KR101955749B1 - Composition for use of an anisotropic conductive film, an anisotropic conductive film thereof and a semiconductor device using the same - Google Patents

Abstract

An embodiment of the present invention relates to a copolymer compound of a fluorene-based compound and a bisphenol-type epoxy compound; An epoxy resin having an epoxy equivalent of 150 g / eq or less; Curing agent; And a composition for an anisotropic conductive film containing conductive particles.
Another embodiment of the present invention is an anisotropic conductive film comprising a copolymer compound of a fluorene compound and a bisphenol epoxy compound, wherein the film is heated at 50 DEG C to 80 DEG C for 1 to 3 seconds and at a pressure of 1.0 MPa to 3.0 MPa The anisotropic conductive film having a particle trapping rate of 30% or more and an adhesive force of 10 MPa or more measured according to the following formula 1 measured after the main compression under the pressure conditions of 120 to 160 캜 for 3 to 6 seconds and 60 to 80 MPa .
[Formula 1]
Percentage of particle capture (%) = (unit area (mm ² ) per unit area (mm ² ) of conductive particles after pressure bonding and main compression bonding / number of conductive particles per unit area (mm ² )

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anisotropic conductive film composition, an anisotropic conductive film, and a semiconductor device using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anisotropic conductive film,

The present invention relates to a composition for an anisotropic conductive film, an anisotropic conductive film and a semiconductor device using the same.

Anisotropic conductive film (ACF) generally refers to a film-like adhesive in which conductive particles are dispersed in a resin such as an epoxy resin. An anisotropic conductive film (ACF) is a film-like adhesive in which conductive particles are dispersed in a resin such as epoxy, Means a polymer membrane having anisotropy and adhesion. 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.

Recently, as display panels have become thinner and higher in resolution, techniques for capturing the largest number of conductive particles at the minimum connection area have been studied. A method of increasing the density of the conductive particles or suppressing the flow of the fluid has been studied in order to improve the capture rate of the conductive particles. This is because the insulation resistance between the adjacent electrodes is deteriorated or the adhesive strength is decreased due to the increase of the modulus after curing .

Therefore, it is necessary to develop an anisotropic conductive film which is excellent in insulation resistance characteristic, has a small risk of occurrence of short circuit between electrodes, and has excellent adhesive strength while effectively suppressing the flow of fluid.

Japanese Patent Application Laid-Open No. 2004-359830 (published Dec. 14, 2004)

An object of the present invention is to provide an anisotropic conductive film which is capable of curing at a low temperature and is excellent in particle capture rate, adhesive force and connection resistance property.

In one embodiment of the present invention, a copolymer compound of a fluorene-based compound and a bisphenol-type epoxy compound; An epoxy resin having an epoxy equivalent of 150 g / eq or less; Curing agent; And a conductive particle. The present invention also provides a composition for anisotropic conductive films.

In another embodiment of the present invention, an anisotropic conductive film comprising a copolymer compound of a fluorene-based compound and a bisphenol-type epoxy compound is used as the anisotropic conductive film. The film is heated at 50 to 80 DEG C for 1 to 3 seconds and at a pressure of 1.0 to 3.0 MPa The anisotropic conductive film having a particle trapping rate of 30% or more and an adhesive force of 10 MPa or more measured according to the following formula 1 measured after the final compression under pressure conditions of 120 to 160 ° C for 3 to 6 seconds and 60 to 80 MPa / RTI >

[Formula 1]

Percentage of particle capture (%) = (unit area (mm ² ) per unit area (mm ² ) of conductive particles after pressure bonding and main compression bonding / number of conductive particles per unit area (mm ² )

In another embodiment of the present invention, there is provided a plasma processing apparatus comprising: a first connected member containing a first electrode; A second connected member containing a second electrode; And a semiconductor device connected by the anisotropic conductive film described herein, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode.

The composition for anisotropic conductive film or the anisotropic conductive film according to one embodiment of the present invention can control the flowability at high temperature to improve the capture ratio of conductive particles and can be cured at a low temperature, This is an excellent advantage.

1 shows a first embodiment of the present invention in which a first connected member 50 including a first electrode 70, a second connected member 60 including a second electrode 80, And an anisotropic conductive film (10) comprising conductive particles (3) according to the present invention, which are located between the two connected members and connect the first electrode and the second electrode. Sectional view of the semiconductor device 30.

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.

An embodiment of the present invention relates to a copolymer compound of a fluorene-based compound and a bisphenol-type epoxy compound; An epoxy resin having an epoxy equivalent of 150 g / eq or less; Curing agent; And a conductive particle. The present invention also relates to a composition for anisotropic conductive films.

The composition for anisotropic conductive films according to an embodiment of the present invention may include a copolymer compound of a fluorene compound and a bisphenol-type epoxy compound as a binder resin.

The fluorene compound may be used as long as it is a compound containing a fluorene structure, and may include two or more hydroxyl groups for copolymerization reaction with a bisphenol type epoxy compound.

In one embodiment, the fluorene compound may be a compound having a structure represented by the following formula (1).

[Chemical Formula 1]

R is independently an alkyl group, an alkoxy group, an aryl group or a cycloalkyl group, m is independently an integer of 0 to 4, and n is an integer of 1 to 5 independently of each other.

Since the copolymer compound contains the unit derived from the fluorene-based compound, the heat resistance of the anisotropic conductive film can be improved.

The bisphenol-type epoxy compound is not particularly limited, and for example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol AD type epoxy compound, a bisphenol E type epoxy compound, a bisphenol S type epoxy compound, have. In one example, a bisphenol A type epoxy compound or a bisphenol F type epoxy compound can be used.

The method of copolymerizing the fluorene compound and the bisphenol epoxy compound to form the copolymer compound is not particularly limited. For example, the fluorene compound and the bisphenol epoxy compound may be dissolved in an appropriate solvent, Followed by stirring for 10 to 40 hours at a temperature in the range of 100 ° C to 150 ° C, washing with methanol and water, and drying the resulting precipitate to obtain a copolymerized compound.

Examples of the solvent include propylene glycol monomethyl ether acetate (PGMEA), dimethylformamide (DMF), tetrahydrofuran (THF) and the like, and specifically propylene glycol monomethyl ether acetate (PGMEA) can be used.

Examples of the polymerization catalyst include acid anhydride, amine, imidazole, hydrazide, and cation. These may be used alone or in combination of two or more.

Specifically, the polymerization catalyst may be selected from the group consisting of 2-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole, Phenyl-4-benzylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, (2-ethyl-5-methylimidazole), 2-aminoethyl-2-methylimidazole, 1-cyanoethyl Phenyl-4,5-di (cyanoethoxymethyl) imidazole and the like, and aromatic diazonium salts, aromatic sulfonium salts, aliphatic sulfonium salts, aromatic iodo aluminum salts, phosphonium salts, Onium salt compounds such as pyridinium salts and selenonium salts; Metal arene complexes, silanol / aluminum complexes and the like; Such as benzoin tosylato-, ortho-Nitrobenzyl tosylato-, and other compounds that have an electron-trapping action. More specifically, an imidazole-based polymerization catalyst such as 2-methylimidazole, 2-ethylimidazole or 2-phenyl-4,5-dihydroxymethylimidazole can be used.

In one embodiment, the copolymer compound may be a compound having a structure of any one of the following formulas (2) to (4).

(2)

(3)

[Chemical Formula 4]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each independently represents hydrogen, a C _1-6 alkyl group, a halogen atom or a hydroxy group, and R ₅ and R ₆ are the same or it is different and each independently represents hydrogen, an alkyl group, a halogen atom, C _6-20 or C _6-20 aromatic ring of a C _1-6 alicyclic ring, n is an integer from 1 to 100.

The copolymer compound contains a structure derived from a fluorene compound and a bisphenol-type epoxy compound as one repeating unit, so that the copolymer compound has high heat resistance due to the fluorene structure, and also has -CH ₂ - _{-CH (CH 3) -, -C} (CH 2) - or -C (CH _{3) 2} -, etc. having a carbon skeleton, or -SO ₂ backbone and flexible, high glass transition temperature due to the backbone such as the (Tg) temperature There is also an upright character. Further, by using the copolymer compound in the composition for anisotropic conductive film, the storage stability of the produced anisotropic conductive film can be improved.

The glass transition temperature of the copolymer compound may be in the range of 140 ° C to 200 ° C. Specifically, 150 占 폚 to 180 占 폚, and more specifically, 160 占 폚 to 170 占 폚. The flowability of the anisotropic conductive film made of the composition for anisotropic conductive film containing the above range can be controlled to improve the coverage of conductive particles when used together with conductive particles.

The weight average molecular weight of the copolymer compound may be in the range of 5,000 to 50,000, and may be in the range of 10,000 to 30,000. The anisotropic conductive film made of the composition for anisotropic conductive film including the above range may have appropriate strength.

The copolymer compound may be contained in an amount of 20% by weight to 70% by weight based on the total weight of the solid content of the composition for anisotropic conductive films. Specifically 30% to 60% by weight, more specifically 35% to 55% by weight. Within the above range, the flowability and adhesion of the prepared composition for anisotropic conductive films can be improved.

In another embodiment, the composition for the anisotropic conductive film may further include other binder resin in addition to the copolymer compound.

Examples of the other binder resin include polyimide resin, polyamide resin, phenoxy resin, polymethacrylate resin, polyacrylate resin, polyurethane resin, polyester resin, polyester urethane resin, polyvinyl butyral resin, styrene -Butylene-styrene (SEBS) resin and its modified product, acrylonitrile-butadiene rubber (NBR) and hydrogenated products thereof, and the like, . These may be included in the composition for anisotropic conductive films, alone or in combination of two or more.

When the binder resin is further contained, the content of the other binder resin may be 1 to 20% by weight based on the total weight of the solid content of the composition for anisotropic conductive films.

The epoxy resin having an epoxy equivalent of not more than 150 g / eq is not particularly limited and may be used without limitation as long as the epoxy equivalent is 150 g / eq or less. Specifically, an epoxy resin having an epoxy equivalent of 80 to 150 g / eq may be used, and more specifically, an epoxy resin of 90 to 145 g / eq may be used. When the epoxy equivalent is within the above range, the viscosity and flow characteristics of the anisotropic conductive film can be favorable and the advantage of being able to achieve low-temperature curing can be achieved.

Non-limiting examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol A type epoxy acrylate resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol E type epoxy resin and bisphenol S type epoxy resin Epoxy compounds; Aromatic epoxy compounds such as polyglycidyl ether epoxy resin, polyglycidyl ester epoxy resin and naphthalene epoxy resin; Alicyclic epoxy compounds; Novolak type epoxy compounds such as cresol novolak type epoxy resin and phenol novolak type epoxy resin; Glycidylamine-based epoxy compounds; Glycidyl ester-based epoxy compounds; And biphenyl diglycidyl ether epoxy compounds. Specifically, the epoxy resin may be an alicyclic epoxy resin, a bisphenol-type epoxy resin, or an aromatic epoxy resin, and more specifically, an alicyclic epoxy resin. Since the alicyclic epoxy resin has an epoxy structure close to the alicyclic ring, the ring-opening reaction is rapid, and the curing can be accelerated as compared with other epoxy resins. The alicyclic epoxy resin may be used without limitation as long as it has a structure in which a direct bond is bonded to an alicyclic ring or an epoxy structure exists through another linking group.

In one embodiment, the epoxy resin having an epoxy equivalent of 150 g / eq or less may comprise a liquid epoxy resin. When the liquid epoxy resin is included, the anisotropic conductive film made of the composition for anisotropic conductive film containing the same has the advantage of imparting fluidity and accelerating the curing rate.

The epoxy resin may be contained in an amount of 20% by weight to 50% by weight, specifically 25% by weight to 45% by weight, more specifically 30% by weight to 40% by weight, based on the total weight of the solid content of the composition for anisotropic conductive films . The anisotropically conductive film made of the composition for anisotropic conductive film containing the anisotropic conductive film is excellent in adhesive strength and appearance and can be stable after reliability.

In one embodiment, the composition for the anisotropic conductive film may further include an epoxy resin having an epoxy equivalent of 150 g / eq or more in addition to an epoxy resin having an epoxy equivalent of 150 g / eq or less.

The composition for anisotropically conductive films contains the copolymer compound and an epoxy resin having an epoxy equivalent of not more than 150 g / eq, so that the flowability can be controlled at a high temperature to improve the trapping rate of the conductive particles, And can be excellent in adhesion and connection resistance. When the epoxy resin further contains an epoxy resin having an epoxy equivalent of more than 150 g / eq, it may be contained in an amount of 1 to 10% by weight based on the total solid weight of the composition for anisotropic conductive films.

The conductive particles are not particularly limited and conductive particles conventionally used in the art can be used. Non-limiting examples of usable conductive particles 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 conductive particles may be in the range of, for example, 1 탆 to 20 탆, specifically 1 탆 to 10 탆, depending on the pitch of the applied circuit.

The conductive particles may be contained in an amount of 1 to 30% by weight based on the total weight of the solid content of the composition for anisotropic conductive films, specifically 10 to 25% by weight, more specifically 15 to 30% 20% by weight. In this range, the conductive particles can be easily pressed between the terminals to ensure stable connection reliability, and the connection resistance can be reduced by improving the electrical conductivity.

The curing agent may be any type of curing agent for epoxy curing without particular limitation, and examples thereof include acid anhydride, amine, imidazole, hydrazide, and cation. These may be used alone or in combination of two or more.

Specifically, the curing agent may be a cationic type, and examples thereof include ammonium / antimony hexafluoride.

Since the curing agent is used in combination with an epoxy resin at room temperature, it must not react with the epoxy resin at room temperature after mixing, and it must be activated at a certain temperature or higher to actively react with the epoxy resin to exhibit physical properties. Accordingly, the curing agent may be a compound capable of generating a cation by thermal activation energy, for example, a cationic latent curing agent may be used.

Specifically, examples of the cationic latent curing agent include onium salt compounds such as aromatic diazonium salts, aromatic sulfonium salts, aliphatic sulfonium salts, aromatic iodo aluminum salts, phosphonium salts, pyridinium salts and cerenonium salts; Metal arene complexes, silanol / aluminum complexes and the like; Benzoin tosylato-, ortho-Nitrobenzyl tosylato-, and other compounds having an electron-trapping action can be used. More specifically, a sulfonium salt compound such as an aromatic sulfonium salt compound or an aliphatic sulfonium salt compound having a high cation generation efficiency can be used.

When such a cationic latent curing agent has a salt structure, hexafluoroantimonate, hexafluorophosphate, tetrafluoroborate, pentafluorophenylborate, or the like is used as a counter ion in forming a reactive side salt .

The curing agent may be included in an amount of 0.5 to 10% by weight based on the total weight of the solid content of the composition for anisotropic conductive films. Specifically 2% to 7% by weight. Within the above range, a sufficient reaction required for curing takes place, and excellent physical properties can be expected in adhesion strength, reliability, etc. after bonding through formation of an appropriate molecular weight.

The composition for anisotropic conductive films of the present invention may further contain additives such as a polymerization inhibitor, an antioxidant, and a heat stabilizer in order to provide additional physical properties without impairing 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 total weight of the solid content of the composition for anisotropic conductive films.

As a non-limiting example, the polymerization inhibitor may be selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, phenothiazine, and mixtures thereof. In addition, the antioxidant may be a phenolic or a hydroxy cinnamate-based material, and specifically may be tetrakis- (methylene- (3,5-di-t-butyl-4-hydrosinnamate) Bis (1,1-dimethylethyl) -4-hydroxybenzenepropanoic acid thiol di-2,1-ethanediyl ester, and the like.

Hereinafter, an anisotropic conductive film according to another embodiment of the present invention will be described.

The anisotropic conductive film according to this embodiment contains a copolymer compound of a fluorene compound and a bisphenol epoxy compound and the film is pressed under conditions of 50 DEG C to 80 DEG C for 1 to 3 seconds and 1.0 MPa to 3.0 MPa, A particle trapping rate of 30% or more according to the following formula 1 measured after the main compression under 120 to 160 ° C for 3 to 6 seconds and a pressure of 60 to 80 MPa, and an adhesive force of 10 MPa or more.

As the copolymerizable compound of the fluorene compound and the bisphenol epoxy compound, the same compounds as described in the above examples can be used.

The anisotropically conductive film is press-bonded under the conditions of 50 占 폚 to 80 占 폚 for 1 to 3 seconds and at a pressure of 1.0 MPa to 3.0 MPa and subjected to measurement after the main compression under 120 占 폚 to 160 占 폚 for 3 to 6 seconds and under a pressure of 60 MPa to 80 MPa A particle capture rate according to the following formula 1 may be 30% or more.

[Formula 1]

Percentage of particle capture (%) = (unit area (mm ² ) per unit area (mm ² ) of conductive particles after pressure bonding and main compression bonding / number of conductive particles per unit area (mm ² )

The particle capture rate may be specifically 40% or more, and more specifically 50% or more. The fluidity of the conductive layer is effectively suppressed within the above range, the conductive particles are sufficiently located on the terminal, the conductivity is improved, and the outflow of the conductive particles is reduced to reduce the short-circuit between the terminals.

The method for measuring the particle capture rate is not particularly limited, and a non-limiting example is as follows. For the prepared anisotropic conductive film, the number of conductive particles (mm ² ) per unit area of the pressure- Calculated using a particle automatic meter. Thereafter, an anisotropic conductive film is placed between the first member to be connected and the second member to be connected and press-fitted under conditions of 50 DEG C to 80 DEG C for 1 to 3 seconds and 1.0 MPa to 3.0 MPa, For 6 seconds and under a pressure of 60 MPa to 80 MPa, the number of conductive particles per unit area (mm ² ) of the connection site is calculated using a particle automatic meter, and the particle capture rate is calculated by the above formula (1).

The anisotropically conductive film may have an adhesive strength of 10 MPa or more, specifically 20 MPa or more, more specifically 30 MPa or more, as measured after the pressure bonding and final pressing. When the adhesive strength of the anisotropic conductive film is in the above range, the semiconductor device using the anisotropic conductive film can be used for a long time.

The produced anisotropic conductive film is placed on a glass substrate having an indium tin oxide circuit having a bump area of 1200 mu m ² and a thickness of 2000 ANGSTROM and heated at 50 DEG C to 80 DEG C for 1 to 3 seconds And a pressure of 1.0 MPa to 3.0 MPa. After the release film was removed, an IC chip having a bump area of 1200 탆 ² and a thickness of 1.5 T was placed, and the IC chip was heated at 120 캜 to 160 캜 for 3 to 6 seconds and at a pressure of 60 MPa to 80 MPa The test specimens are manufactured by pressing and measured using a bond tester Dage Series-4000 under the conditions of Maximum load: 200 kgf and Test speed: 100 μm / sec.

The anisotropic conductive film may further include an epoxy resin having an epoxy equivalent of 150 g / eq or less, conductive particles and a curing agent. The same components as those described in the previous embodiment can be used for the above components.

In one embodiment, the anisotropic conductive film may be used in a COG (chip on glass) or COF (chip on film) mounting method.

The anisotropically conductive film may have a minimum melt viscosity of 5,000 to 20,000 Pa · s at 30 ° C to 200 ° C according to the ARES measurement, and may be specifically 6,000 to 10,000 Pa · s. Sufficient adhesion can be exhibited within the above range, the pressure bonding property can be improved, and the insulating layer between the terminals can be sufficiently filled, thereby improving the connection reliability.

The method of measuring the lowest melt viscosity is not particularly limited and examples are as follows. A sample thickness of 150 占 퐉, a temperature raising rate of 10 占 폚 / min, a stress of 5% , And the lowest melt viscosity of the anisotropic conductive film is measured at 30 DEG C to 200 DEG C at a frequency of 10 rad / sec.

In addition, the anisotropic conductive film may have a curing rate of 80% or more according to the following formula (2), specifically 85% or more, more specifically 90% or more.

[Formula 2]

Curing rate (%) = [(H ₀ -H ₁ ) / H ₀ ] × 100

In the formula (2), H ₀ is an area under the curve in a temperature range of -10 ° C./min and -50 ° C. to 250 ° C. under a nitrogen gas atmosphere using a DSC (thermal differential scanning calorimeter, TA instruments, Q20) H ₁ represents the calorific value measured by the same method after being left at 130 ° C for 5 seconds on a hot plate.

The reason why the curing rate is in the above range is that it reflects rapid progress of curing in a short time of 5 seconds at a low temperature of 130 占 폚, and thus is related to the low temperature fast curing property of the anisotropic conductive film.

In another embodiment, the anisotropic conductive film is press-bonded at 50 to 80 DEG C for 1 to 3 seconds and at a pressure of 1.0 to 3.0 MPa, and subjected to compression bonding at 120 to 160 DEG C for 3 to 6 seconds under a pressure of 60 to 80 MPa The initial connection resistance measured after this can be less than 1.0Ω. Specifically, it may be 0.7 Ω or less, more specifically 0.5 Ω or less.

The anisotropic conductive film may be allowed to stand for 500 hours at a temperature of 85 deg. C and a relative humidity of 85% after the pressurization and final compression, and the connection resistance after the reliability evaluation may be 3? Or less. Specifically, it may be 2? Or less, more specifically, may be 1? Or less.

The anisotropic conductive film having the initial connection resistance and the connection resistance range after the reliability evaluation has an advantage that not only the connection reliability can be improved but also the long-term storage stability can be maintained and used.

The initial connection resistance and the method of measuring the connection resistance after the reliability evaluation are not particularly limited, and a non-limiting example is as follows. An anisotropic conductive film is formed on a glass substrate having an indium tin oxide circuit with a bump area of 1200 탆 ² and a thickness of 2000 Å And the pressure-sensitive adhesive was pressed at 50 to 80 DEG C for 1 to 3 seconds and at 1.0 to 3.0 MPa, respectively. Thereafter, the release film was removed, IC chips having a bump area of 1200 mu m ² and a thickness of 1.5T were placed, , 3 to 6 seconds, and 60 MPa to 80 MPa, and the resistance between the four points is measured using the 4-point probe method. Thereafter, the test piece thus prepared was allowed to stand for 500 hours at a temperature of 85 ° C and a relative humidity of 85%, and the resistance was measured in the same manner. The resistance measuring device applies 1mA, and the resistance is calculated by the measured voltage and averaged.

In one embodiment, the anisotropic conductive film may have a structure in which an insulating layer is laminated on one side or both sides of a conductive layer. That is, a two-layer structure in which a conductive layer and an insulating layer are laminated, or a three-layer structure in which a conductive layer is laminated on an insulating layer and an insulating layer is laminated on the conductive layer. Lt; / RTI > stacked layer structure.

The term " lamination " means that another layer is formed on one side of an arbitrary layer and can be used in combination with coating or lamination. In the case of an anisotropic conductive film having a multilayered structure including a conductive layer and an insulating layer separately, since the layer is separated, even if the content of inorganic particles such as silica is high, the conductive particles are not squeezed, The flowability of the composition for the anisotropic conductive film may be affected, so that the anisotropic conductive film having controlled flowability can be produced.

Another embodiment of the present invention relates to a process for producing an anisotropic conductive film. No special apparatus or equipment is required to form the anisotropic conductive film of the present invention. For example, the composition for anisotropic conductive films containing the respective compositions disclosed in the present application is dissolved in an organic solvent such as toluene and liquefied. Thereafter, the conductive particles are agitated for a predetermined time in a speed range in which the conductive particles are not crushed, For example, 10 占 퐉 to 50 占 퐉 and dried for a predetermined time to volatilize toluene or the like to obtain an anisotropic conductive film.

Hereinafter, a semiconductor device according to another embodiment of the present invention will be described.

The semiconductor device includes: a first connected member containing a first electrode; A second connected member containing a second electrode; And a semiconductor device connected by the anisotropic conductive film according to the embodiments described herein, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode. .

Specifically, the first to-be-connected members or the second to-be-connected members are formed of ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), or the like used for a liquid crystal display A printed wiring board, a ceramic wiring board, a flexible wiring board, a semiconductor silicon chip, an IC chip, or a driver IC chip on which electrodes of the first to-be-connected members and the electrodes to be connected are formed. More specifically, May be an IC chip or a driver IC chip, and the other may be a glass substrate.

1, the semiconductor device 30 includes a first connected member 50 including a first electrode 70 and a second connected member 60 including a second electrode 80, Through the anisotropic conductive film (10) comprising the conductive particles (3) described herein, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode They can be bonded to each other.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. 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.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example

Manufacturing example  1 to 4: Preparation of copolymer compound

Manufacturing example  1: Preparation of Copolymer Compound 1

14 g of 9,9'-bis (4-hydroxyphenyl) fluorene and 16 g of bisphenol F type epoxy resin (YSLV-80XY, Kukdo Chemical) were dissolved in 30 g of PGMEA. Then, 0.1 g of 2-methyl imidazole was added thereto and stirred at 110 ° C. for 24 hours Respectively. After stirring, the mixture was washed with methanol and water, and the resulting precipitate was dried to prepare copolymer compound 1 (Tg: 170 ° C, weight average molecular weight: 25,000) having the following structure.

[Copolymer compound 1]

Manufacturing example  2: Preparation of Copolymer Compound 2

15 g of 9,9'-bis (4-hydroxyphenyl) fluorene and 10 g of bisphenol A type epoxy resin (JER834, Mitsubishi Chemical) were dissolved in 30 g of PGMEA, 0.1 g of 2-methyl imidazole was added and the mixture was stirred at 110 ° C for 24 hours. After stirring and washing with methanol and water, the resulting precipitate was dried to prepare copolymer compound 2 (Tg: 165 ° C, weight average molecular weight: 20,000) having the following structure.

[Copolymer compound 2]

Manufacturing example  3: Preparation of Copolymer Compound 3

15 g of 9,9'-bis (4-hydroxyphenyl) fluorene and 10 g of 1,1'-bis (4-hydroxyphenyl) methane were dissolved in 30 g of PGMEA with bisphenol F type epoxy resin. Then, 0.1 g of 2-methyl imidazole C < / RTI > for 24 hours. After stirring and washing with methanol and water, the precipitate formed was dried to prepare a copolymer compound 3 (Tg: 165 ° C, weight average molecular weight: 22,000) having the following structure.

[Copolymer compound 3]

Example  And Comparative Example

Example  One

40 parts by weight of Copolymer Compound 1 prepared in Preparation Example 1, 35 parts by weight of an epoxy resin having an epoxy equivalent of 130 g / eq (Daicel celloxide 2021P), 30 parts by weight of a thermosetting latent curing agent (HX3741, (AUL-704, average particle diameter: 4 袖 m, SEKISUI Co., Ltd., Japan) as a filler for imparting conductivity to an anisotropic conductive film were mixed to obtain an anisotropic conductive film A composition was prepared. The above composition for anisotropic conductive film was coated on a release film, and then the solvent was evaporated in a drier at 70 캜 for 5 minutes to obtain a dried anisotropic conductive film having a thickness of 15 탆.

Example  2

Example 1 was repeated except that the copolymer compound 2 produced in Production Example 2 was used as the binder resin and the epoxy resin 2 (HP4032D, Dinippon ink) having an epoxy equivalent of 143 g / eq was used as the epoxy resin. The anisotropic conductive film of Example 2 was prepared.

Example  3

Except that the copolymer compound 3 produced in Production Example 3 was used as the binder resin and the epoxy resin 3 (JER630ESD, Japan epoxy resin) having an epoxy equivalent of 97 g / eq was used as the epoxy resin in Example 1 1, an anisotropic conductive film of Example 3 was prepared.

Comparative Example  One

By the same conditions and in the same manner as in Example 1, except that a biphenyl fluorene type binder resin (FX-293, Shinil Chemical Co., Ltd., Tg: 165 ° C, molecular weight: 45,000) was used as the binder resin in Example 1 1 < / RTI >

Comparative Example  2

An anisotropic conductive film of Comparative Example 2 was produced in the same manner as in Example 1 except that an epoxy resin having an epoxy equivalent of 180 g / eq (YDPN 638, Kukdo Chemical) was used as an epoxy resin .

Experimental Example

The minimum melt viscosity, curing rate, particle capture rate, adhesive force and connection resistance of the anisotropic conductive films of Examples 1 to 3 and Comparative Examples 1 and 2 were measured under the following conditions and methods, Respectively.

Experimental Example  1: lowest Melt viscosity  Measure

The anisotropically conductive films produced in the above Examples and Comparative Examples were subjected to a heat treatment under the conditions of a sample thickness of 150 mu m, a temperature raising rate of 10 DEG C / min, a stress of 5% and a frequency of 10 rad / sec from 30 DEG C to 200 DEG C using an ARES G2 rheometer (TA Instruments) The lowest melt viscosity was measured.

Experimental Example  2 : Hardening rate  Measure

1 mg of the anisotropic conductive film prepared in Examples and Comparative Examples was dispensed and analyzed by DSC (thermal differential scanning calorimetry, TA instruments, Q20) under an atmosphere of nitrogen gas at 10 占 폚 / min and an initial The heating value is measured by the area under the curve (H ₀ ), and then the film is left on a hot plate at 130 ° C. for 5 seconds, and the heating value is measured by the same method (H ₁ ) The hardening rate was calculated.

 [Formula 2]

Curing rate (%) = [(H ₀ -H ₁ ) / H ₀ ] × 100

Experimental Example  3: Particle capture rate  Measure

With respect to the anisotropic conductive films produced in the Examples and Comparative Examples, the number of conductive particles (mm ² ) per unit area of the pressure-contact prior anisotropic conductive film was calculated using a particle automatic meter (ZOOTUS).

Further, an anisotropic conductive film was placed on a glass substrate (Neoview Kolon) having an indium tin oxide circuit having a bump area of 1200 탆 ² and a thickness of 2000 Å and pressurized at 70 ° C for 1 second at 1 MPa, (Samsung LSI) having a bump area of 1200 탆 ² and a thickness of 1.5 T was placed on the surface of the substrate and then pressed at 130 캜 for 5 seconds under a pressure of 70 MPa to measure the number of conductive particles (mm ² ) Was calculated using the particle automatic meter, and the particle capture rate was calculated by the following equation (1).

[Formula 1]

Percentage of particle capture (%) = (unit area (mm ² ) per unit area (mm ² ) of conductive particles after pressure bonding and main compression bonding / number of conductive particles per unit area (mm ² )

Experimental Example  4: Measurement of adhesive force

The anisotropic conductive films prepared in the above examples and comparative examples were placed on a glass substrate (Neoview Kolon) having an indium tin oxide circuit having a bump area of 1200 占 퐉 ² and a thickness of 2000 占 and pressed at 70 占 폚 for 1 second at 1 MPa . After releasing the release film, an IC chip (Samsung LSI) having a bump area of 1200 占 퐉 ² and a thickness of 1.5T was prepared, and the resultant was compression-bonded at 130 占 폚 for 5 seconds under a pressure of 70 MPa to prepare a test piece. The average of these measurements was calculated at least three times per each specimen using a bond tester Dage Series-4000 under the conditions of Maximum load: 200 kgf and Test speed: 100 μm / sec.

Experimental Example  5: Measurement of connection resistance after initial and reliability evaluation

The anisotropic conductive films prepared in the above examples and comparative examples were placed on a glass substrate (Neoview Kolon) having an indium tin oxide circuit having a bump area of 1200 占 퐉 ² and a thickness of 2000 占 and pressed at 70 占 폚 for 1 second at 1 MPa . After releasing the releasing film, an IC chip (Samsung LSI) having a bump area of 1200 탆 ² and a thickness of 1.5T was placed thereon, and the resultant was pressed at 130 캜 for 5 seconds under a pressure of 70 MPa to prepare a test piece. The resistance between 4 points was measured using the 4 point probe method, which was expressed as the initial connection resistance. Thereafter, the sample was left for 500 hours under the conditions of a temperature of 85 ° C and a relative humidity of 85%, and the resistance was measured in the same manner.

The resistance measuring instrument is applied with 1 mA, and the resistance is calculated by the measured voltage and averaged.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 The lowest melt viscosity (Pa · s) 10,000 7,000 8,500 25,000 45,000 Curing rate (%) 87 86 88 65 70 Particle capture rate (%) 33 34 32 18 16 Adhesion (MPa) 33 32 34 30 28 Initial connection resistance (Ω) 0.02 0.03 0.03 0.05 0.07 Connection resistance (Ω) after reliability evaluation 0.12 0.13 0.12 1.20 1.50

As shown in Table 1, a copolymer compound of a fluorene compound and a bisphenol-type epoxy resin; And an epoxy resin having an epoxy equivalent of 150 g / eq or less exhibited excellent physical properties both in terms of minimum melt viscosity, curing rate, particle capture rate, adhesion, initial and reliability, and connection resistance . On the other hand, Comparative Example 1 in which a copolymer compound of a fluorene compound and a bisphenol-type epoxy resin was not used had a lowest melt viscosity due to a low Tg of the binder resin, a low curing rate at 130 ° C, After the reliability evaluation, the connection resistance was found to increase greatly. Comparative Example 2 using an epoxy resin having an epoxy equivalent of more than 150 g / eq showed the lowest melt viscosity because the flow characteristics were poor and the cure rate and the particle capture rate were lower than those of the examples as in Comparative Example 1 After the reliability evaluation, the connection resistance was greatly increased.

Claims (19)

20 to 70% by weight of a copolymer compound of a fluorene-based compound and a bisphenol-type epoxy compound based on the total solid weight of the composition for anisotropic conductive film; 20 to 50% by weight of an epoxy resin having an epoxy equivalent of more than 0 g / eq and not more than 150 g / eq; 0.5% to 10% by weight of a hardener; And 1% by weight to 30% by weight of conductive particles,
Wherein the copolymer compound has a glass transition temperature (Tg) of 140 캜 to 200 캜,
The anisotropic conductive film formed from the composition for anisotropic conductive film is pressed under pressure at 50 to 80 DEG C for 1 to 3 seconds and at a pressure of 1.0 to 3.0 MPa and pressurized at 120 to 160 DEG C for 3 to 6 seconds and at a pressure of 60 to 80 MPa Composition for anisotropic conductive films having a particle capture rate of 30% or more according to the following formula (1)
[Formula 1]
Particle capture rate (%) = (the pressure per unit area and the mounting of the connecting portion after the pressing (mm ²⁾ number of conductive particles / pressurized before mounting per unit area of the anisotropic conductive film (mm ²⁾ number of the conductive particles) × 100. The composition for an anisotropic conductive film according to claim 1, wherein the fluorene compound comprises 2 to 10 hydroxyl groups. The composition for an anisotropic conductive film according to claim 2, wherein the fluorene compound has a structure represented by the following formula (1).
[Chemical Formula 1]

In Formula 1, R is independently an alkyl group, an alkoxy group, an aryl group or a cycloalkyl group,
m is independently an integer of 0 to 4,
n is independently an integer of 1 to 5; The anisotropic conductive film according to claim 1, wherein the bisphenol epoxy compound is a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol AD epoxy compound, a bisphenol E epoxy compound, a bisphenol S epoxy compound, / RTI > The composition for an anisotropic conductive film according to claim 1, wherein the copolymer compound has a structure of any one of the following formulas (2) to (4).
(2)

(3)

[Chemical Formula 4]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each independently represents hydrogen, a C _1-6 alkyl group, a halogen atom or a hydroxy group,
R ₅ and R ₆ are the same or different and are each independently hydrogen, a C _1-6 alkyl group, a halogen atom, a C _6-20 aromatic ring or a C _6-20 alicyclic ring,
n is an integer of 1 to 100; The composition for an anisotropic conductive film according to claim 1, wherein the copolymer compound has a weight average molecular weight of 5,000 to 50,000. delete The composition for an anisotropic conductive film according to claim 1, wherein the epoxy resin having an epoxy equivalent of more than 0 g / eq and not more than 150 g / eq is an alicyclic epoxy resin, a bisphenol epoxy resin or an aromatic epoxy resin. delete 20% to 70% by weight of a copolymer compound of a fluorene compound and a bisphenol-type epoxy compound based on the total solid weight; 20 to 50% by weight of an epoxy resin having an epoxy equivalent of more than 0 g / eq and not more than 150 g / eq; 0.5% to 10% by weight of a hardener; And 1 to 30% by weight of conductive particles, wherein the copolymer compound has a glass transition temperature (Tg) of 140 to 200 ° C,
The anisotropic conductive film was measured after press bonding under pressure conditions of 120 ° C to 160 ° C for 3 to 6 seconds and 60 MPa to 80 MPa under pressure at 50 ° C. to 80 ° C. for 1 to 3 seconds and at a pressure of 1.0 MPa to 3.0 MPa An anisotropic conductive film having a particle trapping rate of 30% or more according to the following formula 1 and an adhesive force of 10 MPa or more;
[Formula 1]
Particle capture rate (%) = (the pressure per unit area and the mounting of the connecting portion after the pressing (mm ²⁾ number of conductive particles / pressurized before mounting per unit area of the anisotropic conductive film (mm ²⁾ number of the conductive particles) × 100. The anisotropic conductive film of claim 10, wherein the fluorene compound comprises 2 to 10 hydroxyl groups. The anisotropic conductive film according to claim 11, wherein the fluorene compound has a structure represented by the following formula (1).
[Chemical Formula 1]

In the formula 1, each R is independently an alkyl group, an alkoxy group, an aryl group or a cycloalkyl group,
m is independently an integer of 0 to 4,
n is independently an integer of 1 to 5; The anisotropic conductive film according to claim 10, wherein the copolymer compound has a structure of any one of the following formulas (2) to (4).
(2)

(3)

[Chemical Formula 4]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each independently represents hydrogen, a C _1-6 alkyl group, a halogen atom or a hydroxy group,
R ₅ and R ₆ are the same or different and are each independently hydrogen, a C _1-6 alkyl group, a halogen atom, a C _6-20 aromatic ring or a C _6-20 alicyclic ring,
n is an integer of 1 to 100; The anisotropic conductive film according to claim 10, wherein the anisotropic conductive film is used in a COG (chip on glass) or COF (chip on film) mounting method. The anisotropic conductive film according to claim 10, wherein the lowest melt viscosity at 30 캜 to 200 캜 according to the ARES measurement is 5,000 to 20,000 Pa · s. The anisotropic conductive film according to claim 10, wherein an initial connection resistance measured after press bonding and final pressing is not less than 0 Ω and not more than 1.0 Ω. The anisotropic conductive film according to claim 10, wherein the connection resistance is 0 Ω or more and 3 Ω or less after reliability evaluation, which is performed after the pressurization and final compression bonding and is allowed to stand for 500 hours at a temperature of 85 ° C. and a relative humidity of 85%. The anisotropic conductive film according to claim 10, wherein the curing rate according to formula (2) is 80% or more.
[Formula 2]
Curing rate (%) = [(H ₀ -H ₁ ) / H ₀ ] × 100
In the formula (2), H ₀ is an initial calorific value measured at an area under a curve at a temperature range of -50 ° C to 250 ° C at a rate of 10 ° C / min under a nitrogen gas atmosphere using a differential scanning calorimeter (DSC) H ₁ represents the calorific value measured by the same method after being left for 5 seconds at 130 ° C on a hot plate. A first connected member containing a first electrode;
A second connected member containing a second electrode; And
The semiconductor device being connected by the anisotropic conductive film according to any one of claims 10 to 18, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode. .

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