KR20130068891A - Anisotropic conductive film composition, the anisotropic conductive film thereof and semiconductor device - Google Patents

Abstract

PURPOSE: An anisotropic conductive film and a composition for the film are provided to have a low tensile elongation after curing, thereby decreasing shrinkage ratio. CONSTITUTION: An anisotropic conductive film and a composition for the film has a tensile elongation of 10-100 %, includes 40-80 wt% of a binder resin, and organic particle. An anisotropic conductive film composition comprises a binder including one or more polyester type urethane resin, polyurethane acrylate resin, and urethane resin; an ethylene-vinylacetate copolymer; and a radical polymerizable material including tricyclodecane dimethanol diacrylate or tricyclodecan dimethanol dimethacrylate; and an organic particle.

Description

Anisotropic conductive film composition, the anisotropic conductive film, and semiconductor device

The present invention relates to an anisotropic conductive film composition and an anisotropic conductive film prepared therefrom. More specifically, the present invention is a binder comprising at least one of polyester type urethane resin, polyurethane acrylate resin, urethane resin; Ethylene-vinylacetate copolymers; Radically polymerizable materials including tricyclodecane dimethanol diacrylate or tricyclodecane dimethanol dimethacrylate; And relates to a composition for anisotropic conductive film containing organic particles, in particular, the tensile elongation after curing is 10 to 100%, due to the low shrinkage, expansion rate in the connection structure in the connection structure does not reduce the electrical connection reliability even under high temperature and high humidity It relates to a resin composition for use and a film.

The anisotropic conductive film refers to a film-like adhesive obtained by dispersing conductive particles such as metal particles such as nickel and gold or polymer particles coated with such metals. When the anisotropic conductive film is placed between the circuit to be connected and then heated and pressed under a certain condition, the circuit terminals are electrically connected by the conductive particles, and the pitch between the adjacent circuits is an insulating adhesive resin And the conductive particles are filled independently to each other, so that the insulating property is given.

Such anisotropic conductive films are widely used for electrical connection of LCD panels, COF films, Tape Carrier Packages (hereinafter referred to as TCP), or printed circuit boards, COF films, and TCP.

Conventionally anisotropic conductive films include (i) an epoxy type in which a cured portion made of an epoxy- or phenol-based curing agent is mixed into a binder resin portion which acts as a matrix for film formation, and (ii) a (meth) acrylic oligomer in a binder resin portion. And the (meth) acrylate type which mixed the hardened | cured part which consists of a monomer and a radical initiator.

However, the binder portion of the conventional anisotropic conductive film only plays a role as a film forming agent, does not contribute significantly to the initial adhesive strength or connection reliability, the shrinkage and expansion is repeated in the connection structure due to the polymer resin of the low glass transition temperature used mainly There is a problem that can not guarantee long-term connection and adhesion reliability.

On the other hand, the anisotropic conductive film should have good adhesion. There is a method of adding a high molecular weight polyurethane resin in order to increase the adhesive strength, but when adding a high molecular weight polyurethane resin, the compatibility with other acrylic binders or low molecular weight (meth) acrylate monomers, the anisotropic conductive film production There may be difficulties.

In addition, the anisotropic conductive film has a low shrinkage and expansion rate in the connection structure, so that the electrical connection reliability should be good even under high temperature and high humidity. However, conventional anisotropic conductive films have a high shrinkage or expansion rate after curing, and thus have a limitation in increasing reliability.

Korean Patent Application Publication No. 2008-0060613 discloses a composition for anisotropic conductive films comprising a film-forming polymer resin, an ethylene-vinylacetate copolymer, a radical polymerizable material, and a radical initiator with improved flowability and adhesion. When using a large amount of the radical polymerizable material in the amount of 40 to 70% by weight as in the patent application, there is still a problem of deterioration in adhesion strength, and when the film-forming polymer resin is used in a small amount of 10 to 30% by weight, the ductility of the film is strong and fairness You may have problems.

Accordingly, there is a need to develop a new anisotropic conductive film composition having good compatibility with existing polyurethane binders or polyurethane acrylates, excellent adhesion retention even under short-term main compression conditions, and low tensile elongation to improve connection reliability.

Republic of Korea Patent Application Publication No. 2008-0060613 Korea Patent Registration No. 744685

none

The present invention is to overcome the problems of the prior art described above, one object of the present invention is a low tensile elongation after curing is less shrinkage and expansion in the connection structure is anisotropic conductivity that does not reduce the electrical connection reliability even under high temperature and high humidity To provide a film, a composition for a film.

Another object of the present invention is to provide a composition for anisotropic conductive films having a low degree of increase in connection resistance due to flowability, having a stable electrical conductivity even in short-term main compression conditions, and excellent in maintaining adhesion.

The present invention has a tensile elongation of 10% to 100% after curing, and includes at least one of polyester type urethane resin, polyurethane acrylate resin, and urethane resin of 40 to 80% by weight based on the solid weight of the entire film. It relates to an anisotropic conductive adhesive film containing a binder resin, and organic particles.

The present invention also

A binder containing at least one of polyester type urethane resin, polyurethane acrylate resin and urethane resin;

Ethylene-vinylacetate copolymers;

Radically polymerizable materials including tricyclodecane dimethanol diacrylate or tricyclodecane dimethanol dimethacrylate; And

It relates to a composition for an anisotropic conductive film containing organic particles.

The anisotropic conductive film and the composition for films according to the present invention have a small shrinkage and expansion ratio in the connection structure, and thus the electrical connection reliability does not decrease even under high temperature and high humidity.

In addition, the anisotropic conductive film and the composition for a film according to the present invention is excellent in maintaining the adhesive strength even in the main compression conditions for a short time.

The present invention provides an anisotropic conductive film and a composition for film excellent in flowability, heat resistance and reliability improvement.

Hereinafter, specific embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the specification, each content is on a solids basis.

According to the present invention,

A binder containing at least one of polyester type urethane resin, polyurethane acrylate resin and urethane resin;

Ethylene-vinylacetate copolymers;

Radically polymerizable materials including tricyclodecane dimethanol diacrylate or tricyclodecane dimethanol dimethacrylate; And

It relates to a composition for an anisotropic conductive film containing organic particles.

Tricyclodecane dimethanol diacrylate or tricyclodecane dimethanol dimethacrylate, which is a radically polymerizable material used in the present invention, has a structure of Formula 1 or Formula 2 below, and improves heat resistance and reliability of the composition for anisotropic conductive films. Effective in

[Formula 1]

[Formula 2]

The radically polymerizable material may be included in 10 to 40% by weight based on the solids content of the total composition. Good adhesion and connection reliability can be obtained after the process compression in the range of 10 to 40% by weight.

On the other hand, when the radically polymerizable material is used in a large amount as described above, the adhesive strength of the anisotropic conductive composition tends to be somewhat lower. Thus, in the present invention, by adding an EVA (ethylene-vinylacetate) copolymer having high adhesive strength, it was intended to reinforce the decrease in adhesion caused by the radically polymerizable material.

EVA copolymer is a thermoplastic resin copolymerized with ethylene and vinyl acetate, and has an effect of improving the flowability and adhesion of the composition. Vinyl acetate is preferably from 15 to 35% by weight in the EVA copolymer. When the vinyl acetate content is within this range, the flowability is increased, the adhesion performance is excellent, and it is preferable in terms of elastic modulus and reliability.

When the EVA copolymer is contained in a large amount in the composition, the excessive flowability may cause the adhesive resin not to be sufficiently filled between the circuits, thereby lowering the adhesive strength and increasing the connection resistance after 85 ° C. and 85% reliability. In the present invention, to further include the organic particles to compensate for the excessive flow of the composition due to the EVA copolymer. In addition, the stress can be alleviated under the heat shrinkage accompanying curing by the organic particles, it is possible to lower the heat deformation due to shrinkage and expansion can maintain the adhesion reliability under high temperature and high humidity conditions.

The composition for anisotropic conductive films according to the present invention may further include components commonly used in the composition for anisotropic conductive films, for example, radical initiators and conductive particles.

In the present invention, 40 to 80% by weight of the binder, 5 to 30% by weight of the ethylene-vinylacetate copolymer, and 10 to 40% by weight of the radically polymerizable material, based on the total solid weight of the composition for the anisotropic conductive film. %, And the organic particles may be included in 1 to 10% by weight.

In the present invention, the organic particles may have a single layer structure or a multilayer structure.

According to another embodiment of the present invention, the organic particles are styrene-divinyl benzene, chlorinated polyethylene, dimethyl polysiloxane, methyl methacrylate-butylacrylate-dimethyl Methylmathacrylate-Butylacrylate-Dimethylsiloxane copolymer, Styrene-Butadiene-Styrene block copolymer, Styrene-Butadiene Thermoplastic elastomer, Butadiene Rubber It provides a composition for an anisotropic conductive film, which is at least one selected from the group consisting of styrene-butadiene rubber and ethylene glycidyl methacrylate.

 In particular, the single-layered organic particles include, for example, spherical organic particles made of a crosslinked urethane resin. The polyurethane organic particles may be ion exchange treated. Although there is no restriction | limiting in particular in the ion exchange treatment method of polyurethane organic particle | grains, The method of dilution with a solvent etc., the use of the monomer which does not produce an ion residue, etc. are common. When the polyurethane organic particles are ion-exchanged, the ion content of the polyurethane organic particles is reduced, preferably greater than 0 and 10 ppm or less, more preferably 1 or more and 10 ppm or less. Within this range, the electrical conductivity of the film does not increase and no corrosion occurs during circuit connection.

In one preferred embodiment, organic particles having copolymers of methyl methacrylate, polystyrene and divinylbenzene or copolymers of methyl methacrylate, polystyrene and butadiene can be used in the present invention.

The organic particles having a multilayer structure may have a two-layer or three-layer structure including a core and a shell. For example, the glass transition temperature of the polymer resin constituting the core is lower than the glass transition temperature of the polymer constituting the shell. The organic particle | grains characterized by the above are mentioned. More specifically, the core portion of the organic particles may be composed of a homopolymer of an acrylic monomer or a rubbery polymer having a low glass transition temperature of a copolymer, and the shell portion may be an organic particle composed of a polymer having a high glass transition temperature. In the organic particles, the shell portion having a high glass transition temperature limits the fusion between particles and improves compatibility with the matrix resin, so that the dispersion of particles is easy and the viscosity can be controlled by the organic particles. There is an advantage that can ensure sufficient workability. There is no restriction | limiting in the acrylic monomer for forming the organic fine particle of the said multilayer structure.

The diameter of the organic particle of this invention is not specifically limited, It may be 0.1-10 micrometers, Preferably it is 0.3-5 micrometers. When the size of the organic particles is in the above range, it is preferable that the dispersion of the organic particles is good and the conduction characteristics of the conductive particles are not disturbed by the organic particles.

The organic particles may be included in 1 to 10% by weight based on the total solid weight of the composition for anisotropic conductive film. When the content of the organic particles is less than 1% by weight, it is difficult to produce the effect of the organic particles. When the content of the organic particles exceeds 10% by weight, the adhesiveness of the film may be lowered and the pressure adhesion may be lowered.

The present invention also has a tensile elongation of 10% to 100% after curing, 40 to 80% by weight based on the solid weight of the entire film, at least one of the polyester type urethane resin, polyurethane acrylate resin, urethane resin The anisotropically conductive adhesive film containing the binder resin and organic particle | grains containing.

In the present invention, the tensile elongation of 10 to 100% after curing is related to the property that the electrical connection reliability does not decrease even under high temperature and high humidity due to a small shrinkage or expansion rate in the connection structure. In the present invention, the tensile elongation is measured under a tensile test speed of 50mm / min after the sample is bitten by a grip equipped with a 5N load cell using a universal testing machine (UTM).

In the present invention, a binder resin including at least one of a polyester type urethane resin, a polyurethane acrylate resin, and a urethane resin may be included in an amount of 40 to 80% by weight based on the total weight of the composition or the film. If the content of the binder resin is less than 40% by weight, the ductility of the film is strong and may cause problems in processability, and it is not preferable.

The present invention also provides an anisotropic conductive adhesive film having an adhesive force of 800 gf / cm or more at 1 second at 70 ° C., pressurization of 1.0 MPa and 4 seconds at 150 ° C., and main compression at 4.0 MPa. In a preferred embodiment, the adhesion may be at least 900 gf / cm. The adhesive film of the present invention maintains high adhesion in a short time of main compression conditions because the adhesive force is 800 gf / cm or more even in the main compression conditions of 200 ° C., 4 seconds, and 150 ° C., which is lower than 4.0 MPa. Can be used.

The present invention also provides an anisotropic conductive adhesive film, characterized in that the connection resistance increase rate calculated by the following formula 1 is greater than 0 and 40% or less.

<Equation 1> Connection resistance increase rate (%) = ｜ (A-B) / A | x 100

(In Formula 1, A is the connection resistance after pressing at 70 ℃, 1 second, 1 MPa and main compression at 4 MPa for 4 seconds at 150 ℃, B is 500 at 85 ℃ and 85% after the pressing and main compression Connection resistance after reliability evaluation condition for time)

Hereinafter, each structure of the composition for anisotropic conductive films which concerns on this invention is demonstrated in detail.

Binder resin

The present invention is a binder portion that serves as a matrix required to form an anisotropic conductive film of 40 to 80% by weight based on the solid weight of the entire film, at least one of polyester type urethane resin, polyurethane acrylate resin, urethane resin It may include.

In particular, the composition for anisotropic conductive films of the present invention may include a polyester type urethane resin or a polyurethane acrylate resin in terms of flowability and adhesive strength as a thermoplastic resin component. As the binder portion has a low glass transition temperature, flowability is improved, and high adhesion is expressed by the urethane group in the molecular chain. In particular, when used in an anisotropic conductive film, the curing performance can be improved to lower the temperature of the connection process.

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. Polyester polyols can be obtained by the reaction of dicarboxylic acids and diols.

Examples of the dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, succinic acid, glutaric acid, adipic acid, subberic acid, azelanic acid, sebacic acid, dodecanedicarboxylic acid, hexa Hydrophthalic acid, ortho-phthalic acid, tetrachlorophthalic acid, 1,5-naphthalenedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, tetrahydrophthalic acid, and the like. Or aliphatic dicarboxylic acid is preferred.

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, 1,4-cyclo Hexane dimethanol etc. are mentioned, The above-mentioned glycol is preferable.

As an example of the said diisocyanate, aromatic, aliphatic, alicyclic diisocyanate, a combination thereof, etc. can be used, Specifically, isophorone diisocyanate (IPDI), tetramethylene-1, 4- diisocyanate, hexamethylene- 1,6-diisocyanate, diphenylmethane diisocyanate, cyclohexylene-1,4-diisocyanate, methylenebis (4-cyclohexyl isocyanate), xylene diisocyanate, hydrogenated diphenylmethane diisocyanate and naphthalene diisocyanate and 2 It can be used individually or in mixture of 2 or more types selected from the group which consists of a 4-, or 2, 6-toluene diisocyanate, and aromatic diisocyanate is preferable.

It is preferable that the weight average molecular weights of the said polyester urethane resin are 10,000-100,000, More preferably, the thing of 25,000-70,000 can be used.

Polyurethane Acrylate  Suzy

In particular, the composition for the anisotropic conductive film of the present invention may include a polyurethane acrylate resin in terms of flowability and adhesion as a thermoplastic resin component.

Polyurethane acrylate resin has a low glass transition temperature as a binder portion, while improving the flowability, high adhesive force is expressed by the urethane group in the molecular chain. In particular, when used in an anisotropic conductive film, the curing performance is improved and the temperature of the connection process can be lowered.

Polyurethane acrylate resins may include, but are not limited to, components of diisocyanates, polyols (or diols) and acrylates.

As the diisocyanate, aromatic, aliphatic, cycloaliphatic diisocyanates, combinations thereof, and the like may be used. Specifically, the diisocyanate may be tetramethylene-1,4-diisocyanate, hesamethylene-1,6-diisocyanate, cyclohex. Silylene-1, 4- diisocyanate, methylenebis (4-cyclohexyl diisocyanate), isophorone diisocyanate, 4-4 methylene bis (cyclohexyl diisocyanate), etc. can be used individually or in mixture of 2 or more types.

The polyol has two or more hydroxyl groups in the molecular chain Polyether polyols, polycarbonate polyols and the like can be used. In the case of the polyether polyol, the weight average molecular weight of the polyol is preferably 400 to 10,000 g / mol, and more preferably 400 to 3,000 g / mol. The polycarbonate polyol includes a polyalkylene carbonate and a polycarbonate polyol derived from a silicone.

The diol may be at least one member selected from the group consisting of 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, , Tetraethylene glycol, dibutylene glycol, 2-methyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol and the like.

Acrylates include hydroxy acrylates or amine acrylates.

The polyurethane acrylate resin including the three components described above has a molar ratio of 1.04 to 1.6 of the diisocyanate group (NCO) / hydroxy group (OH) among the three components except for acrylate, and 3 except for acrylate. Addition of hydroxy acrylate or amine acrylate to any one of the polyaddition polymerization step so that the content of the polyol in the branch component and the diisocyanate group which is the terminal functional group of the urethane synthesized by the polymerization reaction It is prepared by the step of reacting at a molar ratio of to 2.1. In addition, residual isocyanate groups can be reacted with alcohols to produce the final polyurethane acrylate resin. At this time, in the middle polymerization step, a known central polymerization method may be used. In the above step, the reaction temperature may be 90 ° C, the reaction pressure may be 1 atm, the time may be 5 hours, and the catalyst may be prepared using a tin-based catalyst.

That is, the polyurethane acrylate resin has a single glass transition temperature of 0 ° C. or higher or at least one glass transition temperature of 0 ° C. or higher by phase mixing of a polyol which is a soft segment and a diisocyanate that is a hard segment. In addition, it shows the function as a binder that plays a role of film formation, and the curing reaction is progressed along with the acrylics of the hardening part through the acrylate group present in the terminal functional group to perform the role of the hardening part, thereby showing excellent adhesion and high connection reliability. do.

The weight average molecular weight of the polyurethane acrylate resin may be 10000-100000 g / mol, preferably 20000-40000 g / mol. In addition, at least one of the two glass transition temperatures (Tg) represented by the polyurethane acrylate resin may be 0 ° C. or more.

Urethane  Suzy

Urethane-based resin 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 urethane-based resin may be a resin having a weight average molecular weight of 50,000 to 100,000 g / mol.

The thermoplastic resin of the present invention is preferably contained in 40 to 80% by weight, preferably 45 to 75% by weight based on the total solid weight of the composition for the anisotropic conductive film. Furthermore, in the present invention, the solid weight ratio of the binder resin and the radical polymerizable material is in the range of 2: 1 to 12: 1, preferably 2.5: 1 to 7: 1, in that it is excellent in adhesive strength and reliability.

Radical Polymerizable  matter

Tricyclodecane dimethanol diacrylate or tricyclodecane dimethanol dimethacrylate, which is a radically polymerizable material used in the present invention, has a structure of Formula 1 or Formula 2 below, and improves heat resistance and reliability of the composition for anisotropic conductive films. Effective in

[Formula 1]

[Formula 2]

The radically polymerizable material may be included in 10 to 40% by weight based on the solids content of the total composition. Good adhesion and connection reliability can be obtained after the process compression in the range of 10 to 40% by weight.

In another aspect of the present invention, in addition to the radically polymerizable material of Formula 1 or Formula 2, the anisotropic conductive film or composition for a film according to the present invention may further include a radically polymerizable material commonly used in the art. Examples thereof include acrylates, methacrylates, maleimide compounds, and the like, but may be used in a monomer, oligomer, or polymer state, or a combination of monomers, oligomers, and polymers is not limited thereto.

Ethylene-Vinyl Acetate Copolymer

In the present invention, the EVA copolymer is an thermoplastic resin copolymerized with ethylene and vinyl acetate, thereby improving the flowability and adhesion of the composition.

In one embodiment of the present invention, the ethylene-vinyl acetate copolymer is a material having excellent flowability, and the weight average molecular weight is in the range of about 100,000 to 600,000, which may be satisfied with the heat compression conditions under which an anisotropic conductive film is used. Particularly, when the weight average molecular weight is in the above range, it is preferable in view of strength in film formation and miscibility with other resins.

The vinyl acetate in the ethylene-vinylacetate copolymer of the present invention is preferably 15 to 35% by weight. When the vinyl acetate content is within this range, the flowability is increased, the adhesion performance is excellent, and it is preferable in terms of elastic modulus and reliability.

The ethylene-vinylacetate copolymer may be included in 5 to 30% by weight, preferably 5 to 20% by weight based on the solids content of the total composition. Flowability is improved in the above range and it is possible to form a dense hardened structure.

Organic particles

In the present invention, the organic particles serve to compensate for the excessive flow of the composition due to the ethylene-vinylacetate copolymer. In addition, the stress can be alleviated under thermal shrinkage accompanying curing by the organic particles, and the thermal deformation due to shrinkage and expansion can be lowered, thereby imparting adhesion reliability to the film under high temperature and high humidity conditions.

In the present invention, the organic particles may have a single layer structure or a multilayer structure.

According to another embodiment of the present invention, the organic particles are styrene-divinyl benzene, chlorinated polyethylene, dimethyl polysiloxane, methyl methacrylate-butylacrylate-dimethyl Methylmathacrylate-Butylacrylate-Dimethylsiloxane copolymer, Styrene-Butadiene-Styrene block copolymer, Styrene-Butadiene Thermoplastic elastomer, Butadiene Rubber It provides a composition for an anisotropic conductive film, which is at least one selected from the group consisting of styrene-butadiene rubber and ethylene glycidyl methacrylate.

In particular, the single layer structured organic particles include, for example, spherical organic particles made of a crosslinked urethane resin. The polyurethane organic particles may be ion exchange treated. Although there is no restriction | limiting in particular in the ion exchange treatment method of polyurethane organic particle | grains, The method of dilution with a solvent etc., the use of the monomer which does not produce an ion residue, etc. are common. When the polyurethane organic particles are subjected to ion exchange treatment, the ion content of the polyurethane organic particles is reduced, and preferably, it is more than 0 and 10 ppm or less. Within this range, the electrical conductivity of the film does not increase and no corrosion occurs during circuit connection.

The organic particles having a multilayer structure may have a two-layer or three-layer structure including a core and a shell. For example, the glass transition temperature of the polymer resin constituting the core is lower than the glass transition temperature of the polymer constituting the shell. The organic particle | grains characterized by the above are mentioned. More specifically, the core portion of the organic particles may be composed of a homopolymer of an acrylic monomer or a rubbery polymer having a low glass transition temperature of a copolymer, and the shell portion may be an organic particle composed of a polymer having a high glass transition temperature. In the organic particles, the shell portion having a high glass transition temperature limits the fusion between particles and improves compatibility with the matrix resin, so that the dispersion of particles is easy and the viscosity can be controlled by the organic particles. There is an advantage that can ensure sufficient workability. There is no restriction | limiting in the acrylic monomer for forming the organic fine particle of the said multilayer structure.

The diameter of the organic particle of this invention is not specifically limited, It may be 0.1-10 micrometers, Preferably it is 0.3-5 micrometers. When the size of the organic particles is in the above range, it is preferable that the dispersion of the organic particles is good and the conduction characteristics of the conductive particles are not disturbed by the organic particles.

The organic particles may be included in 1 to 10% by weight based on the total solid weight of the composition for anisotropic conductive film. When the content of the organic particles is less than 1% by weight, it is difficult to produce the effect of the organic particles. When the content of the organic particles exceeds 10% by weight, the adhesiveness of the film may be lowered and the pressure adhesion may be lowered.

In one preferred embodiment, organic particles having copolymers of methyl methacrylate, polystyrene and divinylbenzene or copolymers of methyl methacrylate, polystyrene and butadiene can be used in the present invention.

Radical  polymerization Initiator

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

As photopolymerization initiator, benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4-methyl diphenyl sulfide, isopropyl thioxanthone, diethyl thioxanthone, 4-diethyl ethyl benzoate, benzoin ether, benzoyl propyl Ether, 2-hydroxy-2-methyl-1-phenyl propane-1-one, diethoxy acetophenone, and the like, but are not limited thereto.

The thermosetting initiator is not particularly limited, and peroxide and azo may be used. Peroxide initiators may be used, for example, lauryl peroxide, benzoyl peroxide, cumene hydroperoxide and the like, but are not limited thereto. Examples of azo initiators include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methyl propionate), 2,2;- Azobis (N-cyclohexyl-2-methyl propionide) etc. can be used, but it is not limited to these.

The radical polymerization initiator is preferably contained in 0.5 to 5% by weight, preferably 1 to 4% by weight based on the total solid weight of the composition for the anisotropic conductive film.

Conductive particle

Electroconductive particle is used as a filler for giving electroconductive performance as a composition of the anisotropic conductive film composition of this invention. As electroconductive particle, Metal particle containing gold (Au), silver (Ag), nickel (Ni), copper (Cu), palladium (Pb), solder, etc .; carbon; Gold (Au), silver (Ag), nickel (Ni), copper (Cu), palladium (Pb) based on resins containing polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol and the like, and modified resin thereof Coated with a metal including solder and the like; One or more insulating particles coated with insulating particles may be used.

The size of the conductive particles is not particularly limited, but is preferably larger than the diameter of the polyurethane beads. Only then, stable electrical characteristics and connection reliability can be good. For example, the diameter of the conductive particles may be 1 μm to 20 μm. Preferably it may be 1 ㎛ to 8 ㎛.

The conductive particles may be included in 1-10% by weight of the anisotropic conductive film composition on a solids basis. Within the above range, stable electrical characteristics can be expressed in consideration of electrical characteristics such as short. Preferably it may be included in 1-5% by weight.

In addition, the anisotropic conductive film composition of the present invention may further contain additives such as a polymerization inhibitor, an antioxidant, a heat stabilizer, etc. to provide additional physical properties without impairing the basic physical properties. The additive is not particularly limited but may be contained in an amount of 0.01 to 10% by weight based on the solid content of the anisotropic conductive film composition.

The polymerization inhibitor may be selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, phenothiazine, and mixtures thereof. As the antioxidant, a phenolic or hydroxycinnamate-based material can be used. For example, tetrakis- (methylene- (3,5-di-t-butyl-4-hydeoxinnamate) methane, 3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanoate thiol di -2,1-ethanediyl ester and the like can be used.

The present invention provides an anisotropic conductive film formed of the anisotropic conductive film composition of the present invention. No special device or equipment is required to form the anisotropic conductive film. For example, the anisotropic conductive film composition of the present invention is dissolved in an organic solvent such as toluene and liquefied, and then stirred for a predetermined time within a speed range in which the conductive particles are not pulverized, which is fixed on a release film, for example, 10- An anisotropic conductive film may be obtained by applying a thickness of 50 μm and drying for a predetermined time to volatilize toluene or the like.

Further, according to the present invention,

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

As a semiconductor device comprising a,

The anisotropic conductive film provides a semiconductor device, which is the film described herein or a film made from the composition described herein.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Example

Example  1-5: Preparation of Anisotropic Conductive Film

After urethane resin, ethylene-vinylacetate copolymer, tricyclodecane dimethanol diacrylate, organic particles, organic peroxides, conductive particles, and toluene as a solvent were added to a magnetoelectric mixer to disperse and disperse the composition shown in Table 1 below, After coating on a peeled PET film, the solvent was dried for 5 minutes in a hot air circulation oven heated at 60 ° C. to obtain an anisotropic conductive film having a thickness of 35 μm.

Comparative example  1-2: Preparation of the Anisotropic Conductive Film

Anisotropic conductive films were produced in the same manner as in Examples 1 to 5 except that the components described in the following Table 1 were added.

The content and specification of each component used in the Examples and Comparative Examples are shown in Table 1, respectively:

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Urethane resin 55 50 45 60 40 60 65 EVA copolymer 5 10 15 10 10 10 Radical polymerizable materials1 20 20 20 10 30 20 20 Radical polymerizable materials2 Organic particles 15 15 15 15 15 15 Organic peroxide 2 2 2 2 2 2 2 Conductive particle 3 3 3 3 3 3 3 Sum 100 100 100 100 100 100 100

1) urethane resin

60 wt% of polyol (polytetramethylene glycol), 39.97 wt% of three components of 1,4-butanediol, toluene diisocyanate and hydroxyethyl methacrylate, and 0.03 wt% of dibutyl tin dilaurate used as a catalyst To synthesize. First, a polyol, 1,4-butadiol, and toluene diisocyanate are reacted to synthesize an isocyanate terminated prepolymer. The thus prepared isocyanate-terminated prepolymer and hydroxyethyl methacrylate were further reacted to prepare a polyurethane acrylate resin, wherein the hydroxyethyl methacrylate / prepolymer-terminated isocyanate molar ratio was 0.5. Polyurethane acrylate which is a weight average molecular weight of 25,000 synthesize | combined by carrying out a polyaddition polymerization reaction using the temperature of 90 degreeC, a pressure of 1 atmosphere, the reaction time of 5 hours, and dibutyl tin dilaurylate as a catalyst.

2) Ethylene-Vinyl Acetate Copolymer

80 g of an EVA copolymer having a vinyl acetate content of 33% was dissolved in a mixed solvent of toluene / methylethyl ketone 2: 1 in a weight ratio to obtain a solution of 35% solids. ((Mitsubishi DuPont Polychemical Co., Ltd. Rex EV180)

3) radically polymerizable material 1

Tricyclodecane dimethanol diacrylate (TCDDMA) (KARAYAD R-684, Nippon Gunpowder)

4) radically polymerizable material 2

Epoxy Acrylate Polymer (SP1509, Showa Polymer)

5) organic particles

Methyl methacrylate / styrene / divinyl benzene copolymers:

100 ml of acetonitrile as a solvent was placed in a three-neck round flask reactor equipped with a cooler under a nitrogen atmosphere, and methyl methacrylate, styrene monomer, and divinylbenzene were fixed at 2% by weight based on the solvent. The concentration of the divinylbenzene, the crosslinking agent, was maintained at 70 ° C. in the mixture added to be 50% by weight relative to the styrene monomer concentration. 0.04 g of 2,2'-azobisisobutyronitrile as an initiator was added to the mixture, followed by precipitation polymerization for 24 hours while stirring at 30 rpm to obtain a polystyrene divinylbenzene copolymer having an average particle size of 3 to 4 µm.

6) organic peroxide

Benzoyl Peroxide (Hansol)

7) conductive particles

Conductive particles (Ni) having a size of 3 ~ 5㎛

Experiment using the adhesive film prepared in Examples 1 to 5 and Comparative Examples 1 to 2 as described below, the results are shown in Table 2 below.

1. Measurement of connection resistance and adhesion

In order to measure the poor adhesion and adhesion of the anisotropic conductive films prepared from the above examples and comparative examples, each film was coated with a PCB (pitch 200 μm, terminal width 100 μm, terminal distance 100 μm, terminal height 35 μm) and COF. The film (pitch 200 micrometers, terminal width 100 micrometers, terminal distance 100 micrometers, and terminal height 8 micrometers) was connected on condition of the following.

1) pressing condition; 70 ° C., 1 second, 1.0 MPa,

2) main compression conditions; Five specimens of 150 ° C., 4 seconds, 4.0 MPa (condition 1), 200 ° C., 4 seconds, and 4.0 MPa (condition 2) were prepared, and the adhesive force was measured using a sample of condition 1.

2. Tensile Elongation Measurement

For the sample for tensile elongation measurement, place the secured 35um thick anisotropic conductive film on a heat press, place a 0.2mm thick silicone rubber on it, heat / press 190 ℃ -30MPa-15min, and harden the connecting material. It is cut and used to cut 2.0mm in width and 30mm in length.

Tensile tests are measured using a universal testing machine (UTM). UTM equipment used HunKfeild H5KT model, the test method is as follows.

1) After installing 5N Load cell (Adhesion force is 100N) 2) When loading cell is completed, install the grip to finish the preparation. 3) After the sample is bitten by the grip, measure the tensile elongation at 50mm / min tensile test speed. .

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Connection resistance
85 ℃ 85%
Condition 1 Early 0.30 0.31 0.30 0.30 0.30 0.30 0.29 500 hr 0.40 0.39 0.39 0.40 0.40 4.15 0.42 Condition 2 Early 0.30 0.31 0.30 0.30 0.30 0.30 0.29 500 hr 0.40 0.39 0.39 0.40 0.40 1.17 X Adhesion (Condition 1) 953 1027 1189 1201 1057 854 1134 Tensile elongation 33 37 43 45 22 113 201

(X means no connection)

In the adhesive compositions of Examples 1 to 5, the connection resistance, the tensile elongation and the adhesive strength were all good, whereas in Comparative Example 1, the flowability was reduced due to the absence of the ethylene-vinyl acetate copolymer, resulting in poor connection resistance. 2, the stress relaxation effect disappeared due to the absence of organic particles, the tensile elongation increased significantly, and partial lifting occurred at high temperature compression, resulting in poor connection resistance.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (19)

Tensile elongation after curing is 10% to 100%,
An anisotropic conductive adhesive film comprising 40 to 80% by weight based on the solid weight of the entire film, a binder resin containing at least one of polyester type urethane resin, polyurethane acrylate resin, urethane resin, and organic particles.
The anisotropic conductive adhesive film according to claim 1, wherein the adhesive force at the time of press bonding at 1.0 MPa for 1 second at 70 ° C., and press bonding at 1.0 MPa for 4 seconds at 4.0 ° C. is 800 gf / cm or more.
The anisotropically conductive adhesive film according to claim 1 or 2, wherein the connection resistance increase rate calculated by the following formula 1 is more than 0 and 40% or less.
(1) Connection resistance increase rate (%) = | (AB) / A | x 100
(In Formula 1, A is the connection resistance after pressing at 70 ℃, 1 second, 1 MPa and main compression at 4 MPa for 4 seconds at 150 ℃, B is 500 at 85 ℃ and 85% after the pressing and main compression Connection resistance after reliability evaluation condition for time)
The anisotropic conductive adhesive film according to claim 1 or 2, wherein the organic particles are 1 to 10% by weight based on the solid weight of the entire film.
The anisotropic conductive adhesive film according to claim 1 or 2, wherein the organic particles have a single layer structure or a multilayer structure.
The anisotropic conductive adhesive film according to claim 5, wherein the organic particles of the single layer structure are polyurethane particles.
The anisotropic conductive adhesive film according to claim 6, wherein an ion content of the polyurethane particles is more than 1 and 10 ppm or less.
The method of claim 5, wherein the organic particles of the multilayer structure has a two-layer structure comprising a core and a shell, wherein the glass transition temperature of the polymer resin constituting the core is lower than the glass transition temperature of the polymer resin constituting the shell. Anisotropic conductive adhesive film.
The anisotropic conductive adhesive film according to claim 1 or 2, wherein the organic particles are a copolymer of methyl methacrylate, polystyrene and divinylbenzene or a copolymer of methyl methacrylate, polystyrene and butadiene.
A binder containing at least one of polyester type urethane resin, polyurethane acrylate resin and urethane resin;
Ethylene-vinylacetate copolymers;
Radically polymerizable materials including tricyclodecane dimethanol diacrylate or tricyclodecane dimethanol dimethacrylate; And
Composition for anisotropic conductive films containing organic particles.
The method according to claim 10, wherein the binder is 40 to 80% by weight, the ethylene-vinylacetate copolymer is 5 to 30% by weight, the radical polymerizable material is 10 to 40 based on the total solid weight of the composition for anisotropic conductive film Wt%, and the composition for an anisotropic conductive film containing 1 to 10% by weight of the organic particles.
The composition of claim 10, wherein the ethylene-vinylacetate copolymer has a vinyl acetate content of 15 to 35 wt%.
The composition for anisotropic conductive films according to claim 10, wherein the organic particles have a single layer structure or a multilayer structure.
The composition for anisotropic conductive films according to claim 13, wherein the organic particles of the single layer structure are polyurethane particles.
The composition for anisotropic conductive films according to claim 14, wherein an ion content of the polyurethane particles is more than 1 and 10 ppm or less.
The method of claim 13, wherein the organic particles of the multilayer structure has a two-layer structure comprising a core and a shell, wherein the glass transition temperature of the polymer resin constituting the core is lower than the glass transition temperature of the polymer resin constituting the shell. Composition for anisotropic conductive film.
The composition for anisotropic conductive films according to claim 10, wherein the organic particles are a copolymer of methyl methacrylate, polystyrene, and divinylbenzene or a copolymer of methyl methacrylate, polystyrene, and butadiene.
The composition for anisotropic conductive films of Claim 10 which further contains a radical polymerization initiator and electroconductive particle.
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 film of Claim 1, or a film manufactured from the composition of Claim 10. The semiconductor device.