TWI623569B - An anisotropic conductive film thereof and a display device using the same - Google Patents

Abstract

The invention discloses an anisotropic conductive film and a display device including the same. The anisotropic conductive film is formed of a composition for an anisotropic conductive film (containing 1 to 14% by weight of an oxetane-containing sesquioxane compound in terms of solid content), And has a storage modulus of 2.5 GPa to 4 Gpa measured at 30 ° C after the film is cured, and 20% measured by differential scanning calorimetry (DSC) after 5 days at 25 ° C or Less than 20% heat change rate.

Description

Anisotropic conductive film and display device using the same

The present invention relates to an anisotropic conductive film and a display device using the same.

In general, an anisotropic conductive film (ACF) refers to a film-type adhesive prepared by dispersing conductive particles in a resin such as an epoxy resin, and is formed of an anisotropic adhesive polymer film The polymer film exhibits conductive properties in a thickness direction of the film and exhibits insulating properties in a surface direction thereof. When the anisotropic conductive film placed between the circuit boards to be connected is subjected to heating / compression under specific conditions, the circuit terminals of the circuit board are electrically connected to each other via conductive particles, and the insulating adhesive resin fills the space between adjacent electrodes. In order to isolate conductive particles from each other, thereby providing high insulation performance.

Recently, due to the reduction in the thickness of display panels, thinner glass substrates have been required. However, when the driver IC is mounted on a glass substrate via an anisotropic conductive film, the glass substrate is easily warped during heating and compression. The warpage of the glass substrate causes light leakage, which causes the display device to malfunction. The thinner the glass substrate, the more severe the warpage, and the higher the failure rate.

In order to prevent warping of the glass substrate, an anisotropic conductive film that can be rapidly cured at a low temperature of 150 ° C. or less at 5 seconds or less is required. Although curable compounds and curing agents having high reactivity can be used to achieve this need, the use of curing compounds and curing agents results in a decrease in storage stability due to their high reactivity and requires an excessive amount of stabilizer. Japanese Patent Publication No. 2012-171980A discloses an anisotropic conductive film using an alicyclic epoxy compound and an oxetane compound as a curable compound and a fluorene-type latent cationic catalyst having a specific structure. However, this anisotropic conductive film has a problem of low storage stability due to high reactivity among alicyclic epoxy compounds, oxetane compounds, and fluorene-based cationic catalysts.

On the other hand, in order to achieve high resolution of a display device, a driver IC chip having terminals arranged at a fine pitch is connected to a glass substrate. Therefore, the anisotropic conductive film is required to capture a sufficient amount of conductive particles in order to ensure sufficient conductivity in the fine connection region while stably ensuring insulation between adjacent terminals. In order to improve the particle capture rate, it has been studied to suppress fluid flow by increasing the density of conductive particles or using an excessive amount of inorganic particles. However, in this situation, there is a problem of achieving rapid curing at a low temperature. Therefore, the present invention is directed to provide an anisotropic conductive film which has an improved particle capture rate; can be rapidly cured at a temperature of 150 ° C or less; and allows connection at low temperatures while ensuring storage stability and reliability.

The object of the present invention is to provide a method that allows rapid curing at low temperatures; Particle capture rate; and an anisotropic conductive film exhibiting improved storage stability and reliability.

Another object of the present invention is to provide a display device using the anisotropic conductive film.

One aspect of the present invention relates to an anisotropic conductive film. In one embodiment, the anisotropic conductive film is composed of a composition for an anisotropic conductive film (including 1% by weight (wt%) to 14% by weight of oxetanyl group in terms of solid content) Group of silsesquioxane compounds), and has a storage modulus of 2.5 GPa to 4 Gpa measured at 30 ° C after the film is cured and determined by differential scanning calorimetry after 5 days of retention at 25 ° C ( differential scanning ealorimetry (DSC) and a thermal change rate of 20% or less as measured by Equation 1.

[Equation 1] Heat change rate (%) = [| (H ₀ -H ₁ ) | / H ₀ ] × 100

Wherein H ₀ is the DSC heat of the anisotropic conductive film as measured immediately after the production of the anisotropic conductive film, and H ₁ is the same as measured after remaining at 25 ° C. for 5 days. DSC heat of the anisotropic conductive film.

In another embodiment, the anisotropic conductive film includes a sesquioxane compound containing an oxetanyl group, a binder resin, an epoxy resin, conductive particles, and a curing agent, and The temperature difference between the peak exothermic temperature measured by scanning calorimetry (DSC) and the initial temperature of exotherm is 10 ℃ or less, and 10,000 Pa at a temperature of 80 ℃ to 100 ℃. scc to 200,000Pa. Minimum melt viscosity in sec.

Another aspect of the present invention relates to a display device, including: A first connection member of an electrode; a second connection member including a second electrode; and the above-mentioned anisotropic conductive film disposed between the first connection member and the second connection member and connecting the first electrode and the second electrode.

Embodiments of the present invention provide an anisotropic conductive film that can improve the capture rate of conductive particles by adjusting the fluidity; allow rapid curing at low temperatures; and exhibit good storage stability and reliability.

According to an embodiment of the present invention, the anisotropic conductive film has a high storage modulus of 2.5 GPa to 4 GPa to provide a high particle capture rate and a low DSC heat change rate to provide good storage stability.

3‧‧‧ conductive particles

10‧‧‧ Anisotropic conductive film

30‧‧‧ display device

50‧‧‧First connecting part

60‧‧‧Second connection part

70‧‧‧first electrode

80‧‧‧Second electrode

FIG. 1 is a cross-sectional view of a display device 30 according to an embodiment of the present invention.

FIG. 2 is a differential scanning calorimetry (DSC) chart of the anisotropic conductive films of Examples 1 to 3. FIG.

Hereinafter, embodiments of the present invention will be described in detail. Detailed descriptions obvious to those skilled in the art will be omitted in this article.

Unless otherwise defined, the term "substituted" as used herein means that a hydrogen atom in a compound is substituted with a substituent selected from the group consisting of a halogen atom (F, Br, Cl, and I), a halogenated alkyl (halogenated alkyl group, hydroxyl group, alkoxy group, nitro group, cyano group, amino group, azido group, formamyl group (amidino group), hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, a carboxyl group (carboxyl group) or a salt thereof, a sulfo acyl (sulfonyl group) or a salt thereof, a phosphoric acid group (phosphate group) or a salt thereof, C ₁ to C ₂₀ alkyl _{(C 1 to C 20 alkyl group} ), C 6 to C ₃₀ aryl group _{(C 6 to C 30 aryl group} ), C 7 to C ₃₀ aralkyl group _{(C 7 to C 30 arylalkyl group} ), C 1 to C ₂₀ alkoxy _{(C 1 to C 20 alkoxy group} ), C ₁ to C ₂₀ heteroalkyl _{(C 1 to C 20 heteroalkyl group} ), C 3 to C ₂₀ heteroarylalkyl group _{(C 3 to C 20 heteroarylalkyl group} ), C 3 to C ₂₀ cycloalkyl (C ₃ to C ₂₀ cycloalkyl group) , (Meth) acrylate group ((meth) acrylate group), C 2 to C ₂₀ heterocycloalkyl _{(C 2 to C 20 heterocycloalkyl group} ) , and combinations thereof.

As used herein, alkyl means a fully saturated or partially unsaturated C ₁ to C ₂₀ straight or branched chain hydrocarbon group, and cycloalkyl means a fully saturated or partially unsaturated C ₃ to C ₂₀ cycloalkyl group. Heteroalkyl means fully saturated or partially unsaturated C ₁ to C ₂₀ hydrocarbon groups, including heteroatoms instead of carbon or hydrogen atoms in its backbone; and heterocycloalkyl means fully saturated or partially unsaturated C ₂ to C _{A 20-} ring hydrocarbyl group including heteroatoms instead of carbon or hydrogen atoms in its ring.

The anisotropic conductive film according to an embodiment of the present invention is formed of a composition for an anisotropic conductive film, the composition containing 1 to 14% by weight of oxetane in terms of solid content Group of silsesquioxane compounds, and the anisotropic conductive film has a storage modulus of 2.5 GPa to 4 GPa measured at 30 ° C after the film is cured, and after being left at 25 ° C for 5 days by 20% or less heat change rate measured by differential scanning calorimetry (DSC) and calculated by Equation 1: [Equation 1] Heat change rate (%) = [| (H ₀ -H ₁ ) | / H ₀ ] × 100

Where H ₀ is the DSC heat of the anisotropic conductive film measured immediately after the production of the anisotropic conductive film, and H _{1 is the same} as that measured after remaining at 25 ° C. for 5 days. The DSC heat of the anisotropic conductive film is described.

Storage modulus

The anisotropic conductive film according to the embodiment of the present invention may have a storage modulus of 2.5 GPa to 4 GPa, specifically 3.0 GPa to 4.0 GPa, measured at 30 ° C.

The storage modulus can be measured by any typical method known in the art. For example, by laminating multiple anisotropic conductive films to form a 100 μm thick anisotropic conductive film, and then curing 90% or more of the laminated anisotropic conductive film on a hot press, Prepare specimens with storage modulus. Next, the storage modulus was measured using a Dynamic Mechanical Analyzer (DMA) (TA Instruments Corporation) when the specimen was heated from -40 ° C to 200 ° C at a heating rate of 10 ° C / min.

Within the above range of the storage modulus at 30 ° C, the anisotropic conductive film exhibits a good particle capture rate.

DSC heat change rate

An anisotropic conductive film according to an embodiment of the present invention may have 20% or less of 20% or less measured by differential scanning calorimetry (DSC) after remaining at 25 ° C for 5 days and calculated by Equation 1. , Exactly 15% or less than 15%, more precisely 10% or less than the rate of change in calories.

[Equation 1] Heat change rate (%) = [| (H ₀ -H ₁ ) | / H ₀ ] × 100

Wherein H ₀ is the DSC heat of the anisotropic conductive film measured immediately after the production of the anisotropic conductive film, and H ₁ is the measured heat quantity after 5 days at 25 ° C. The DSC heat of the anisotropic conductive film is described.

The DSC (Differential Scanning Calorimetry) heat of the anisotropic conductive film can be measured by any typical method used in this technology. For example, it can be based on when a specimen is heated in a temperature range of -50 ° C to 250 ° C using a DSC (Differential Scanning Calorimeter) (Q20, TA Instruments) under a nitrogen atmosphere at a heating rate of 10 ° C / min , The measured calories of the anisotropic conductive film depend on the temperature to calculate the DSC heat of the anisotropic conductive film. In the DSC chart, heat is defined as the area surrounded by the reference curve by the exothermic curve and the baseline.

Within the above range of the heat change rate, the anisotropic conductive film has good storage stability.

Silsesquioxane compounds containing oxetane groups

The silsesquioxane compound containing an oxetanyl group is a compound in which R of the silsesquioxane compound represented by R-SiO _3/2 is partially substituted with an oxetanyl group. Specifically, the sesquioxane compound containing an oxetanyl group may include a structure represented by Chemical Formula 2. In addition, the sesquioxane compound containing an oxetanyl group may include a repeating unit of a structure represented by Chemical Formula 2.

In Chemical Formula 2, R ₁₁ is an oxetanyl group and R ₁₂ is hydrogen or a substituted or unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, heteroalkyl, Heterocycloalkyl or alkenyl, and x and y can satisfy 0 <x in terms of mole ratio 1.0, 0 y <1.0 and x + y = 1. In one embodiment, x may be at 0.5 x Within 1.0 range. Within this range of x, the silsesquioxane compound contains a sufficient amount of oxetanyl group and the ring-opening reaction of the oxetanyl group can be sufficiently performed, thereby achieving rapid curing at a low temperature.

The sesquioxane compound containing an oxetane group may include a polyhedral oligomeric silsesquioxane (POS) structure represented by Chemical Formula 3 to Chemical Formula 6, a random structure represented by Chemical Formula 7, A ladder structure represented by 8 or a partial cage structure represented by Chemical Formula 9.

In Chemical Formulas 3 to 9, R is each independently an oxetanyl group, hydrogen, or a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkaryl group, and a heteroalkane And at least one of R is an oxetanyl group.

Specifically, the silsesquioxane compound containing an oxetane group may include a polyhedral oligomeric silsesquioxane (POS) structure represented by Chemical Formula 3 to Chemical Formula 6.

The sesquioxane compound containing an oxetanyl group is present in an amount of 1 to 14% by weight, specifically, 5 to 10% by weight based on the total amount of the composition. Within this range, the anisotropic conductive film may have suitable fluidity to provide good indentation characteristics while improving particle capture rate and connection reliability.

In one embodiment, the composition for an anisotropic conductive film may further include a binder resin, an epoxy resin, conductive particles, and a curing agent other than a sesquioxane compound containing an oxetane group. .

Examples of the binder resin may include polyimide resin, polyimide resin, phenoxy resin, polymethacrylate resin, polypropylene resin, polyurethane resin, polyester resin, polyesteramine Formate resin, polyvinyl butyral resin, styrene-butadiene-styrene (SBS) resin and its epoxy compound, styrene-ethylene / butene-styrene -ethylene / butylene-styrene (SEBS) resin and its modified compounds, acrylonitrile butadiene rubber (NBR) and its hydrogenated compounds, and combinations thereof. In particular, the binder resin may be a phenoxy resin, more specifically a phenoxy resin. As the fluorene phenoxy resin, any phenoxy resin containing a fluorene structure can be used (but not limited to).

The binder resin may be present in an amount of 15% to 70% by weight based on the total amount of the composition in terms of solid content. In particular, the binder resin may be present in an amount of 18 to 60% by weight, more specifically 20 to 50% by weight.

Examples of the epoxy resin may 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, and bisphenol A type epoxy resin. Phenol E type epoxy resin and bisphenol S type epoxy resin; aromatic epoxy resins such as polyglycidyl ether epoxy resin, polyglycidyl ester epoxy resin, and Naphthalene epoxy resin; cycloaliphatic epoxy resin; novolac type epoxy resin, such as cresol novolac epoxy resin and phenol novolac type epoxy resin; glycidylamine Epoxy resin; glycidyl ester epoxy resin; biphenyl diglycidyl ether epoxy resin; and hydrogenated epoxy resin. These epoxy resins can be used alone or in combination. In particular, an alicyclic epoxy resin can be used. by Since the alicyclic epoxy resin has an epoxy resin existing near the alicyclic ring, the alicyclic epoxy resin allows a rapid ring-opening reaction, and therefore exhibits better curing reactivity than other epoxy resins. As the alicyclic epoxy resin, any alicyclic epoxy resin including, but not limited to, an epoxy structure directly coupled to the alicyclic ring or coupled thereto via another bond site can be used. In one embodiment, an alicyclic epoxy resin represented by Chemical Formula 10 to Chemical Formula 13 may be used.

In Chemical Formula 11 to Chemical Formula 13, n, s, t, u, v, m, and f Each may be an integer from 1 to 50, and R ′ may be an alkyl group, an ethenyl 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 ethenyl group, or an alkoxy group.

In terms of solid content, the epoxy resin may be present in an amount of 15 to 50% by weight, specifically 20 to 40% by weight, based on the total amount of the composition. Within this range, the anisotropic conductive film may have good properties in terms of adhesion, external appearance, and the like, and may exhibit good stability after a reliability test.

As the curing agent, any curing agent capable of curing the epoxy resin can be used (but not limited to). Examples of the curing agent may include acid anhydride, amine, imidazole, isocyanate, amidine, hydrazine, phenol, and cationic curing agent. These curing agents may be used alone or in combination.

In particular, the curing agent may be a cationic curing agent or an amine curing agent. In terms of rapid curing reactions, cationic curing agents are advantageous; and in terms of stability, amine curing agents are advantageous and therefore provide the advantage of using less stabilizers. In one embodiment, the curing agent may be a rhenium curing agent or an amine curing agent, such as a rhenium curing agent represented by Chemical Formula 14, Chemical Formula 15, or Chemical Formula 16 or a fourth ammonium curing agent represented by Chemical Formula 17.

In Chemical Formula 14, R ₁₃ is one selected from the group consisting of hydrogen, C ₁ to C ₆ alkyl, C ₆ to C ₁₄ aryl, -C ₁ to C ₆ alkyl-C ₆ to C ₁₄ aryl, -C (= O) R ₃₁ , -C (= O) OR ₃₂ , and -C (= O) NHR ₃₃ (R ₃₁ , R ₃₂ and R ₃₃ are each independently selected from C ₁ to One of C ₆ alkyl and C ₆ to C ₁₄ aryl); R ₁₄ to R ₁₇ are each independently hydrogen or C ₁ to C ₆ alkyl; R ₁₈ and R ₁₉ are each independently selected from One of the group consisting of: C ₁ to C ₆ alkyl, nitrobenzyl, dinitrobenzyl, trinitrobenzyl, substituted or unsubstituted by C ₁ to C ₆ alkyl Benzyl and naphthylmethyl; and Y ₁ ^- are AsF ₆ , SbF ₆ , SbCl ₆ , (C ₆ F ₅ ) ₄ B, SbF ₅ (OH), PF ₆ or BF ₄ .

In Chemical Formula 15, R ₂₀ is hydrogen; R ₂₁ is C ₁ to C ₆ alkyl; R ₂₂ is -OH, -OC (= O) R ₃₄ or -OC (= O) OR ₃₅ (R ₃₄ and R ₃₅ Each is C ₁ to C ₆ alkyl); and Y ₂ ^- is AsF ₆ , SbF ₆ , SbCl ₆ , (C ₆ F ₅ ) ₄ B, SbF ₅ (OH), PF ₆ or BF ₄ .

In Chemical Formula 16, R ₂₃ and R ₂₄ are each independently one selected from the group consisting of C ₁ to C ₂₀ alkyl, C ₃ to C ₁₂ alkenyl, C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkaryl, C ₇ to C ₂₀ alkaryl, C ₁ to C ₂₀ alkanol and C ₅ to C ₂₀ cycloalkyl; Ar ₁ is substituted or unsubstituted C ₆ to C ₂₀ aryl; Ar ₂ is substituted or unsubstituted C ₆ to C ₂₀ arylene; and Y ₃ ^- is a monovalent anion selected from the group consisting of BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , SbCl ₆ , (C ₆ F ₅ ) ₄ B, SbF ₅ (OH), HSO ₄ , p-CH ₃ C ₆ H ₄ SO ₃ , HCO ₃ , H ₂ PO ₄ , CH ₃ COO, and halogen anions. Here, the halogen anion means a monovalent monoatomic anion of a halogen atom.

In Chemical Formula 17, R ₂₆ , R ₂₇ , R _28, and R ₂₉ are each independently one of the following: a substituted or unsubstituted C ₁ to C ₆ alkyl group or a C ₆ to C ₂₀ aryl group ; and M ^- is the following person in 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 Chemical Formula 17, R ₂₆ , R ₂₇ , R _28, and R ₂₉ are each independently one of the following: methyl, ethyl, propyl, isopropyl, butyl, isobutyl Group, s-butyl, third butyl, pentyl, n-pentyl, third pentyl, isopentyl, hexyl, cyclohexyl, phenyl, anthracenyl, and phenanthryl.

Certain words, in Chemical Formula 17, M ^- can be SbF ₆ ^- and _{B (C 6 F 5) 4} - at least one. More precisely, M ⁻ may be B (C ₆ F ₅ ) ₄ ⁻ , which does not cause environmental problems.

In terms of solid content, the curing agent may be present in an amount of 1 to 10% by weight, specifically 1 to 5% by weight, based on the total weight of the anisotropic conductive film. Within this range, the curing agent can ensure a sufficient reaction for curing via an appropriate molecular weight, and can ensure good properties in terms of bonding strength, reliability, and the like after bonding.

The conductive particles are not particularly limited and may be selected from typical conductive particles used in the technology. Examples of the conductive particles may include: metal particles including Au, Ag, Ni, Cu, and solder; carbon particles; by coating polymer resin particles such as polyethylene with a metal (including Au, Ag, Ni, and the like) , Polypropylene, polyester, polystyrene Particles obtained by ethylene, polyvinyl alcohol, and modified resins thereof; and insulating particles obtained by subjecting the surface of the particles obtained by coating a polymer resin particle with a metal to an insulating treatment. Depending on the circuit pitch, the conductive particles may have a particle size of, for example, 1 μm to 20 μm, specifically 1 μm to 10 μm.

In terms of solid content, the conductive particles may be present in an amount of 1% to 30% by weight, specifically 10% to 25% by weight, and more specifically 15% to 20% by weight based on the total amount of the composition. Within this range, the conductive particles can be easily compressed between the terminals to ensure stable connection reliability, while reducing the connection resistance through improved conductivity.

In one embodiment, the anisotropic conductive film may further include a compound represented by Chemical Formula 1 and a curing agent.

In Chemical Formula 1, R ₁ is one selected from the group consisting of hydrogen, C ₁ to C ₆ alkyl, C ₆ to C ₁₄ aryl, -C ₁ to C ₆ alkyl-C ₆ to C ₁₄ aryl, -C (= O) R ₈ , -C (= O) OR ₉ and -C (= O) NHR ₁₀ (R ₈ , R ₉ and R ₁₀ are each independently selected from C ₁ to C ₆ alkyl and one of C ₆ to C ₁₄ aryl); R ₂ to R ₅ are each independently hydrogen or C ₁ to C ₆ alkyl; R ₆ and R ₇ are each independently C ₁ to C ₆ alkyl Group, nitrobenzyl, dinitrobenzyl, trinitrobenzyl, benzyl substituted or unsubstituted with C ₁ to C ₆ alkyl, and naphthylmethyl; and X ₁ ^- is Alkyl sulfate.

Specifically, in Chemical Formula 1, R ₁ may be hydrogen or C ₁ to C ₄ alkyl or ethenyl; R ₂ to R ₅ may each independently be hydrogen or C ₁ to C ₄ alkyl; and R ₆ And R ₇ may be methyl or benzyl. More precisely, R ₁ to R ₅ are each independently hydrogen and R ₆ and R ₇ may be methyl. X ₁ ^- may be methyl sulfuric acid.

The compound of Chemical Formula 1 is used to improve the storage stability of a composition for an anisotropic conductive film, and includes a silsesquioxane compound containing an oxetanyl group. Specifically, the compound of Chemical Formula 1 suppresses curing at room temperature by capturing cations generated by the curing agent, thereby improving the storage stability of the composition for an anisotropic conductive film. In addition, the anisotropic conductive film containing the compound of Chemical Formula 1 can be attributed to the small difference between its DSC exothermic peak temperature and the DSC exothermic onset temperature to achieve rapid curing at low temperatures, thereby improving the anisotropic conductive film. Reliability.

The compound of Chemical Formula 1 may be present in an amount of 0.001 to 10% by weight based on the total amount of the composition in terms of solid content. In particular, the compound of Chemical Formula 1 may be present in an amount of 0.01 to 5% by weight, more specifically 0.01 to 1% by weight. Within this range, the compound of Chemical Formula 1 can improve the storage stability of the anisotropic conductive film without interrupting the rapid curing of the anisotropic conductive film at a low temperature.

The composition for an anisotropic conductive film may further include a phenol novolak oxetane compound. The phenol novolak oxetane compound can be represented by Chemical Formula 18.

Wherein R ₃₀ is a hydrogen atom, C ₁ to C ₆ alkyl (such as methyl, ethyl, propyl, and butyl), C ₁ to C ₆ fluoroalkyl, or aryl, and k is an integer from 0 to 10.

Phenolic novolak oxetane compounds have a reaction delay effect to interrupt the reaction at low temperatures without significantly reducing the reactivity at the curing temperature. Therefore, the phenol novolak oxetane compound is used as the curable compound together with the oxetane group-containing silsesquioxane compound, so that the anisotropic conductive film can have the effect through the silsesquioxane compound. Improved particle capture and improved storage stability, while allowing rapid curing at low temperatures. In addition, the anisotropic conductive film containing these compounds has a high glass transition temperature under high temperature / high humidity conditions after curing, and thus has a low connection resistance increase rate.

In terms of solids content, the phenol novolak oxetane compound may be present in an amount of 5 to 40% by weight, specifically 10 to 35% by weight, based on the total weight of the anisotropic conductive film.

In one embodiment, the composition for an anisotropic conductive film may further include a silane coupling agent.

The silane coupling agent may include at least one selected from the group consisting of, for example, a polymerizable fluorine-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane And (meth) acryloxypropyltrimethoxysilane; (meth) acryloxypropyltrimethoxysilane; epoxy-containing silicon compounds such as 3-glycidoxypropyltrimethoxysilane, 3 -3-glycidoxypropylmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane (2- (3,4-epoxycyclohexyl)- ethyltrimethoxysilane); silicon compounds containing amine groups, such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (N -(2-aminoethyl) -3-aminopropyltrimethoxysilane) and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane); And 3-chloropropyltrimethoxysilane, but not limited thereto.

In terms of solids content, the silane coupling agent may be present in an amount of 0.5% to 10% by weight based on the total amount of the composition.

The anisotropic conductive film may further include an inorganic filler.

The inorganic filler can prevent electric short circuit and improve connection properties by improving the dispersibility of the conductive particles, and can improve the film formability.

The inorganic filler may include, without limitation, any suitable inorganic filler known in the art. Examples of the inorganic filler may include aluminum oxide, silicon dioxide, titanium dioxide, zirconia, magnesium oxide, cerium oxide, zinc oxide, iron oxide, silicon nitride, titanium nitride, boron trioxide, calcium carbonate, aluminum sulfate , Aluminum hydroxide, calcium titanate, talc, calcium silicate, and magnesium silicate, but not limited thereto. In particular, the inorganic filler may be alumina, silicon dioxide, calcium carbonate, or aluminum hydroxide. In one embodiment, the inorganic filler may be alumina or silicon dioxide.

The inorganic filler may be surface-treated with a compound such as phenylamino, phenyl, methacryl, vinyl, and epoxy to improve dispersibility in the anisotropic conductive film.

The method of surface-treating an inorganic filler is not specifically limited. By way of example, a dry surface treatment can be performed using a Henschel mixer The surface treatment agent is directly mixed with the inorganic filler, followed by heat treatment as necessary. In addition, a surface treatment agent diluted with a suitable solvent can be used.

The inorganic filler may be present in an amount of 5 to 40% by weight, specifically 5 to 30% by weight, and more specifically 15 to 30% by weight based on the total weight of the anisotropic conductive film. Within this range, the inorganic filler can effectively disperse the conductive particles and can appropriately adjust the fluidity of the anisotropic conductive film. In addition, the inorganic filler can increase the post-cure storage modulus of the anisotropic conductive film measured at 30 ° C, thereby improving the particle capture rate.

In one embodiment, the inorganic filler may have a particle diameter of 1 nm to 1,000 nm, and two or more inorganic particles having different particle diameters may be used. The two inorganic fillers may include a first inorganic filler having a particle diameter of about 1 nm to about 40 nm and a second inorganic filler having a particle diameter of about 50 nm to about 1,000 nm.

In another embodiment, the composition for an anisotropic conductive film may further include additives such as a polymerization inhibitor, an antioxidant, and a heat stabilizer to provide additional properties without affecting its basic properties. The additive may be present in an amount of about 0.01% by weight to about 10% by weight based on the total weight of the composition for the anisotropic conductive film in terms of solid content, but is not limited thereto.

Examples of the polymerization inhibitor may include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, phenothiazine, and mixtures thereof. The antioxidant may be a phenol or hydroxycinnamate antioxidant. For example, the antioxidant may include tetrakis [methylene (3,5-di-t-butyl-4) methane (3,5-di-third-butyl-4-hydroxycinnamate)] methane -hydroxycinnamate)) methane), 3,5-bis (1,1-dimethylethyl) -4-hydroxyphenylpropanoic acid thiodi-2,1-ethanediyl ester (3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanoic acid thiodi-2,1-ethanediyl ester), and similar Like it.

The anisotropic conductive film according to this embodiment can be manufactured without using special equipment or facilities. For example, the composition for an anisotropic conductive film containing the components as explained above is dissolved in an organic solvent such as toluene, and then stirred at a stirring time that does not cause the conductive particles to be broken for a certain period of time An anisotropic conductive film is obtained by applying the obtained material to a release film to a thickness of, for example, 10 μm to 50 μm, followed by drying for a period of time to volatilize toluene and the like.

The anisotropic conductive film may have a post-cured glass transition temperature (Tg) of 150 ° C to 250 ° C, specifically 160 ° C to 200 ° C. Within this range of the glass transition temperature, the anisotropic conductive film may have improved particle capture rate and indentation characteristics. The glass transition temperature can be measured by a typical method. For example, after the anisotropic conductive film is cured on a hot press and it is determined that the anisotropic conductive film is sufficiently cured, a Dynamic Mechanical Analyzer (DMA) (TA Instruments Corporation) at 10 ° C / min is used. The glass transition temperature was measured when the anisotropic conductive film was heated from -40 ° C to 200 ° C at a heating rate.

In another embodiment, the anisotropic conductive film includes a sesquioxane compound containing an oxetanyl group, a binder resin, an epoxy resin, conductive particles, and a curing agent, and has a DSC exothermic peak temperature and a DSC. The difference between 10 ℃ or less between the exothermic onset temperature and 10,000Pa. sec to 200,000Pa. Minimum melt viscosity at 80 ° C to 100 ° C in sec.

In this embodiment, the sesquioxane compound containing an oxetane group, a binder resin, an epoxy resin, conductive particles, and a curing agent may be the same as those described in the above embodiments.

For the anisotropic conductive film according to this embodiment, the difference between the DSC exothermic peak temperature and the DSC exothermic onset temperature may be 10 ° C or less, or more specifically 9 ° C or less. Within this range, the anisotropic conductive film can achieve rapid curing at low temperatures and has improved reliability.

The DSC exothermic peak temperature and DSC exothermic onset temperature can be measured by the following exemplary methods, but are not limited thereto. In this method, an anisotropic conductive film is heated at a rate of 10 ° C / min in a temperature range of -50 ° C to 250 ° C under a nitrogen atmosphere, followed by using a differential scanning calorimeter (DSC) (Q20, TA instrument The company) measured the peak exothermic temperature and the initial exothermic temperature to obtain a DSC chart. On the DSC chart, the DSC exothermic start temperature is defined as the temperature at the point where the extension line between the heat generation start point and the heat generation end point intersects with the tangent line from the peak to the point where the slope of the DSC chart begins to increase , And the DSC exothermic peak temperature is defined as the temperature at the highest peak of heat.

The anisotropic conductive film may have 10,000 Pa as measured using ARES at a temperature of 80 ° C to 100 ° C. s to 200,000Pa. s, exactly 90,000Pa. s to 150,000Pa. The minimum melt viscosity of s. Within this range, the anisotropic conductive film can exhibit suitable fluidity, thereby improving the capture rate of conductive particles.

The minimum melt viscosity of the anisotropic conductive film can be measured by the following exemplary methods, but is not limited thereto. In this method, an ARES G2 rheometer (TA instrument) is used under conditions of a sample thickness of 150 μm, a heating rate of 10 ° C / min, a stress of 5%, a frequency of 10 radians per second, and a temperature range of 80 ° C to 100 ° C. The company) measured the minimum melt viscosity of an anisotropic conductive film.

The anisotropic conductive film may further include a compound represented by Chemical Formula 1. The compound of Chemical Formula 1 is the same as in the above examples.

In Chemical Formula 1, R ₁ is one selected from the group consisting of hydrogen, C ₁ to C ₆ alkyl, C ₆ to C ₁₄ aryl, -C ₁ to C ₆ alkyl-C ₆ to C ₁₄ aryl, -C (= O) R ₈ , -C (= O) OR ₉ and -C (= O) NHR ₁₀ (R ₈ , R ₉ and R ₁₀ are each independently selected from C ₁ to C ₆ alkyl and one of C ₆ to C ₁₄ aryl); R ₂ to R ₅ are each independently hydrogen or C ₁ to C ₆ alkyl; R ₆ and R ₇ are each independently C ₁ to C ₆ alkyl Group, nitrobenzyl, dinitrobenzyl, trinitrobenzyl, benzyl substituted or unsubstituted with C ₁ to C ₆ alkyl, and naphthylmethyl; and X ₁ ^- is Alkyl sulfate.

The anisotropic conductive film may have particle capture of 30% to 70% measured after 4 seconds to 7 seconds of main compression at a temperature of 100 ° C to 150 ° C at a pressure of 50 MPa to 90 MPa and calculated by Equation 2. rate.

[Equation 2] the particle capture rate (%) = (the number of conductive particles per unit area (mm ²⁾ in the connection region after the main compression anisotropic conductive film / before compression per unit area (mm ²⁾ of Number of conductive particles) × 100

In particular, the anisotropic conductive film may have a particle capture rate of 35% to 60%. Within this range of particle capture rate, the fluidity of the conductive layer can be effectively suppressed, so that the conductive particles can be sufficiently placed on the terminal to improve the current-carrying properties and reduce the outflow of the conductive particles, thereby reducing the terminal Short circuit.

The particle capture rate can be measured by the following exemplary methods, but is not limited thereto. In this method, first, the number of conductive particles per unit area (mm ² ) of the anisotropic conductive film before compression is calculated using an automatic particle counter. Next, an anisotropic conductive film was placed on a glass substrate including an ITO circuit having a bump area of 1,200 μm ² and a thickness of 2,000 Å, and subjected to preliminary compression at 70 ° C. for 1 second at 1 MPa. Next, after the release film was removed, an IC wafer having a bump area of 1,200 μm ² and a thickness of 1.5T was placed on the anisotropic conductive film, followed by main compression at 130 ° C. for 5 seconds at 70 MPa. Next, the number of conductive particles in the connection area is calculated using an automatic particle counter, and then the particle capture rate is calculated according to Equation 2.

In addition, the anisotropic conductive film may have a main compression such as under a pressure of 50 MPa to 90 MPa at a temperature of 100 ° C to 150 ° C for 4 to 7 seconds, and then the anisotropic conductive film is placed at 85 ° C and 85% relative humidity to 250 A post-reliability connection resistance of 0.5 Ω or less measured at 0.5 hours, or 0.3 Ω or less, measured after an hour.

Within this range of connection resistance after the reliability test, the anisotropic conductive film can exhibit improved properties in connection reliability and long-term storage stability.

The connection resistance after the reliability test can be measured by the following exemplary method, but is not limited thereto. In this method, first, an anisotropic conductive film is placed on a glass substrate containing an ITO circuit. The ITO circuit has a bump area of 1,200 μm ² and a thickness of 2,000 Å, and then is initially compressed at 70 ° C. at 1 MPa. 1 second; and after removing the release film, an IC wafer having a bump area of 1,200 μm ² and a thickness of 1.5 T was placed on the anisotropic conductive film, followed by main compression at 130 ° C. and 70 MPa 5 In this way, a specimen is prepared. Next, a 4-point probe method was used to measure the resistance value between the 4 points of the prepared specimen using a resistance meter (20 million multimeter, Keithley Instruments) to find the initial connection resistance. Next, the specimen was allowed to stand at 85 ° C. and 85% relative humidity for 250 hours, and then the resistance was measured in the same manner, thereby discovering the connection resistance after the reliability test. Here, the resistance value is calculated based on the voltage measured after a 1 mA current is applied by a resistance meter, and an average value is taken.

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

The anisotropic conductive film according to the embodiment of the present invention may have a single-layer structure, but is not limited thereto. Alternatively, the anisotropic conductive film may have a multilayer structure such as a double-layer structure or a triple-layer structure.

In particular, the anisotropic conductive film may have a structure in which a dielectric layer is stacked on one or both surfaces of the conductive layer. That is, the anisotropic conductive film may have a two-layer structure of a conductive layer and a dielectric layer, a three-layer structure in which a conductive layer is stacked on the dielectric layer and another dielectric layer is stacked on the conductive layer, or includes a conductive layer and a dielectric A multilayer structure of four or more electrical layers.

As used herein, the term "stack" means that a layer is formed on the surface of another layer and is interchangeable with "coated" or "laminated." For an anisotropic conductive film having a two-layer structure with a conductive layer and a dielectric layer, since the conductive layer is separated from the dielectric layer and therefore the compression of the conductive particles is not affected by the high content of inorganic particles such as silicon dioxide, This can affect the fluidity of the composition for the anisotropic conductive film without affecting the conductivity of the anisotropic conductive film, thereby enabling the production of the anisotropic conductive film while controlling the flow of the anisotropic conductive film Sex.

For example, the anisotropic conductive film according to the present invention can be formed in a single layer structure by the following method. First, after preparing a composition for an anisotropic conductive film containing the above-mentioned components, the composition is dissolved in an organic solvent such as toluene, and then stirred at a stirring speed that does not cause the conductive particles to break. time segment. Next, the obtained material is coated on a release film to a thickness of, for example, 3 μm to 50 μm, and dried for a certain period of time to volatilize toluene and the like, thereby obtaining an anisotropic conductive film having a single-layer structure.

Alternatively, after the composition containing conductive particles and the composition containing no conductive particles are separately prepared, the composition containing conductive particles may be coated on a release film to form a conductive film, and the conductive particles may not be contained The composition of is coated on another release film to form a non-conductive film, and then the conductive film is laminated on the non-conductive film, thereby forming an anisotropic conductive film having a double-layered structure.

Next, a display device according to an embodiment of the present invention will be described.

A display device according to an embodiment of the present invention may include: a first connection member including a first electrode; a second connection member including a second electrode; and a first connection member disposed between the first connection member and the second connection member to place the first connection member The electrode is connected to an anisotropic conductive film of the second electrode, wherein the anisotropic conductive film may be an anisotropic conductive film according to an embodiment of the present invention.

The first connection member or the second connection member includes an electrode for electrical connection. Specifically, the first connection member or the second connection member may be a glass or plastic substrate, a printed wiring board, a ceramic wiring board, a flexible wiring board, a semiconductor silicon wafer, an IC chip, or a driver IC chip, which is formed for an LCD Indium tin oxide (ITO) or indium zinc oxide (IZO) electrode. More specifically, one of the first connection member and the second connection member may be an IC chip or a driver IC chip, and the other may be a glass substrate.

1, a display device 30 according to an embodiment of the present invention may include a first connection member 50 including a first electrode 70 and a second connection member including a second electrode 80 that may be connected to each other via an anisotropic conductive film 10. 60, the anisotropy The anisotropic conductive film 10 is disposed between the first connection member and the second connection member and includes the conductive particles 3 connecting the first electrode to the second electrode, wherein the anisotropic conductive film may be the aforementioned anisotropic conductive film.

Next, examples of the present invention and comparative examples will be described in detail. However, it should be understood that the present invention is not limited to the following examples.

For the sake of clarity, detailed descriptions obvious to those skilled in the art will be omitted.

Examples Example 1: Preparation of an anisotropic conductive film

By mixing 35% by weight of a biphenylfluorene-type adhesive resin (FX-293, Nippon Steel), 35.95% by weight of an alicyclic epoxy resin having an epoxy equivalent of 130 g / eq (hereinafter referred to as "epoxy Resin 1 ", Celloxide 2021P, DAICEL), 5% by weight oxetane group-containing sesquioxane compound (TX-100, Toa Synthetic Corporation), 0.05% by weight of the compound of Chemical Formula 1-1 ( SI-S, Sanshin Chemical Industry Co., Ltd., Japan), 4% by weight of cationic curing agent (SI-B3A, Sanshin Chemical Industry Co., Ltd., Japan), and 20% by weight of insulating particles (AUL- 704F, average particle diameter: 4 μm, Sekisui Co., Ltd.) to prepare a composition for an anisotropic conductive film.

The composition for an anisotropic conductive film was coated on a release film and dried at 60 ° C. for 5 minutes in a drying machine to volatilize the solvent, thereby preparing a 16 μm thick Anisotropic conductive film (Tg: 195 ° C).

Example 2: Preparation of an anisotropic conductive film

An anisotropic conductive film (Tg: 198 ° C) was prepared in the same manner as in Example 1, but the epoxy resin, the sesquioxane compound containing an oxetane group, and the chemical formula 1 were changed as listed in Table 1. -1 amount of compound.

Example 3

An anisotropic conductive film (Tg: 195 ° C) was prepared in the same manner as in Example 1, but YX4000 (hereinafter "epoxy resin 2", Mitsubishi Chemical, Japan) was used as the epoxy resin.

Example 4

By mixing 40% by weight of a biphenylstilbene type adhesive resin (FX-293, Nippon Steel), 35% by weight of a phenol novolac oxetane compound (PNOX-1009, Toa Synthetic Corporation), 5 weights % Sesquioxane compound containing oxetanyl group (SSQ-TX100, Toa Synthesis Co., Ltd.), and 5% by weight of a fourth ammonium compound as a cationic curing agent (CXC-1821, King Industry Co., Ltd.) And 15% by weight of conductive particles (AUL-704F, average particle diameter: 4 μm, Sekisui Co., Ltd., Japan) to prepare a composition for an anisotropic conductive film.

The composition for an anisotropic conductive film was coated on a release film and dried at 60 ° C. for 5 minutes in a drying machine to volatilize the solvent, thereby preparing an 18 μm thick anisotropic conductive film (Tg: 195 ° C. ).

Example 5

An anisotropic conductive film (Tg: 195 ° C) was prepared in the same manner as in Example 4, but an oxetane group-containing silsesquioxane compound was used in terms of solid content (TX-100, Toa Synthetic Corporation) was changed to 10% by weight and the amount of phenol novolak oxetane compound (PNOX-1009, Toa Synthetic Corporation) was changed to 30% by weight.

Comparative Example 1

An anisotropic conductive film (Tg: 196 ° C) was prepared in the same manner as in Example 1, but the compound of Chemical Formula 1-1 was not used and the amount of the epoxy resin was changed to 36% by weight in terms of solid content.

Comparative Example 2

An anisotropic conductive film (Tg: 205 ° C) was prepared in the same manner as in Example 1, but the epoxy resin, the sesquioxane compound containing an oxetane group, and the chemical formula 1 were changed as listed in Table 1. -1 amount of compound.

Comparative Example 3

An anisotropic conductive film (Tg: 168 ° C) was prepared in the same manner as in Example 1, but an oxetane group-containing silsesquioxane was not used in the preparation of the composition for the anisotropic conductive film. Compounds and compounds of Chemical Formula 1-1 and 5.05 wt% silica nanoparticles (R812, particle diameter: 7 nm, Tokuyama Corporation) were used.

Details of each of the components used in the examples and comparative examples are shown in Table 1. The amount of the component is measured in% by weight.

Each of the anisotropic conductive films prepared in Examples 1 to 5 and Comparative Examples 1 to 3 was evaluated for the DSC exothermic onset temperature, DSC exothermic peak temperature, minimum melt viscosity, and particle capture rate according to the following methods. , Uniformity of connection resistance and back bonding indentation, storage modulus and rate of change of heat. The results are shown in Tables 2 and 3.

Experimental Example 1: Measurement of glass transition temperature

After the anisotropic conductive film is cured on a hot press and it is determined that the anisotropic conductive film is sufficiently cured, a Dynamic Mechanical Analyzer (DMA) (TA Instruments) is used at a heating rate of 10 ° C / min. The glass transition temperature of each of the anisotropic conductive films prepared in the examples and comparative examples was measured when the anisotropic conductive film was heated from -40 ° C to 200 ° C.

Experimental example 2: Measurement of exothermic onset temperature and peak exothermic temperature on DSC

When the anisotropic conductive film is heated at a rate of 10 ° C / min in a temperature range of -50 ° C to 250 ° C under a nitrogen atmosphere, a differential scanning calorimeter Q20 (TA Instruments Corporation) is used to measure and compare examples The heat of each of the anisotropic conductive films prepared in. FIG. 2 is a diagram depicting the heat of the anisotropic conductive films prepared in Examples 1 to 3 (Example 1 is indicated by line a, Example 2 is indicated by line b, and Example 3 is indicated by line c). On the DSC chart, the DSC exothermic onset temperature is defined as the extension line between the heat generation start point and the heat generation end point and from the highest peak to The temperature at the point where the tangent of the point where the slope of the DSC graph begins to increase. In addition, the DSC exothermic peak temperature is defined as the temperature at the highest peak of heat on the DSC chart.

Experimental Example 3: Measurement of minimum melt viscosity

Measured with ARES G2 rheometer (TA Instruments) under 150 μm sample thickness, 10 ° C / min heating rate, 1% strain, 10 radians / second angular frequency, and 30 ° C to 220 ° C temperature range The minimum melt viscosity of each of the anisotropic conductive films prepared in the examples and comparative examples.

Experimental Example 4: Measurement of Particle Capture Rate

For each of the anisotropic conductive films prepared in the examples and comparative examples, the number of conductive particles per unit area (mm ² ) of the anisotropic conductive film before compression was calculated using an automatic particle counter (ZOOTUS).

Next, an anisotropic conductive film was placed on a glass substrate including an ITO circuit having a bump area of 1,200 μm ² and a thickness of 2,000 Å, and subjected to preliminary compression at 70 ° C. for 1 second at 1 MPa. Next, after the release film was removed, an IC wafer having a bump area of 1,200 μm ² and a thickness of 1.5T was placed on the anisotropic conductive film, followed by main compression at 130 ° C. for 5 seconds at 70 MPa. Next, the number of conductive particles in the connection area is calculated using an automatic particle counter, and then the particle capture rate is calculated according to Equation 2.

[Equation 2] the particle capture rate (%) = (per unit area (mm ²⁾ of the number of conductive particles in the connection area / number of conductive particles prior to compression after main compression anisotropic conductive film per unit area (mm ²⁾ of ) × 100

Experimental example 5: Measurement of initial connection resistance and post-reliability connection resistance

Each of the anisotropic conductive films prepared in the examples and comparative examples was placed on a glass substrate (Neoview Kolon Co., Ltd.) including an ITO circuit having a bump area of 1,200 μm ² and a thickness of 2,000 Å and was Initial compression was performed at 70 ° C for 1 second at 1 MPa. Next, after the release film was removed, an IC wafer (Samsung LSI) having a bump area of 1,200 μm ² and a thickness of 1.5 T was placed on the anisotropic conductive film, followed by main compression at 130 ° C. and 70 MPa. 5 seconds, thereby preparing a specimen. Next, a 4-point probe method was used to measure the resistance value between the 4 points of the prepared specimen using a resistance meter (20 million multimeter, Keithley Instruments) to find the initial connection resistance. Next, the specimen was allowed to stand at 85 ° C. and 85% relative humidity for 250 hours, and then the resistance was measured in the same manner, thereby discovering the connection resistance after the reliability test.

Here, the resistance value is calculated based on the voltage measured after a 1 mA current is applied by a resistance meter, and an average value is taken.

Experimental Example 6: Measurement of uniformity of back-joint indentation

Each of the anisotropic conductive films prepared in the examples and comparative examples was placed on a glass substrate (Neoview Kolon Co., Ltd.) including an ITO circuit having a bump area of 1,200 μm ² and a thickness of 2,000 Å and was Initial compression was performed at 70 ° C for 1 second at 1 MPa. Next, after the release film was removed, an IC wafer (Samsung LSI) having a bump area of 1,200 μm ² and a thickness of 1.5T was placed on the anisotropic conductive film, and then was 70 MPa at 130 ° C. Lower main compression for 5 seconds. Next, the uniformity of the indentation was observed with the naked eye. In particular, when the indentation at both sides of the IC wafer is as clear as the indentation in its center region, this result is rated as good (○); and when the indentation at both sides of the IC wafer is clear When it is not clear as compared with the indentation in its center region, this result is evaluated as uneven (×).

Experimental Example 7: Measurement of storage modulus

For the storage modulus measurement, a plurality of corresponding anisotropic conductive films were laminated to form a 100 μm-thick anisotropic conductive film, and then cured by a hot press at 90% or more of each of the laminated anisotropic conductive films. The anisotropic conductive film is a specimen of each of the anisotropic conductive films prepared in the preparation examples and the comparative examples. Next, the storage modulus was measured using a Dynamic Mechanical Analyzer (DMA) (TA Instruments Corporation) when the specimen was heated from -40 ° C to 200 ° C at a heating rate of 10 ° C / min.

Among the various storage modules, the storage module at 30 ° C was confirmed.

Experimental example 8: Measurement of DSC thermal change rate of anisotropic conductive film

After each of the anisotropic conductive films prepared in the 1 mg example and the comparative example was equally divided into specimens, a differential scanning calorimeter (DSC) (Q20, TA Instrument Co., Ltd.) The specimen was heated at a heating rate of 10 ° C / min in a temperature range of -50 ° C to 250 ° C to measure the initial heat (H ₀ ) of the specimen. Next, after the specimen was left to stand at 25 ° C. for 5 days, the amount of heat (H ₁ ) of the specimen was measured in the same manner. The heat change rate is calculated by the following Equation 1.

[Equation 1] Heat change rate (%) = [| (H ₀ -H ₁ ) | / H ₀ ] × 100

In Table 2, it can be seen that the anisotropic conductive films of Examples 1 to 5 have a high storage modulus in the range of 2.5 GPa to 4 GPa, exhibit less change in heat to provide good storage stability, and have high particles. Capture rate. In addition, each of the anisotropic conductive films of Examples 1 to 5 has a low DSC exothermic starting temperature and a low DSC exothermic peak temperature, and provides a relatively small difference between the DSC exothermic starting temperature and the DSC exothermic peak temperature. The difference, thereby achieving rapid curing at low temperatures.

In contrast, in Table 3, each of Comparative Example 1 having a post-cure storage modulus at 30 ° C. of less than 2.5 GPa and a DSC heat change rate higher than 20% as calculated by Equation 1 can be seen. Comparison of anisotropic conductive film, silsesquioxane compound containing excessive oxetanyl group, and anisotropic conductive film of Example 2 and comparison of silsesquioxane compound without oxetanyl group The indentation of the anisotropic conductive film of Example 3 at both sides of the IC wafer is not clear as compared with the indentation in the center region thereof, thereby providing an uneven indentation.

Although some embodiments and features of the invention have been described above, it should be understood that these embodiments and features are given for illustrative purposes only and are not intended to be construed as limiting the invention in any way. Therefore, the scope and spirit of the present invention should be defined only by the scope of the appended patent applications and their equivalents.

Claims (22)

An anisotropic conductive film is formed of a composition for an anisotropic conductive film, the composition including a compound represented by Chemical Formula 1 and from 1% by weight to a total weight of the composition in terms of solid content 14% by weight of an oxetane-containing silsesquioxane compound, the anisotropic conductive film has a storage modulus of 2.5 GPa to 4 GPa measured at 30 ° C after curing and is retained at 20% or less heat change rate measured by differential scanning calorimetry (DSC) and calculated by Equation 1 after 5 days at 25 ° C: [Equation 1] Heat change rate (%) = [ | (H ₀ -H ₁ ) | / H ₀ ] × 100 where H ₀ is the DSC heat of the anisotropic conductive film measured immediately after the production of the anisotropic conductive film, and H ₁ The DSC heat of the anisotropic conductive film measured after being left at 25 ° C for 5 days; and Wherein R ₁ is one selected from the group consisting of hydrogen, C ₁ to C ₆ alkyl, C ₆ to C ₁₄ aryl, -C ₁ to C ₆ alkyl-C ₆ to C ₁₄ aryl, -C (= O) R ₈ , -C (= O) OR ₉ and -C (= O) NHR ₁₀ (R ₈ , R ₉ and R ₁₀ are each independently selected from C ₁ to C ₆ alkyl and C _{One of 6} to C ₁₄ aryl); R ₂ to R ₅ are each independently hydrogen or C ₁ to C ₆ alkyl; R ₆ and R ₇ are each independently C ₁ to C ₆ alkyl, nitrobenzene Methyl, dinitrobenzyl, trinitrobenzyl, benzyl substituted or unsubstituted with C ₁ to C ₆ alkyl, and naphthylmethyl; and X ₁ ^- is alkylsulfuric acid. The anisotropic conductive film according to item 1 of the scope of patent application, wherein the sesquioxane compound containing an oxetanyl group includes a structure represented by Chemical Formula 2: Where R ₁₁ is an oxetanyl group; R ₁₂ is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, heteroalkyl, heterocycloalkyl Or alkenyl; and x and y satisfy 0 <x 1.0, 0 y <1.0 and x + y = 1. Anisotropic conductive film as described in item 2 of the patent application, where x is 0.5 x Within 1.0 range. The anisotropic conductive film according to item 1 of the patent application scope, wherein the composition further includes a binder resin, an epoxy resin, conductive particles, and a curing agent. The anisotropic conductive film according to item 4 of the scope of patent application, wherein the adhesive resin is a phenphenoxy resin. The anisotropic conductive film according to item 4 of the scope of patent application, wherein the epoxy resin includes at least one selected from the group consisting of: bisphenol type epoxy resin, aromatic epoxy resin, grease Cyclic epoxy resin, novolac type epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, biphenyl diglycidyl ether epoxy resin, hydrogenated epoxy resin, and combinations thereof. The anisotropic conductive film according to item 6 of the scope of patent application, wherein the alicyclic epoxy resin has at least one of the structures represented by Chemical Formula 10 to Chemical Formula 13: Wherein n, s, t, u, v, m, and f are each independently an integer of 1 to 50, and R ′ is an alkyl group, an ethylfluorenyl group, an alkoxy group, or a carbonyl group. The anisotropic conductive film according to item 4 of the scope of patent application, wherein the curing agent is at least one selected from the group consisting of acid anhydride, amine, imidazole, isocyanate, ammonium, hydrazine, phenol And cationic curing agents. The anisotropic conductive film according to item 8 of the scope of the patent application, wherein the cationic curing agent has one of the structures represented by Chemical Formula 14, Chemical Formula 16, Chemical Formula 16, and Chemical Formula 17: Wherein R ₁₃ is one selected from the group consisting of hydrogen, C ₁ to C ₆ alkyl, C ₆ to C ₁₄ aryl, -C ₁ to C ₆ alkyl-C ₆ to C ₁₄ aryl -C (= O) R ₃₁ , -C (= O) OR ₃₂ , and -C (= O) NHR ₃₃ (R ₃₁ , R ₃₂ and R ₃₃ are each independently selected from C ₁ to C ₆ alkyl And one of C ₆ to C ₁₄ aryl); R ₁₄ to R ₁₇ are each independently hydrogen or C ₁ to C ₆ alkyl; and R ₁₈ and R ₁₉ are each independently selected from the group consisting of One of the group: C ₁ to C ₆ alkyl, nitrobenzyl, dinitrobenzyl, trinitrobenzyl, benzyl substituted or unsubstituted by C ₁ to C ₆ alkyl And naphthylmethyl; and Y ₁ ^- is AsF ₆ , SbF ₆ , SbCl ₆ , (C ₆ F ₅ ) ₄ B, SbF ₅ (OH), PF ₆ or BF ₄ , Where R ₂₀ is hydrogen; R ₂₁ is C ₁ to C ₆ alkyl; R ₂₂ is -OH, -OC (= O) R ₃₄ or -OC (= O) OR ₃₅ (R ₃₄ and R ₃₅ are each independently C ₁ to C ₆ alkyl); and Y ₂ ^- is AsF ₆ , SbF ₆ , SbCl ₆ , (C ₆ F ₅ ) ₄ B, SbF ₅ (OH), PF ₆ or BF ₄ , Wherein R ₂₃ and R ₂₄ are each independently one selected from the group consisting of C ₁ to C ₂₀ alkyl, C ₃ to C ₁₂ alkenyl, C ₆ to C ₂₀ aryl, C ₇ to C ₂₀ alkaryl, C ₇ to C ₂₀ alkaryl, C ₁ to C ₂₀ alkanol, and C ₅ to C ₂₀ cycloalkyl; Ar ₁ is a substituted or unsubstituted C ₆ to C ₂₀ aryl; Ar ₂ is a substituted or unsubstituted C ₆ to C ₂₀ arylene group; and Y ₃ ^- is a monovalent anion selected from the group consisting of BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , SbCl ₆ , (C ₆ F ₅ ) ₄ B, SbF ₅ (OH), HSO ₄ , p-CH ₃ C ₆ H ₄ SO ₃ , HCO ₃ , H ₂ PO ₄ , CH ₃ COO, and halogen anions, Wherein R _26, R _27, R ₂₈ and R ₂₉ are each independently of those of the following one: a substituted or unsubstituted C ₁ to C ₆ alkyl or C ₆ to C ₂₀ aryl; and M ^- of the following persons of ^{_{one: 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} -. The anisotropic conductive film according to item 1 of the scope of patent application, wherein, in Chemical Formula 1, R ₁ is hydrogen or C ₁ to C ₄ alkyl or ethenyl; R ₂ to R ₅ are each independently hydrogen Or C ₁ to C ₄ alkyl; and R ₆ and R ₇ are methyl or benzyl. The anisotropic conductive film according to item 1 of the patent application scope, wherein the anisotropic conductive film has a post-cured glass transition temperature (Tg) of 150 ° C to 250 ° C. The anisotropic conductive film according to item 4 of the scope of application for a patent, wherein the composition includes the binder resin in terms of solid content of 15 to 70% by weight; 15 to 50% by weight The epoxy resin; 1 to 10% by weight of the curing agent; and 1 to 30% by weight of the conductive particles. The anisotropic conductive film according to item 12 of the scope of patent application, wherein the composition further includes 0.001% to 10% by weight of a compound represented by Chemical Formula 1: Wherein R ₁ is one selected from the group consisting of hydrogen, C ₁ to C ₆ alkyl, C ₆ to C ₁₄ aryl, -C ₁ to C ₆ alkyl-C ₆ to C ₁₄ aryl , -C (= O) R ₈ , -C (= O) OR ₉ and -C (= O) NHR ₁₀ (R ₈ , R ₉ and R ₁₀ are each independently selected from C ₁ to C ₆ alkyl and One of C ₆ to C ₁₄ aryl); R ₂ to R ₅ are each independently hydrogen or C ₁ to C ₆ alkyl; R ₆ and R ₇ are each independently C ₁ to C ₆ alkyl, nitro Benzyl, dinitrobenzyl, trinitrobenzyl, benzyl substituted or unsubstituted with C ₁ to C ₆ alkyl, and naphthylmethyl; and X ₁ ^- is alkylsulfuric acid. The anisotropic conductive film according to item 1 of the scope of patent application, wherein the composition further includes an inorganic filler in an amount of 5% to 40% by weight. An anisotropic conductive film includes a sesquioxane compound containing an oxetanyl group, a binder resin, an epoxy resin, conductive particles, and a curing agent. The anisotropic conductive film has a differential The difference between the peak exothermic temperature measured by scanning calorimetry (DSC) and the initial exothermic temperature of 10 ° C or less, and 10,000Pa at a temperature of 80 ° C to 100 ° C. sec to 200,000Pa. The minimum melt viscosity of sec, including the compound represented by Chemical Formula 1: Wherein R ₁ is one selected from the group consisting of hydrogen, C ₁ to C ₆ alkyl, C ₆ to C ₁₄ aryl, -C ₁ to C ₆ alkyl-C ₆ to C ₁₄ aryl , -C (= O) R ₈ , -C (= O) OR ₉ and -C (= O) NHR ₁₀ (R ₈ , R ₉ and R ₁₀ are each independently selected from C ₁ to C ₆ alkyl and One of C ₆ to C ₁₄ aryl); R ₂ to R ₅ are each independently hydrogen or C ₁ to C ₆ alkyl; R ₆ and R ₇ are each independently C ₁ to C ₆ alkyl, nitro Benzyl, dinitrobenzyl, trinitrobenzyl, benzyl substituted or unsubstituted with C ₁ to C ₆ alkyl, and naphthylmethyl; and X ₁ ^- is alkylsulfuric acid. The anisotropic conductive film according to item 15 of the scope of patent application, wherein the sesquioxane compound containing an oxetanyl group includes a repeating unit represented by Chemical Formula 2: Where R ₁₁ is an oxetanyl group; R ₁₂ is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkaryl, heteroalkyl, heterocycloalkyl Or alkenyl; and x and y satisfy 0 <x 1.0, 0 y <1.0 and x + y = 1. The anisotropic conductive film according to item 15 of the scope of patent application, wherein the curing agent is at least one selected from the group consisting of acid anhydride, amine, imidazole, isocyanate, amidine, hydrazine, phenol And cationic curing agents. The anisotropic conductive film according to item 15 of the scope of patent application, wherein the anisotropic conductive film has a main compression at a pressure of 50 MPa to 90 MPa at a temperature of 100 ° C to 150 ° C for 4 seconds to 7 seconds. Measure and calculate the particle capture rate from 30% to 70% by Equation 2: [Equation 2] Particle capture rate (%) = (conductive unit per unit area (mm ² ) in the connection area after the main compression) Number / the number of conductive particles per unit area (mm ² ) of the anisotropic conductive film before compression) × 100. The anisotropic conductive film according to item 15 of the scope of application for a patent, wherein the anisotropic conductive film has a main compression at a temperature of 100 to 150 ° C for a period of 4 to 7 seconds under a pressure of 50 MPa to 90 MPa, and then The anisotropic conductive film has a post-reliable connection resistance of 0.5 Ω or less measured after 250 hours at 85 ° C. and 85% relative humidity. The anisotropic conductive film according to item 15 of the scope of patent application, wherein the anisotropic conductive film is used in a chip on glass (COG) or chip on film (COF) mounting method . An anisotropic conductive film formed from a composition for an anisotropic conductive film, the composition including an oxygen-containing impurity in an amount of 1 to 14% by weight based on the total weight of the composition in terms of solid content Cyclobutane group silsesquioxane compound and 5% to 40% by weight phenol novolac oxetane compound, the anisotropic conductive film has a 2.5 measured at 30 ° C after curing. GPa to 4GPa storage modulus and heat change rate of 20% or less measured by differential scanning calorimetry (DSC) after 5 days at 25 ° C and calculated by Equation 1: Equation 1] Thermal change rate (%) = [| (H ₀ -H ₁ ) | / H ₀ ] × 100 where H ₀ is the each measured immediately after the production of the anisotropic conductive film DSC to heat an anisotropic conductive film, and H ₁ is retained at 25 deg.] C in 5 days after the measured DSC heat the anisotropic conductive film. A display device includes: a first connection member including a first electrode; a second connection member including a second electrode; and the anisotropic conductive film according to any one of claims 1 to 21 of a patent application range. The anisotropic conductive film is disposed between the first connection member and the second connection member and connects the first electrode and the second electrode.