacrylate;

c) a curing initiator; And

d) conductive particles

It provides the anisotropic conductive film containing.

a) binder

The binder portion used in the present invention is characterized by including a polyester urethane resin.

Polyester urethane resin

As a polyester urethane resin used by this invention, resin obtained by reaction of polyester polyol and diisocyanate can be used.

The polyester polyol refers to a polymer having a plurality of ester groups and a plurality of hydroxyl groups. The polyester polyol can be obtained by the reaction of dicarboxylic acid and diol.

Examples of the dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, succinic acid, glutaric acid, subberic acid, azelanic acid, dodecanedicarboxylic acid, hexahydrophthalic acid, ortho-phthalic acid, Tetrachlorophthalic acid, 1,5-naphthalenedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid or tetrahydrophthalic acid, and the like. Preferred are aromatic dicarboxylic acids or aliphatic dicarboxylic acids.

Examples of the diol include ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, dipropylene glycol, dibutylene glycol, 2-methyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol or 1,4-cyclo Hexane dimethanol etc. are mentioned, The above-mentioned glycol is preferable.

Examples of the diisocyanate include isophorone diisocyanate (IPDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), xylene diisocyanate, hydrogenated diphenylmethane di Isocyanate, naphthalene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, etc. are mentioned, Aromatic, alicyclic, or aliphatic diisocyanate is preferable.

The polyester urethane resin preferably has a weight average molecular weight of 10,000 to 100,000 g / mol, more preferably 25,000 to 70,000 g / mol can be used.

The polyester urethane resin may be contained in an amount of preferably 5 to 40 parts by weight, and more preferably 15 to 40 parts by weight, based on 100 parts by weight of the solid content of the anisotropic conductive film. Within this range, the storage modulus and the adhesive force are balanced, thereby obtaining a film having a hard physical property and excellent adhesion.

The binder resin used in the present invention together with the polyester urethane resin is not particularly limited, and resins commonly used in the art may be used. Non-limiting examples of the binder resin usable in the present invention include acrylic resins, polyurethane resins, NBR resins, and the like.

Acrylic resin

The acrylic resin usable in the present invention can be obtained by polymerizing an acrylic monomer and / or a monomer polymerizable therewith. For example, the acrylic resin is a copolymer obtained by polymerizing at least one monomer selected from the group consisting of (meth) acrylates having 2 to 10 carbon atoms, (meth) acrylic acid, vinyl acetate and acrylic monomers modified therefrom Lt; / RTI > The polymerization method is not particularly limited.

Polyurethane-based resin

Polyurethane resins usable in the present invention is a polymer resin having a urethane bond, for example, may be prepared by polymerizing isophorone diiso cyanate, polytetramethylene glycol and the like, but is not limited thereto. The polyurethane-based resin may be a resin having a weight average molecular weight of 50,000 to 100,000 g / mol.

NBR Resin

The NBR resins usable in the present invention are copolymers prepared by emulsion polymerization of acrylonitrile and butadiene, and the content of acrylonitrile and butadiene in the copolymer is not particularly limited, and the polymerization method is not particularly limited. . The NBR-based resin may be a resin having a weight average molecular weight of 50,000 to 2,000,000 g / mol.

The binder portion of the present invention may be contained preferably 40 to 80 parts by weight, more preferably 55 to 80 parts by weight with respect to 100 parts by weight of the solid content of the anisotropic conductive film. Within this range, the storage modulus and the adhesive force are balanced, thereby obtaining a film having a hard physical property and excellent adhesion.

b) radically polymerizable materials

The radically polymerizable material used in the present invention is characterized by including tricyclodecane dimethanol diacrylate.

The tricyclodecane dimethanol diacrylate used in the present invention may be contained in an amount of preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight, based on 100 parts by weight of the solid content of the anisotropic conductive film. have.

The radically polymerizable material used in the present invention with tricyclodecane dimethanol diacrylate is not particularly limited and may be a resin commonly used in the art. Non-limiting examples of the radically polymerizable material usable in the present invention include acrylates, methacrylates, maleimide compounds, and the like, and may be used in combination with monomers, oligomers or monomers and oligomers.

Acrylate  or Methacrylate

Examples of acrylates or methacrylates that can be used in the present invention include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimetholpropane Triacrylate, tetra methylol methane tetra acrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis [4- (acryloxypolymethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, dicyclopentenyl acrylate, tricyclodecanyl acrylate, tris (acryloyloxyethyl) isocyanate, tricyclodecane dimethanol diacrylate, 2-methacryloyl hydroxy phosphate, pentaerythritol tri (meth) acrylate or 2-hydroxyethyl (meth) acrylate, and the like. It is not limited. These may be used alone or in combination of two or more.

Maleimide

As a maleimide compound which can be used by this invention, what contains at least 2 maleimide group in a molecule | numerator can be used. For example 1-methyl-2,4-bismaleimidebenzene, N, N'-m-phenylenebismaleimide, N, N'-p-phenylenebismaleimide, N, N'-m-toyl Renbismaleimide, N, N'-4,4-biphenylenebismaleimide, N, N'-4,4- (3,3'-dimethylbiphenylene) 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-diphenylmethanebismaleimide, N, N'-4,4-diphenylpropanebismaleimide, N, N'-4,4-diphenyletherbismaleimide, N, N'-3,3 '-Diphenylsulfonebismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-s-butyl-4-8 (4-maleimidephenoxy C) phenyl) propane, 1,1-bis (4- (4-maleimidephenoxy) phenyl) decane, 4,4'-cyclohexythylidenebis (1- (4-maleimidephenoxy) -2 -Cyclohexyl benzene, 2,2-bis (4- (4-maleimidephenoxy) phenyl) hexafluoro propane and the like can be used But, this is not limited. These may be used alone or in mixture of two or more.

The radically polymerizable material of the present invention may be contained in an amount of preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight, based on 100 parts by weight of the solid content of the anisotropic conductive film. When the content of the radically polymerizable material is less than 5 parts by weight, reliable characteristics are lowered and overall flowability is lowered due to the lowering of the curing density after the main compression, and there is a possibility that the contact between the conductive particles and the circuit substrate may be deteriorated at the time of adhesion and the connection resistance. There is a concern that the rise of and resulting connection reliability may be lowered. On the other hand, when the content of the radically polymerizable material exceeds 50 parts by weight, there is a fear that the formation of the anisotropic conductive film is difficult, and there is a fear that the adhesive properties are lowered.

c) Curing initiator

The curing initiator used in the present invention is not particularly limited and may be a curing initiator commonly used in the art. Non-limiting examples of curing initiators that can be used in the present invention include, but are not limited to, peroxide and azo.

Peroxide Initiator

Peroxide initiators usable in the present invention include benzoyl peroxide, lauryl peroxide, t-butylteroxylaurate, 1,1,3,3-tetramethylbutyl peroxypivalate, cumene hydroperoxide, and the like. Can be used, but is not limited to these.

Azo Initiator

Azo initiators usable in the present invention 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) and the like can be used, but is not limited thereto.

The curing initiator used in the present invention may be contained in an amount of preferably 0.1 to 10 parts by weight based on 100 parts by weight of the solid content of the anisotropic conductive film.

d) conductive particles

The conductive particles used in the present invention are not particularly limited and conductive particles commonly used in the art can be used.

Non-limiting examples of the conductive particles usable in the present invention include metal particles including Au, Ag, Ni, Cu, solder, and the like; carbon; Particles comprising a resin including polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol or the like and particles of the modified resin coated with a metal such as Au, Ag, Ni or the like; Insulating particles coated with insulating particles, and the like.

The size of the said conductive particle can be selected and used according to a use in the range of 2-30 micrometers by the pitch of the circuit applied.

The conductive particles used in the present invention may preferably contain 0.1 to 10 parts by weight based on 100 parts by weight of the solid content of the anisotropic conductive film. Within the above range, the occurrence of connection and / or insulation failure can be prevented to obtain excellent connectivity.

According to another aspect of the present invention, there is provided an anisotropic conductive film further containing organic or inorganic particles in addition to the components a), b), c) and d).

The organic or inorganic particles are not particularly limited and particles commonly used in the art may be used.

Non-limiting examples of the organic particles used in the present invention are acrylate resins such as acrylate resins, ethylene acrylate copolymers, ethylene acrylic acid copolymers, olefin resins such as ethylene resins, ethylene propylene copolymers, butadiene resins, acrylonitrile Butyl-butadiene copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, carboxylated styrene-ethylenebutadiene-styrene block copolymer, ethylene styrene-butylene block copolymer, butadiene rubber Rubbers such as nitrile-butadiene rubber, styrene butadiene rubber, chloroprene rubber, vinyl resins such as vinylbutylal resin and vinylform resin, ester resins such as polyester and cyanate ester resin, phenoxy resin, silicone rubber or The particle | grains which consist of polyurethane resins, etc. are mentioned. These may be used singly or in combination of two or more.

The inorganic particles used in the present invention may include silica particles, but are not limited thereto.

The organic or inorganic particles may have a size of preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm. The particles can be dispersed to an appropriate extent within the above range, and the problem that the pressure-bonding property is deteriorated due to the stickiness of the film is prevented can be prevented.

The organic or inorganic particles may be contained in an amount of preferably 1 to 20 parts by weight based on 100 parts by weight of the solid content of the anisotropic conductive film. It is possible to sufficiently obtain the effect of adding the organic fine particles within the above range and to prevent the phenomenon that the toughness of the film is excessively increased to prevent the problem of deterioration of the tackiness.

According to another aspect of the present invention, an anisotropic conductive film having a storage modulus at 40 ° C. of 100 MPa or more is provided.

The method of measuring the storage modulus is not particularly limited, and a method commonly used in the art may be used. One non-limiting example of a method of measuring storage modulus is as follows: The anisotropic conductive film is cut to a certain size (eg, 5 mm x 30 mm) so that the measurement temperature range is -30 ° C to 170 ° C. And temperature rising conditions 4 degree-C / min, frequency shall be 10 Hz. Under the above conditions, the storage elastic modulus may be measured using a DMA (Q800).

The storage modulus of the invention may preferably be at least 100 MPa at 40 ° C. Within this range, the film may have sufficiently hard physical properties to suppress volume change due to heat.

According to still another aspect of the present invention, an anisotropic conductive film having a bubble area of 20% or less based on the inter-electrode space area after 500 hours at a temperature of 85 ° C. and a relative humidity of 85% after main compression. to provide.

The main compression refers to compression performed at 185 ° C., 4.5 MPa, 4 seconds.

Physical properties after being left for 500 hours at 85 ° C. and 85% relative humidity mean reliable physical properties.

The inter-electrode space is a space between the electrode and the electrode, and means a space in which the anisotropic conductive film composition is filled during compression.

The method of measuring the bubble area is not particularly limited, and a method commonly used in the art can be used. As a non-limiting example of the method of measuring the bubble area, the space between the electrodes filled with the film composition can be observed (or photographed) by a microscope, and the bubble area can be calculated using an image analyzer or scale coordinates.

In the case of the anisotropic conductive film having the above reliability bubble area of more than 20%, there is a problem in that it is difficult to use the semiconductor device connected by using the same for a long time and the life is shortened.

According to still another aspect of the present invention, an anisotropic conductive film having an adhesive strength of 500 gf / cm or more after being left for 500 hours at a temperature of 85 ° C. and a relative humidity of 85% after main compression is provided.

The main crimping conditions are the same as those described above.

The method for measuring the adhesive force is not particularly limited and may be a method commonly used in the art.

Non-limiting examples of the method of measuring the adhesive force is 185 ° C, 4.5 MPa, after pressing at a condition of 4 seconds, peeling angle (Peeling angle) (H5KT, Tinius Olsen) Peeling angle (Peeling angle) 90 ° and peel rate ( Peeling speed) Can be measured under the condition of 50 mm / min.

In the case of the anisotropic conductive film having the above-mentioned reliable adhesive strength of less than 500 gf / cm, there is a problem in that it is difficult to use the semiconductor device connected by using the same for a long time and shorten the life.

The method for forming the anisotropic conductive film of the present invention is not particularly limited and a method commonly used in the art can be used.

The method for forming the anisotropic conductive film does not require any special apparatus or equipment. The binder resin is dissolved in an organic solvent to be liquefied, and then the remaining components are added and stirred for a predetermined time. An anisotropic conductive film can be obtained by apply | coating to the thickness of 50 micrometers, drying for a fixed time, and volatilizing an organic solvent.

According to another aspect of the present invention, there is provided a semiconductor device connected with the anisotropic conductive film.

The semiconductor device includes: a wiring board; An anisotropic conductive film attached to the chip mounting surface of the wiring board; And a semiconductor chip mounted on the film.

The wiring board and the semiconductor chip used in the present invention are not particularly limited, and those known in the art may be used.

The method for manufacturing the semiconductor device of the present invention is not particularly limited and may be performed by a method known in the art.

Hereinafter, the present invention will be described in more detail by describing Examples, Comparative Examples, and Experimental Examples. However, the following Examples, Comparative Examples and Experimental Examples are only examples of the present invention, and the contents of the present invention should not be construed as being limited thereto.

Example  One

Polyester urethane resin and Tricyclodecane Dimethanol Diacrylate  Containing Anisotropy  Production of conductive film

With respect to 100 parts by weight of the solid content of the anisotropic conductive film,

a) 30 parts by weight of a polyester urethane resin (NPC8750, Nanox) as a binder part; And 27 parts by weight of acrylic resin (AOF-7003, Aekyung Chemical),

b) 14 parts by weight of tricyclodecane dimethanol diacrylate as a radically polymerizable material; 12 parts by weight of urethane acrylate (NPC7007, Nanox); 1 part by weight of 2-methacryloyloxyethyl phosphate; 5 parts by weight of pentaerythritol tri (meth) acrylate; And 5 parts by weight of 2-hydroxyethyl (meth) acrylate,

c) using 3 parts by weight of lauryl peroxide as a curing initiator,

d) 3 parts by weight of conductive particles (Sekisui Co., Ltd.) having a size of 3 μm as conductive particles were mixed to prepare a composition for an anisotropic film.

The combined solution was stirred at room temperature (25 DEG C) for 60 minutes in a speed range in which conductive particles were not crushed. The combined solution was formed into a film having a thickness of 35 탆 in a polyethylene base film subjected to a silicone release surface treatment, and a casting knife was used for film formation. The film was dried at 60 DEG C for 5 minutes.

Example  2

Polyester urethane resin and Tricyclodecane Dimethanol Diacrylate  Contains, Additionally  Containing organic particles Anisotropy  Production of conductive film

In Example 1, except that 23 parts by weight of polyester urethane resin and 5 parts by weight of polyurethane beads (MM-101-MS, Negami) was used, the anisotropic conductive film by the same method as in Example 1 Was prepared.

Example  3

Polyester urethane resin and Tricyclodecane Dimethanol Diacrylate  Contains, Additionally  Containing organic particles Anisotropy  Production of conductive film

In Example 1, 15 parts by weight of polyester urethane resin is used; 5 parts by weight of NBR resin (N-34, Nippon Xeon) was used; 20 parts by weight of acrylic resin is used; 25 parts by weight of tricyclodecane dimethanol diacrylate is used; 10 parts by weight of 2-hydroxyethylisocyanurate diacrylate is used; 2 parts by weight of conductive particles are used; Example 1, except that polyurethane beads (MM-101-MS, Negami) is used in 7 parts by weight, and pentaerythritol tri (meth) acrylate and 2-hydroxyethyl (meth) acrylate are not used. An anisotropic conductive film was prepared by the same method as described above.

Example  4

Polyester urethane resin and Tricyclodecane Dimethanol Diacrylate  Containing Anisotropy  Production of conductive film

In Example 3, the polyester urethane resin is used in 40 parts by weight; Tricyclodecane dimethanol diacrylate is used in 10 parts by weight; Urethane acrylate is used in 5 parts by weight; 13 parts by weight of 2-hydroxyethylisocyanurate diacrylate; Anisotropic conductive films were prepared in the same manner as in Example 3, except that the conductive particles were used at 3 parts by weight and no polyurethane beads were used.

Comparative Example  One

Polyester urethane resin, Tricyclodecane Dimethanol Diacrylate is  Not containing Anisotropy  Production of conductive film

An anisotropic conductive film was prepared in the same manner as in Example 1, except that tris 2-hydroxyethyl isocyanurate diacrylate was used instead of tricyclodecane dimethanol diacrylate. It was.

Comparative Example  2

Tricyclodecane Dimethanol Diacrylate  Containing but not containing polyester urethane resin Anisotropy  Production of conductive film

In Example 1, an anisotropic conductive film was prepared in the same manner as in Example 1, except that polyol urethane resin (NPC7007T, Nanux) was used instead of polyester urethane resin.

Comparative Example  3

Polyester urethane resin and Tricyclodecane Dimethanol Diacrylate  Not containing Anisotropy  Production of conductive film

In Example 1, a polyol urethane resin (NPC7007T, Nanux) is used instead of the polyester urethane resin, and tris 2-hydroxy ethyl isocyanurate diacrylate is used instead of tricyclodecane dimethanol diacrylate. Except that, an anisotropic conductive film was prepared in the same manner as in Example 1.

Tables 1 and 2 show the compositions of the anisotropic conductive films of Examples 1 to 4 and Comparative Examples 1 to 3 by weight.

Detailed ingredient Example  One Example  2 Example  3 Example  4
bookbinder Polyester urethane resin 30 25 15 40 NBR resin - - 5 5 Acrylic resin 27 27 20 20 Polyol Urethane Resin - - - -

Radical
Polymerizable  matter Tricyclodecane dimethanol diacrylate 14 14 25 10 Urethane acrylate 12 12 12 5 2-methacryloyloxyethyl phosphate One One One One Pentaerythritol tri (meth) acrylate 5 5 - - 2-hydroxyethyl (meth) acrylate 5 5 - - 2-hydroxyethylisocyanurate
Diacrylate - - 10 13 Hardening Initiator Lauryl peroxide 3 3 3 3 Conductive particles 3 μm conductive particles (Sekisui) 3 2 2 3 Organic particles Polyurethane beads - 5 7 -

Detailed ingredient Comparative Example  One Comparative Example  2 Comparative Example  3
bar In the Polyester urethane resin 28 - - NBR resin 2 2 2 Acrylic resin 27 27 27 Polyol Urethane Resin - 28 28

Radical
Polymerizable  matter Tricyclodecane dimethanol diacrylate - 14 - Urethane acrylate 12 12 12 2-methacryloyloxyethyl phosphate One One One Pentaerythritol tri (meth) acrylate 5 5 5 2-hydroxyethyl (meth) acrylate 5 5 5 2-hydroxyethylisocyanurate diacrylate 14 - 14 Hardening Initiator Lauryl peroxide 3 3 3 Conductive particles 3 μm conductive particles (Sekisui) 3 3 3 Organic particles Polyurethane beads - - -

Experimental Example  One

Measurement of storage modulus

In order to measure the storage modulus at 40 ° C. of Examples 1 to 4 and Comparative Examples 1 to 3, experiments were performed as follows.

Each anisotropic conductive film was cut into a predetermined size (5 mm × 30 mm) and left in a 150 ° C. oven for 1 hour to completely cure the sample, and the measurement temperature range was -30 ° C. to 170 ° C. The storage elastic modulus was measured using DMA (Dynamic Mechanical Analyzer; TA, Q800) at 4 ° C / min and a frequency of 10 Hz.

Experimental Example  2

Initial and Reliability Measurement of Adhesion

Each of the anisotropic conductive films of Examples 1 to 4 and Comparative Examples 1 to 3 was press-bonded for 1 second at a measurement temperature of 70 ° C. using metal electrode glass (Mo / Al / Mo structure, Samsung Electronics) and COF (Samsung Electronics). 10 specimens of each of the above specimens were prepared by connecting to the conditions and the main compression conditions of 185 ° C, 4 seconds, and 4.5 MPa.

For each of these, an initial adhesive force was measured under a condition of a peel angle of 90 ° and a peel rate of 50 mm / min using a peel strength measuring instrument (H5KT, Tinius Olsen), and then an average value was calculated.

Each of the ten specimens was allowed to stand at a temperature of 85 ° C. and a relative humidity of 85% for 500 hours for high temperature and high humidity reliability evaluation, and then each of these reliable adhesive strengths was measured in the same manner as described above. Calculated.

Experimental Example  3

Initial and Reliability Measurement of Connection Resistance

After leaving each of the anisotropic conductive films of Examples 1 to 4 and Comparative Examples 1 to 3 for 1 hour at room temperature (25 ° C.), 4-terminal measurement was performed on a patternless glass in which an ITO layer was coated at 1000 t with 0.5 t glass. Using the COF (Samsung Electronics) in which possible paddles were formed, 10 specimens were prepared by connecting each of the specimens at a measurement temperature of 70 ° C. under a 1 second press condition and at 185 ° C., 4 seconds and a 4.5 MPa main press condition. Each of these was measured by the four-terminal measuring method (based on ASTM F43-64T method) and the average value was calculated.

Each of the ten test specimens was allowed to stand for 500 hours under the conditions of a temperature of 85 캜 and a relative humidity of 85% to carry out a high temperature / high humidity reliability evaluation, and then each of these reliability connection resistors was measured (according to ASTM D117) The mean value was calculated.

Experimental Example  4

Initial and Reliability bubble  Area measurement

After leaving each of the anisotropic conductive films of Examples 1 to 4 and Comparative Examples 1 to 3 for 1 hour at room temperature (25 ° C.), 4-terminal measurement was performed on a patternless glass in which an ITO layer was coated at 1000 t with 0.5 t glass. Using the COF (Samsung Electronics) in which possible paddles were formed, 10 specimens were prepared by connecting each of the specimens at a measurement temperature of 70 ° C. under a 1 second press condition and at 185 ° C., 4 seconds and a 4.5 MPa main press condition. Ten pictures were taken using an optical microscope, and then the average value was calculated by measuring the bubble area of the inter-electrode space part using an image analyzer.

Each of the ten specimens was allowed to stand at a temperature of 85 ° C. and a relative humidity of 85% for 500 hours to perform high temperature and high humidity reliability evaluation, and then the bubble area was measured in the same manner as above to calculate the average value.

Table 3 shows the measurement results of Experimental Examples 1 to 4.

Early 500 hr  responsibility Adhesion
( gf Of cm ) Connection resistance
(Ω) bubble  area
(%) Adhesion
( gf Of cm ) Connection resistance
(Ω) bubble  area
(%) Example  One 782 0.82 2 695 1.54 7 Example  2 796 0.83 2 711 1.52 5 Example  3 824 0.84 2 745 1.48 5 Example  4 842 0.83 2 752 1.44 4 Comparative Example  One 757 0.83 8 427 2.42 22 Comparative Example  2 762 0.87 9 412 2.52 29 Comparative Example  3 672 1.05 15 357 2.98 35

Looking at Table 3, Examples 1 to 4 prepared by using a polyester urethane resin and tricyclodecane dimethanol diacrylate together, Comparative Example 3, which does not include both of the two materials, as well as each one It was confirmed that the physical properties were excellent in all items over initial and reliable adhesive strength, connection resistance, and bubble area than those of Comparative Examples 1 and 2 including branches.

In particular, the anisotropic conductive film including the two materials was found to be very excellent in the adhesive strength, the bubble area after the reliability was measured to 20% or less, it was determined that the reliability will be maintained even if the film is used for a long time.

On the other hand, when comparing the Examples 1 and 2, when the organic particles are added to the polyester urethane resin and tricyclodecane dimethanol diacrylate, in particular, it was confirmed that the adhesion and bubble properties are more excellent. This was judged to be because the organic particles and / or inorganic particles relieve the stresses acting upon contraction and expansion of the anisotropic conductive film.

Claims (13)

a) a binder portion comprising a polyester urethane resin;
b) radically polymerizable materials including tricyclodecane dimethanol diacrylate;
c) a curing initiator; And
d) conductive particles
An anisotropic conductive film containing a. 2. The anisotropic conductive film according to claim 1, wherein, based on 100 parts by weight of the solid content of the anisotropic conductive film,
a) 40 to 80 parts by weight of a binder part comprising a polyester urethane resin;
b) 5 to 50 parts by weight of a radically polymerizable material comprising tricyclodecane dimethanol diacrylate;
c) 0.1 to 10 parts by weight of a curing initiator; And
d) 0.1 to 10 parts by weight of conductive particles
An anisotropic conductive film containing a. The anisotropic conductive film of Claim 2 which contains the said polyester urethane resin in 5-40 weight part with respect to 100 weight part of solid content of the said anisotropic conductive film. The anisotropic conductive film of Claim 2 which contains 5-30 weight part of said tricyclodecane dimethanol diacrylates with respect to 100 weight part of solids of the said anisotropic conductive film. The anisotropic conductive film of any one of Claims 1-4 whose storage elastic modulus in 40 degreeC is 100 Mpa or more. The bubble area according to any one of claims 1 to 4, wherein the bubble area after standing for 500 hours at a temperature of 85 ° C. and a relative humidity of 85% after the main compression is 20% or less based on the inter-electrode space area. , Anisotropic conductive film. As an anisotropic conductive film containing polyester urethane resin and tricyclodecane dimethanol diacrylate,
a) the storage modulus at 40 ° C. is at least 100 MPa;
b) The anisotropic conductive film whose bubble area after leaving for 500 hours in the conditions of 85 degreeC of temperature and 85% of a relative humidity after main compression is 20% or less based on the space area between electrodes. The anisotropic conductive film of Claim 1 or 7 which further contains organic or inorganic particle. The method of claim 8, wherein the organic particles, acrylate resin, acrylic resin, ethylene resin, olefin resin, butadiene resin, acrylonitrile butadiene copolymer, styrene-butadiene block copolymer (Styrene-Butadiene block copolymer), styrene Butadiene-styrene block copolymer, carboxylated styrene-ethylenebutadiene-styrene block copolymer, ethylene styrene-butylene block copolymer, butadiene rubber, chloroprene rubber, silicone rubber, vinyl resin, ester resin, phenoxy resin and polyurethane resin An anisotropic conductive film, which is at least one particle selected from the group consisting of: The anisotropic conductive film of claim 8, wherein the inorganic particles are silica particles. The anisotropic conductive film of Claim 8 which contains 1-20 weight part of said organic or inorganic particles with respect to 100 weight part of solid content of the said anisotropic conductive film. The anisotropic conductive film of Claim 1 or 7 whose adhesive force after leaving for 500 hours in the conditions of 85 degreeC and 85% of a relative humidity after main compression is 500 gf / cm or more. a) a wiring board;
b) an anisotropic conductive film attached to the chip mounting surface of the wiring board; And
c) a semiconductor chip mounted on the anisotropic conductive film
A semiconductor device comprising:
The said anisotropic conductive film is a semiconductor device of Claim 1 or 7 which is a film.