KR20170099299A - Anisotropic conductive film and electronic device using the same - Google Patents

Abstract

Provided are an anisotropic conductive film and an electronic device using the same. According to an embodiment of the present invention, the anisotropic conductive film has a modulus of 2.5-4 GPa measured at 30C after curing the film and has a calorific value change rate, represented by Formula 1, calorific value change rate (%) = [(H_0-H_1)/H_0]100, on a differential scanning calorimeter (DSC) which is 20% or smaller. In Formula 1, H_0 represents a calorific value on the DSC, which is measured immediately after manufacturing the film with respect to the anisotropic conductive film, and H_1 represents a calorific value on the DSC, which is measured five days after storing the anisotropic conductive film at 25C.

Description

TECHNICAL FIELD [0001] The present invention relates to an anisotropic conductive film and an electronic device using the same.

The present invention relates to an anisotropic conductive film and an electronic 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 anisotropic conductive film is placed between the circuit terminals to be connected and subjected to the heating and pressing process under a certain condition, the circuit terminals overlapping each other are electrically connected to each other by the conductive particles. On the other hand, since the insulating adhesive resin is filled between the neighboring circuit terminals to isolate the conductive particles from each other, the neighboring circuit terminals are insulated from each other.

The anisotropic conductive film can be used for bonding a driving IC, a printed circuit board, and the like to a glass substrate in a flat panel display such as a liquid crystal display device, an organic light emitting diode display device, and the like.

In recent years, a thinner glass substrate is required as the display panel is thinned. However, when a driver IC is mounted on a glass substrate using an anisotropic conductive film, a warpage phenomenon occurs in which a thin glass substrate is bent by a heating and pressing process. The warping of the substrate causes a light leakage phenomenon, which causes a display failure. The warping of the glass substrate becomes worse as the substrate becomes thinner, thereby increasing the defective display ratio.

In order to prevent warpage of the glass substrate, an anisotropic conductive film that can be rapidly cured at a low temperature of 150 DEG C or less within 5 seconds is required. In order to meet such a demand, it is necessary to use a highly reactive curable compound and a curing agent. However, storage stability is poor due to high reactivity, and an excessive amount of a stabilizer is required. Japanese Unexamined Patent Application Publication No. 2012-171980 uses an alicyclic epoxy compound and an oxetane compound as a curing compound and uses a sulfonium-based latent cation catalyst having a specific structure, but an alicyclic epoxy compound and an oxetane compound and a sulfone-based cation Storage stability is lowered due to the high reactivity of the catalyst.

On the other hand, in order to realize a high resolution of a display, it is necessary to connect a driving IC chip having terminals arranged at a finer pitch to a glass substrate. Accordingly, the anisotropic conductive film must be able to secure sufficient insulation between neighboring terminals and to capture sufficient conductive particles so as to have sufficient conductive properties at a connection area of a fine area.

Japanese Laid-Open Patent Publication No. 2012-171980 (published on 09., 2012.)

It is an object of the present invention to provide an anisotropic conductive film which improves the particle trapping rate and has a high storage stability while rapidly curing at a temperature of 150 ° C or lower.

It is still another object of the present invention to provide an electronic device using the anisotropic conductive film.

In an embodiment of the present invention, the elastic modulus measured at 30 ° C after the film curing is 2.5 to 4 GPa, and the anisotropic conductivity (the Young's modulus of elasticity) in which the rate of change in calorific value on the DSC of the following formula Film is provided.

[Formula 1]

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

In the above formula (1), H ₀ represents the calorific value on the DSC of the anisotropic conductive film measured immediately after the film is formed, H ₁ represents the heat parallax measured after storing the anisotropic conductive film at 25 ° C for 5 days And shows the calorific value on the scanning calorimeter.

In another embodiment of the present invention, the binder resin; Silsesquioxane compounds containing an oxetane group; Phenol novolac oxetane compounds; Potential cationic curing agents; And an anisotropic conductive film containing conductive particles.

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 an anisotropic conductive film according to the present invention, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode.

The anisotropic conductive film according to an embodiment of the present invention has a high modulus of elasticity ranging from 2.5 GPa to 4 GPa and thus has a good particle capture rate and a low rate of change in the calorific value on the thermal differential scanning calorimeter. In addition, the anisotropic conductive film according to one embodiment of the present invention includes a silsesquioxane compound containing an oxetane group to achieve a good particle capture rate, and further includes a phenol novolac oxetane compound, Storage stability can be maintained.

1 shows the first to-be-connected member 50 including the first electrode 70, the second connected member 60 including the second electrode 80, and the first to-be-connected members 50, And a cured film (10) positioned between the first electrode (70) and the second connected member (60) and connecting the first electrode (70) and the second electrode (80). The cured film 10 is a cured anisotropic conductive film as described herein.

Hereinafter, embodiments of the present invention will be described in 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.

The anisotropic conductive film according to an embodiment of the present invention has a modulus of elasticity of 2.5 to 4 GPa measured at 30 ° C after curing the film and maintained at 25 ° C for 5 days, 20% or less.

[Formula 1]

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

In the above formula (1), H ₀ represents the calorific value on the DSC of the anisotropic conductive film measured immediately after the film is formed, H ₁ represents the heat parallax measured after storing the anisotropic conductive film at 25 ° C for 5 days It shows the calorific value on the scanning calorimeter (DSC).

Elastic modulus

The anisotropic conductive film according to the present invention may have an elastic modulus measured at 30 ° C of 2.5 to 4 GPa, and more specifically 3.0 to 4.0 GPa.

The method for measuring the modulus of elasticity is not particularly limited, and a method commonly used in the art can be used. As a non-limiting example of a method of measuring the elastic modulus, a lamination technique is used to laminate several layers of a film to form an anisotropic conductive film having a thickness of 100 mu m, curing the film with a hot press, Using a Dynamic Mechanical Analyzer, the elastic modulus is measured while raising the temperature from -40 ° C to 200 ° C at a rate of 10 ° C / min.

Among the measured values of the modulus of elasticity, when the modulus of elasticity at 30 캜 is within the above range, the particle capture rate is excellent.

Thermal differential scanning calorimeter (DSC) phase  Change in calorific value

The anisotropic conductive film according to the present invention may have a calorific value change rate of 20% or less, specifically 15% or less, more specifically 10% or less, after storage at 25 ° C for 5 days.

 [Formula 1]

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

In the above formula (1), H ₀ represents the calorific value on the DSC of the anisotropic conductive film measured immediately after the film is formed, H ₁ represents the heat parallax measured after storing the anisotropic conductive film at 25 ° C for 5 days It shows the calorific value on the scanning calorimeter (DSC).

As a method for calculating the calorific value on the thermal differential scanning calorimeter, a commonly used method can be used. As a non-limiting example, the anisotropic conductive film is heated at 10 DEG C (20 DEG C) under a nitrogen gas atmosphere using a thermal differential scanning calorimeter (DSC, TA instruments, Q20) / min to 30 < 0 > C to 250 < 0 > C.

When the rate of change in caloric value in the above range is satisfied, the storage stability of the anisotropic conductive film is good.

Connection resistance after leaving film

In one embodiment of the present invention, the anisotropic conductive film may have a connection resistance after curing at 130 캜 after being left within 3 to 7 days after the film is made, of 1 Ω or less.

The connection resistance can be measured in a conventional manner and includes, but is not limited to, a glass substrate with a bump area of 1200 탆 ² , a 2000 Å thick indium tin oxide (ITO) circuit, and a bump area 1200 μm ² , Using an anisotropic conductive film, the upper and lower interfacial surfaces were pressed and bonded under the conditions of 70 DEG C, 1.0 MPa, and 1 second under pressure and at 130 DEG C and 70 MPa for 5 seconds, and the IC was bonded to ITO And the voltage between four points is measured by using four probes connected to the resistance measuring instrument. The resistance measuring device measures the voltage by applying 1 mA, and uses this voltage to calculate the resistance.

When the connection resistance is in the above range, the storage stability of the anisotropic conductive film is very good.

Glass transition temperature ( Tg )

In one embodiment of the present invention, the anisotropic conductive film may have a glass transition temperature (Tg) after film curing of 150 to 250 캜, specifically, 180 to 200 캜.

The glass transition temperature can be measured by a conventional method. As a non-limiting example, the film is cured using a hot press, and after confirming that the film has been sufficiently cured by DSC, Tg is measured while increasing the temperature from -40 ° C to 200 ° C.

The anisotropic conductive film of this example has a relatively high glass transition temperature after curing, which is attributable to the phenol novolac oxetane compound. When the glass transition temperature is in the above range, reliability against high temperature and high humidity after curing of the anisotropic conductive film is good.

Oxetane group  Containing Silsesquioxane  compound

In one embodiment of the present invention, the anisotropic conductive film may include a silsesquioxane compound containing an oxetane group. The silsesquioxane compound containing an oxetane can be part of the molecular formula R-SiO process chamber of the extractor dioxane compound R represented by the _3/2 it refers to a compound substituted with an oxetane. Specifically, the silsesquioxane compound containing an oxetane group may contain a repeating unit represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ is an oxetane group and R ₂ is hydrogen, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an alkylaryl group, a heteroalkyl group, a heterocycloalkyl group, or an alkenyl group X and y may be in the range of 0 < x < 1.0, 0 < y < 1.0 and x + y = 1. In one embodiment, x may range from 0.5? X? 1.0. When x is within the above range, the oxetane group is sufficiently contained, and when the curing is carried out, the ring-opening reaction thereof is sufficiently generated, and there is an advantage that the curing at low temperature can be achieved.

Unless defined otherwise herein, 'substituted' means that a hydrogen atom in the compound is replaced by a halogen atom (F, Br, Cl, I), a halogenated alkyl, a hydroxy group, an alkoxy group, a nitro group, a cyano group, A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₂₀ alkoxy group, to about C ₃₀ aryl, C ₇ to C ₃₀ arylalkyl group, C ₁ to C ₂₀ alkoxy group, C ₁ to C ₂₀ heteroaryl group, a C ₃ to C ₂₀ heteroaryl group, a C ₃ to C ₂₀ cycloalkyl group, a (meth) Acrylate group, a C ₂ to C ₂₀ heterocycloalkyl group, and combinations thereof.

As used herein, the term "alkyl group" means a straight or branched chain fully saturated or partially unsaturated hydrocarbon group having 1 to 20 carbon atoms, and "cycloalkyl group" means a hydrocarbon group having a fully saturated or partially unsaturated ring having 3 to 20 carbon atoms do. The 'heteroalkyl group' means a fully saturated or partially unsaturated hydrocarbon group of 1 to 20 carbon atoms containing a hetero atom other than carbon or hydrogen in the main chain, and the 'heterocycloalkyl group' Means a hydrocarbon group having a fully saturated or partially unsaturated ring of 2 to 20 carbon atoms containing an atom.

The silsesquioxane-containing silsesquioxane compound has a polyhedral oligomeric silsesquioxane (POS) structure represented by the following Chemical Formulas 2 to 5, a random structure represented by Chemical Formula 6, a ladder ) Structure, or a partial cage structure of the following formula (8).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above Chemical Formulas 2 to 8, R is an oxetane group, hydrogen, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an alkylaryl group, a heteroalkyl group, a heterocycloalkyl group or an alkenyl group.

Specifically, the silsesquioxane compound containing an oxetane group may include the polyhedral oligomeric silsesquioxane structure of the above formulas (2) to (5).

The silsesquioxane-containing silsesquioxane compound may be contained in an amount of 1 to 20% by weight based on the total solid weight of the anisotropic conductive film. Specifically 5 to 15% by weight. Within the above range, the anisotropic conductive film has appropriate fluidity so that the particle attraction rate can be improved while the indentation characteristics are excellent, and the connection reliability can also be improved.

Phenol novolac Oxetane  compound

In one embodiment of the present invention, the anisotropic conductive film may comprise a phenol novolac oxetane compound. The phenol novolac oxetane compound can be represented by the following general formula (9).

[Chemical Formula 9]

R ₃ is an alkyl group having 1 to 6 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group propyl group or a butyl group, a fluoroalkyl group having 1 to 6 carbon atoms or an aryl group, and m is an integer of 0 to 10.

The phenol novolak oxetane compound has a reaction retarding effect that prevents the reaction at a low temperature and does not significantly decrease the reactivity at the curing temperature. Therefore, by using a phenol novolac oxetane compound as a curing compound together with a silsesquioxane compound containing an oxetane group, it is possible to improve the particle capture rate by the silsesquioxane compound and to improve the storage stability and the anisotropic conductivity A film can be provided. In addition, it is possible to provide an anisotropic conductive film having a high glass transition temperature and a low connection resistance rise rate at high temperature / high humidity after curing.

The phenol novolac oxetane compound may be contained in an amount of 10 to 40% by weight based on the total solid weight of the anisotropic conductive film. Specifically, 25 to 35% by weight can be included.

Binder resin

In one embodiment of the present invention, the anisotropic conductive film may comprise a binder resin.

Examples of the binder resin include polyimide resin, polyamide resin, phenoxy resin, polymethacrylate resin, polyacrylate resin, polyurethane resin, polyester resin, polyester urethane resin, polyvinyl butyral resin, styrene- Butadiene rubber (NBR) and its hydrogenated product, or a combination thereof, and a styrene-butylene-styrene (SBS) resin and an epoxy modified product, a styrene- . Specifically, a phenoxy resin can be used as the binder resin, and more specifically, a fluorene-based phenoxy resin can be used. The fluorene-based phenoxy resin can be used without limitation as long as it is a phenoxy resin containing a fluorene structure.

The binder resin may include 30 to 60% by weight based on the total solid weight of the anisotropic conductive film. Specifically 35 to 50% by weight.

Potential cation curing agent

In one embodiment of the present invention, the anisotropic conductive film may comprise a latent cationic curing agent. As the latent cationic curing agent, a sulfonium type curing agent and an amine type cationic curing agent can be used, and in particular, quaternary ammonium compounds can be used in terms of stability.

As the quaternary ammonium compound, a compound having a structure represented by the following formula (10) can be used.

[Chemical formula 10]

In Formula 10, R ₄ , R ₅ , R _6, and R ₇ are each a substituted or unsubstituted C ₁ C ₆ to C ₆ alkyl or C ₆ to C ₂₀ aryl; M ^- is one of Cl, BF ₄ , PF ₆ , N (CF ₃ SO ₂ ) ² , CH ₃ CO ₂ , CF ₃ CO ₂ , CF ₃ SO ₃ , HSO ₄ , SO ₄ ² , SbF ₆ ^- , and B (C ₆ F ₅ ) ₄ ^- .

Specifically, in the quaternary ammonium compound of Formula 10, R ₄ , R ₅ , R ₆ and R ₇ are each a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, An n-pentyl group, a t-pentyl group, an isopentyl group, a hexyl group, a cyclohexyl group, a phenyl group, an anthryl group and a phenanthryl group. In the case where the term "substituted" is used herein, the group which may be substituted may be, for example, an alkyl group, an alkoxy group, an amino group, a halogen or a nitro group.

The quaternary ammonium compound accelerates the ring-opening reaction of the epoxy compound at a specific temperature and promotes the development reaction of the silsesquioxane and phenol novolak oxetane compounds containing oxetane groups by the ring-opening reaction of the epoxy compound, So that it can be rapidly cured in the range. Furthermore, the quaternary ammonium compound can delay the ring-opening reaction of the epoxy compound and provide excellent storage stability at a temperature lower than the curing temperature, for example, at room temperature.

In the formula (10), M ^- may be specifically one of SbF ₆ ^- and B (C ₆ F ₅ ) ₄ ^- . More specifically, M ^- can be B (C ₆ F ₅ ) ₄ ^- , which is preferred because it does not cause environmental problems.

The latent cationic curing agent may be included in an amount of 1 to 5% by weight based on the total weight of the solid content of the anisotropic conductive film.

Epoxy compound

The anisotropic conductive film according to one embodiment of the present invention may include an epoxy compound as a curable compound. Examples of the epoxy compound include bisphenol-type epoxy compounds such as bisphenol A type epoxy compound, bisphenol A type epoxy acrylate compound, bisphenol F type epoxy compound, bisphenol AD type epoxy compound, bisphenol E type epoxy compound and bisphenol S type epoxy compound; Aromatic epoxy compounds such as polyglycidyl ether epoxy compounds, polyglycidyl ester epoxy compounds and naphthalene epoxy compounds; Alicyclic epoxy compounds; Novolak type epoxy compounds such as cresol novolak type epoxy compounds and phenol novolak type epoxy compounds; Glycidylamine-based epoxy compounds; Glycidyl ester-based epoxy compounds; And biphenyl diglycidyl ether epoxy compounds. These may be used alone or in combination of two or more. Specifically, an alicyclic epoxy compound can be used. The alicyclic epoxy compound has an epoxy structure close to the alicyclic ring, so that the ring opening reaction is rapid and the curing reaction is better than the other epoxy compounds. The alicyclic epoxy compound 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 in another linkage group. In one example, alicyclic epoxy compounds of the following general formulas (11) to (14) can be used.

 (11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

In the general formulas 12 to 14, n, s, t, u, v, m and f may each independently be an integer of 1 to 50, and R may be an alkyl group, an acetyl group, an alkoxy group or a carbonyl group. More specifically, n, s, t, u, v, m and f may each independently be an integer of 1 to 25, and R may be an alkyl group, an acetyl group or an alkoxy group.

In the embodiments of the present invention, the alicyclic epoxy compound may be used singly or in combination of two or more.

Meanwhile, in the embodiments of the present invention, the epoxy compound may be contained in an amount of 1 to 20% by weight based on the total weight of the solid content of the anisotropic conductive film.

Conductive particle

The conductive particles are not particularly limited, and conductive particles conventionally used in the art can be used. Non-limiting examples of the conductive particles usable in the present invention include metal particles including Au, Ag, Ni, Cu, solder and the like; carbon; Particles comprising a resin including polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol or the like and particles of the modified resin coated with a metal such as Au, Ag, Ni or the like; Insulating particles coated with insulating particles, and the like. The size of the conductive particles may be in the range of, for example, 1 to 20 mu m, specifically 1 to 10 mu m, depending on the pitch of the applied circuit.

The conductive particles may be included in an amount of 5 to 40% by weight based on the total weight of the solid content of the anisotropic conductive film, specifically 10 to 35% by weight, and more specifically 15 to 30% 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.

Other additives

In one embodiment, the anisotropic conductive film may further comprise a silane coupling agent in addition to the above components.

Examples of the silane coupling agent include polymerizable fluorinated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane and (meth) acryloxypropyltrimethoxysilane; Silicon compounds having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. ; And 3-chloropropyltrimethoxysilane, and the like, but are not limited thereto.

The silane coupling agent 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 anisotropic conductive film 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 the basic physical properties. The additive is not particularly limited, but may be included in an amount of 0.01 to 10% by weight based on the total solid weight of the anisotropic conductive film.

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.

Thermal differential scanning calorimeter ( DSC ) Phase start temperature and exothermic peak temperature

The anisotropic conductive film of the present invention may have a starting temperature of 70 to 90 ° C on a DSC and a maximum peak temperature of 90 to 100 ° C.

Onset temperature in DSC refers to the temperature at the point where the tangent meets the temperature axis by drawing a tangent to the graph where the heat starts to rise at the highest peak of the graph measured by the thermal differential scanning calorimeter Refers to the temperature at the time when the calorific value shows the highest peak in the graph.

As a non-limiting example of measuring the initiation temperature and the exothermic peak temperature on the DSC, the curable resin composition is heated at 10 ° C / min under a nitrogen gas atmosphere using a thermal differential scanning calorimeter (DSC, TA instruments, Q20) min at a temperature in the range of 30 캜 to 250 캜, and a method of measuring the initiation temperature and exothermic peak temperature of the thermal differential scanning calorimeter.

If the thermal differential scanning calorimetric phase start temperature and exothermic peak temperature are in the above ranges, they can be cured at a relatively low temperature of 150 ° C or less, for example, in the range of 130 to 150 ° C, and there is little difference between the initiation temperature and exothermic peak temperature, .

Method for producing an anisotropic conductive film

The anisotropic conductive film of the present invention may be formed into a single layer structure, but not limited thereto, and may be formed into a multilayer structure such as a double layer or a triple layer. For example, a composition for an anisotropic conductive film containing each composition disclosed in one example of the present invention is prepared, the composition is liquefied by dissolving it in an organic solvent such as toluene, stirred for a predetermined time within a speed range at which the conductive particles are not crushed, This is coated on the release film to a certain thickness, for example, 10 to 50 탆, and then dried for a predetermined time to volatilize toluene or the like to obtain a single layer of anisotropic conductive film. Alternatively, a composition containing conductive particles and a composition containing no conductive particles may be respectively formed, and a conductive film may be formed using a composition containing conductive particles in one release film, and conductive particles may be contained in the other release film A non-conductive film may be formed using a composition that does not contain the conductive film, and then the conductive film and the non-conductive film may be laminated using a lamination technique to produce an anisotropic conductive film having a double-layer structure.

On the other hand, another example of the present invention includes: a first connected member containing a first electrode; A second connected member containing a second electrode; And a cured film that is located between the first connected member and the second connected member and connects the first electrode and the second electrode, the cured film comprising: Is a film formed by curing an anisotropic conductive film.

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 (Integrated Circuit Chip), or a driver IC chip (Driver Integrated Circuit Chip) , Either one of the first connected member and the second connected member may be an IC chip or a driver IC chip and the other may be a glass substrate.

1, the electronic device 30 includes a first connected member 50 including a first electrode 70, a second connecting member 50 including a second electrode 80, And a cured film (10) positioned between the first connected member (50) and the second connected member (60). The cured film 10 connects the first electrode 70 and the second electrode 80 to each other. The cured film 10 is a film formed by curing an anisotropic conductive film comprising the conductive particles 3 described herein and in which the conductive particles 3 are sandwiched between the first electrode 70 and the second electrode 80, Respectively.

The electronic device 30 may be, but is not limited to, an electronic device including a display, and an electronic device including two kinds of connected members 50 and 60 connected by using an anisotropic conductive film Either of these is included in the present electronic device.

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. Those skilled in the art will abbreviate the matters which can be sufficiently technically derived.

Example

Preparation of anisotropic conductive film

Example 1

Composition of Anisotropic Conductive Film A composition for anisotropic conductive film was prepared by mixing each composition component in accordance with the target content, and dried anisotropically conductive film having a thickness of 18 μm was produced using the composition. The compositional target content of the anisotropic conductive film is based on the total solid weight of the film as follows:

40% by weight of biphenyl fluorene-type phenoxy resin (FX-293, manufacturer);

5% by weight of silsesquioxane compound containing oxetane group (SSQ-TX100, TOAGOSEI);

35% by weight of a phenol novolac oxetane compound (PNOX-1009, TOAGOSEI);

5 wt% quaternary ammonium compound (CXC-1821, King Industry); And

15% by weight of conductive particles (AUL-704F, average particle diameter 4 탆, SEKISUI, Japan).

Example 2

The silsesquioxane compound (SSQ-TX100, TOAGOSEI) containing oxetane groups in Example 1 was adjusted to 10 wt% based on the total solid weight of the film, and the phenol novolac oxetane compound (PNOX-1009 , Manufactured by TOAGOSEI CO., LTD.) Was changed to 30% by weight, a composition for anisotropic conductive films was prepared in the same manner as in Example 1, and an anisotropic conductive film was obtained using the composition.

Example 3

The silsesquioxane compound (SSQ-TX100, TOAGOSEI) containing oxetane groups in Example 1 was adjusted to 15 wt% based on the total solid weight of the film and the phenol novolak oxetane compound (PNOX-1009 , Manufactured by TOAGOSEI CO., LTD.) Was changed to be 25% by weight, a composition for anisotropic conductive films was prepared and the anisotropic conductive film was obtained.

Comparative Example 1

Same as Example 1 except that phenol novolac epoxy compound (PNOX-1009, TOAGOSEI) was changed to 35 wt% based on the total solid weight of the film in Example 1 instead of phenol novolac oxetane compound To prepare an anisotropic conductive film, and an anisotropic conductive film was obtained using the composition.

Comparative Example 2

Same as Example 1 except that the ether type oxetane compound (OXT-221, manufactured by TOAGOSEI) was changed to 35 wt% based on the total solid weight of the film in Example 1 instead of the phenol novolac oxetane compound To prepare an anisotropic conductive film, and an anisotropic conductive film was obtained using the composition.

Comparative Example 3

A composition for anisotropic conductive films was prepared in the same manner as in Example 3, except that the phenol novolac epoxy compound was changed to 25% by weight based on the total solid weight of the film in place of the phenol novolak oxetane compound And an anisotropic conductive film was obtained therefrom.

Comparative Example 4

In Example 1, the silsesquioxane compound containing a oxetane group and the phenol novolak oxetane compound were omitted, and an ether type oxetane compound (OXT-221, manufactured by TOAGOSEI) was added in an amount of 40 wt% %, The composition for anisotropic conductive films was prepared in the same manner as in Example 1, and an anisotropic conductive film was obtained using the composition.

The composition and content (% by weight) of the above Examples and Comparative Examples are shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Fluorene-based phenoxy 40 40 40 40 40 40 40 Curable compound Oxetane group-containing silsesquioxane 5 10 15 5 5 15 Phenol novolac oxetane 35 30 25 Phenol novolac epoxy 35 25 Oxetane compound 35 40 Quaternary ammonium compound 5 5 5 5 5 5 5 Conductive particle 15 15 15 15 15 15 15

Experimental Example  1: Initial Indentation

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 탆 ² and a thickness of 2000 Å and pressed at 1 MPa for 1 second at 70 캜 Thereafter, the release film was removed and an IC chip (Samsung LSI) having a bump area of 1200 탆 ² and a thickness of 1.5 mm was placed thereon. The IC chip was pressed at 130 캜 for 5 seconds under a pressure of 70 MPa, and indentations were visually observed .

Concretely, it was judged that the indentations exceeding 5 were good, and the indentations were judged to be poor.

Experimental Example  2: bubble  Area measurement

Each of the anisotropically conductive films produced in the above Examples and Comparative Examples was allowed to stand at room temperature (25 DEG C) for 1 hour. Thereafter, a glass substrate with an indium tin oxide circuit having a bump area of 1200 mu m ² and a thickness of 2000 ANGSTROM ), And pressed at 1 MPa for 1 second at 70 ° C. Thereafter, the release film was removed, and an IC chip (Samsung LSI) having a bump area of 1200 μm ² and a thickness of 1.5 mm was placed thereon. , And the bubbles in the pressed area were observed with an optical microscope to calculate the ratio of the bubble area to the pressed area.

When the ratio of the bubble area to the squeeze area exceeds 20%, it is determined to be defective.

Experimental Example  3: Particle Capture rate  Measure

The number of conductive particles per unit area (mm ² ) of the anisotropic conductive film produced in the Examples and Comparative Examples before compression 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 with a bump area of 1200 占 퐉 ² and a thickness of 2000 占 and pressed at 1 MPa for 1 second at 70 占 폚, An IC chip (manufactured by SAMSUNG LSI) having a bump area of 1200 탆 ² and a thickness of 1.5 mm was placed and pressed at 130 캜 for 5 seconds under a pressure of 70 MPa to measure the number of conductive particles per unit area (mm ² ) The particles were calculated using the particle automatic meter and the particle capture rate was calculated by the following equation (2).

[Formula 2]

(Mm ² ) number of conductive particles per unit area (mm ² ) of anisotropically conductive film before compression bonding (%) = (number of conductive particles per unit area (mm ² )

A particle capture rate of 20% or less was determined to be defective.

Experimental Example  4: Connection resistance measurement

A glass substrate having an indium tin oxide (ITO) circuit with a bump area of 1200 mu m ² and a thickness of 2000 ANGSTROM and an IC having a bump area of 1200 mu m ² and a thickness of 1.5 mm (manufacturer: Samsung LSI) And the anisotropic conductive films of Comparative Examples 1 to 4 were subjected to pressure bonding under the conditions of 70 DEG C, 1.0 MPa, and 1 second, respectively, under the conditions of 130 DEG C, 70 MPa, and 5 seconds, Five specimens were prepared.

For the connection resistance measurement, a 4 point probe was used. The resistance between the four points was measured using four probes connected to the resistance measuring instrument. The resistance measuring instrument is applied with 1 mA, and the resistance is calculated by the measured voltage and averaged.

The connection resistance of the manufactured specimen was measured, and this was referred to as an initial connection resistance (T ₀ ).

For the anisotropically conductive film left for 3 days and 7 days, the test piece was made in the same manner, and the connection resistance was measured. The resistance was measured as a 3-day left connection resistance (T ₁ ) and a 7-day left connection resistance (T ₂ ).

For each connection resistance, a value of 1? Or less was indicated by a numerical value, and more than that was judged to be defective.

Experimental Example  5: Anisotropic conductive film Thermal differential scanning calorimeter ( DSC ) Onset temperature and exothermic peak temperature measurement

The anisotropic conductive films of Examples 1 to 6 and Comparative Examples 1 to 4 thus prepared were subjected to heat treatment at a rate of -50 ° C / min at a rate of 10 ° C / min in a nitrogen gas atmosphere using a thermal differential scanning calorimeter (DSC, TA Instruments, Q20) To 250 占 폚, and the initiation temperature and exothermic peak temperature of the thermal differential scanning calorimeter were measured. The onset temperature of the thermal differential scanning calorimeter is the temperature at which the slope of the graph is first increased due to the heat generated during the measurement of the thermal differential scanning calorimeter and the peak value of the heat on the differential scanning calorimeter is the peak Is the temperature at the point of time.

Experimental Example  6: Anisotropic conductive film Thermal differential scanning calorimeter ( DSC ) Calculation of the rate of change in the calorific value

1 mg of each of the anisotropically conductive films of Examples 1 to 3 and Comparative Examples 1 to 4 prepared above was dispensed and measured at a rate of 10 ° C / min in a nitrogen gas atmosphere using DSC (thermal differential scanning calorimeter, TA instruments, Q20) (H ₀ ) and a calorific value (H ₁ ) after storage for 5 days at 25 ° C were measured, and the calorific value change rate was calculated according to the following formula (1).

[Formula 1]

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

Experimental Example  7: Modulus of elasticity  Measure

The prepared specimens of Examples 1 to 3 and Comparative Examples 1 to 4 were laminated by several layers using a lamination technique to form an anisotropic conductive film having a thickness of 100 탆 and cured using a hot press , And DSC, and the modulus of elasticity was measured while raising the temperature from -40 ° C to 200 ° C at a rate of 10 ° C / min using a TA Dynamic Mechanical Analyzer (DMA).

Of these elastic modulus values, the elastic modulus values at 30 占 폚 were confirmed.

Experimental Example  8: Glass transition temperature measurement

The prepared specimens of Examples 1 to 3 and Comparative Examples 1 to 4 were cured using a hot press and confirmed to have been sufficiently cured by DSC. Using DMA (Dynamic Mechanical Analyzer) / min and the Tg was measured while raising the temperature from -40 ° C to 200 ° C.

The results of Experimental Examples 1 to 8 are shown in Table 2 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Initial indentation after curing at 135 ℃ OK OK OK NG OK NG OK Bubble after curing at 135 ℃ OK OK OK NG OK NG OK (%) After 135 캜 curing 24 40 43 NG NG 43 44 Curing at 135 ℃ Initial
Connection resistance (T ₀ ) (Ω) 0.04 0.04 0.04 NG 0.04 NG 0.04 Leave for 3 days
Connection resistance (T ₁ ) (Ω) 0.05 0.05 0.05 NG NG NG NG 7 days left contact resistance
(T ₂ ) (Ω) 0.06 0.06 0.08 NG NG NG NG Heat generation start temperature (캜) 95 78 81 65 55 58 70 Exothermic peak temperature (℃) 105 85 94 86 79 90 85 Rate of change in calorific value (%) 5 8 8 25 27 21 27 Elastic modulus
(GPA) 3.3 3.1 3.2 2.7 2.5 2.2 2.5 Glass transition temperature (캜) 195 195 186 178 176 159 165

As can be seen from the above Table 2, Examples 1 to 3 of the present invention showed a very high elastic modulus and a small amount of change in calorific value, indicating excellent storage stability. Further, it was confirmed from Examples 1 to 3 that the particle capture rate increases as the content of the silsesquioxane compound containing an oxetane group increases. Particularly, when the content of the silsesquioxane compound containing oxetane group is 10% by weight or more, the particle capture rate exceeds 40%. In addition, it was found that the low-temperature fast-curing was possible because the heat generation starting temperature and the exothermic peak temperature on the DSC were low and the difference therebetween was relatively small. Also, after 7 days of storage, good connection resistance characteristics were maintained and storage stability was shown.

Claims (15)

The elastic modulus measured at 30 캜 after the film curing is 2.5 to 4 GPa,
Wherein the rate of change in calorific value on the DSC of the following formula (1) is 20% or less after being stored at 25 占 폚 for 5 days.
[Formula 1]
Heating rate change rate (%) = [(H ₀ -H ₁ ) / H ₀ ] × 100
In the above formula (1), H ₀ represents the calorific value on the DSC of the anisotropic conductive film measured immediately after the film is formed, H ₁ represents the heat parallax measured after storing the anisotropic conductive film at 25 ° C for 5 days And shows the calorific value on the scanning calorimeter. The method according to claim 1,
The anisotropic conductive film having a connection resistance after curing at 130 占 폚 after being allowed to stand within 3 to 7 days from the production of the film. The method according to claim 1,
Wherein an anisotropic conductive film having a glass transition temperature (Tg) after film curing of 150 deg. C to 250 deg. The method according to claim 1,
Silsesquioxane compounds containing an oxetane group; And
An anisotropic conductive film comprising a phenol novolac oxetane compound. The method of claim 4,
Based on the total solid weight of the anisotropic conductive film,
1 to 20% by weight of a silsesquioxane compound containing an oxetane group; And
And 10 to 40% by weight of a phenol novolak oxetane compound. The method of claim 4,
Binder resin;
Potential cationic curing agents; And
An anisotropic conductive film further comprising conductive particles. The method of claim 6,
Wherein the binder resin is a fluorene-based phenoxy resin. The method of claim 6,
Wherein the latent cationic curing agent comprises an amine-based cationic curing agent. The method of claim 8,
Wherein the amine cationic curing agent comprises a quaternary ammonium compound. The method of claim 4,
An anisotropic conductive film further comprising an epoxy compound. The method of claim 10,
The epoxy compound may be an anisotropic conductive film containing an alicyclic epoxy Binder resin;
Silsesquioxane compounds containing an oxetane group;
Phenol novolac oxetane compounds;
Potential cationic curing agents; And
An anisotropic conductive film comprising conductive particles. The method of claim 12,
Based on the total solid weight of the anisotropic conductive film,
The binder resin may contain 30 to 60 wt%
The oxetane group-containing silsesquioxane compound is contained in an amount of 1 to 20% by weight,
The phenol novolac oxetane compound is contained in an amount of 10 to 40% by weight,
The latent cation curing agent may be used in an amount of 1 to 10% by weight,
Wherein the conductive particles are contained in an amount of 5 to 40% by weight. 14. The method of claim 13,
Wherein the oxetane group-containing silsesquioxane compound is contained in an amount of 10 to 20 wt%. A first connected member containing a first electrode;
A second connected member containing a second electrode; And
A cured film formed by curing the anisotropic conductive film of any one of claims 1 to 14, which is located between the first to-be-connected members and the second to-be-connected members and connects the first electrode and the second electrode ≪ / RTI >

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