TW201643203A - Polymer resin having formula 1 or 2, adhesive film comprising the same, and display device connected by adhesive film - Google Patents

Abstract

The present invention relates to a polymer resin represented by Formula 1 or 2, an adhesive film including the same, and a display apparatus connected by the adhesive film. [Formula 1][Formula 2], In Formula 1 or 2, each substituent is the same as defined in the specification.

Description

Polymer resin having Formula 1 or Formula 2, adhesive film containing the same, and display device connected by the adhesive film

The present invention relates to a polymer resin represented by Formula 1 or Formula 2, an adhesive film containing the same, and a display device connected by an adhesive film.

With the recent miniaturization and high functionality of electronic devices, the development of narrow components for connecting terminals has been promoted for bonding integrated circuit (IC) chips and flexible printed circuits (flexible printed circuits, The FPC) board and the field of electronic packaging for bonding IC chips and glass substrates and indium tin oxide (ITO) electrode circuits use various film-like adhesives which can promote the connection between the terminals.

The adhesive film as a film-like adhesive containing conductive particles in the resin composition allows the resin in the adhesive to flow while being heated and compressed, thereby sealing the gap between the electrodes facing each other on the connection target and allowing a certain The conductive particles fill the gap between the electrodes, thereby achieving an electrical connection between the electrodes.

In general, the adhesive film is composed of an epoxy composition containing a thermosetting resin and a curing agent as essential components. However, the epoxy resin composition (Japanese Patent Publication No. 2009-161755 A) has a problem of insufficient film formability or flexibility when forming a film. Specifically, as electronic devices have become lighter and shorter, the substrate has become thinner and the bonding heat and pressure have become lower. Therefore, film formation properties and flexibility have become more important. Therefore, there is a need for a new polymer resin which exhibits excellent flowability at low temperatures and which has excellent adhesion, adhesion properties and reliability.

An object of the present invention is to provide a polymer resin which has good heat resistance and flowability, ensures high film formability when forming a film, and exhibits excellent flexibility, heat resistance and bonding properties. .

Another object of the present invention is to provide an adhesive film and a display device connected by the film, which can achieve connection even at a low connection temperature and exhibit excellent storage stability, adhesion strength and reliability.

According to an aspect of the invention, there is provided a polymer resin having a unit represented by Formula 1 or Formula 2: [Formula 1] ; [Formula 2] Wherein X ₁ and X ₂ are each a difunctional epoxy compound-derived unit or a mesogen compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has a crosslinking functional group; Y ₁ and Y ₂ are each a difunctional epoxy compound-derived unit, and each of Z ₁ and Z ₂ is a liquid crystal original compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has cross-linking The functional group, or Y ₁ and Y _{2 ,} each is a liquid crystal original compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has a crosslinking functional group, and each of Z ₁ and Z ₂ is a double a functional epoxy compound-derived unit; and n ₁ , n ₂ , m ₁ and m ₂ each independently represent an integer from 1 to 10.

According to another aspect of the invention, an adhesive film comprises a polymer resin having a unit represented by Formula 1 or Formula 2.

According to still another aspect of the present invention, there is provided an adhesive film having a minimum melt viscosity of from 1,000 centipoise to 40,000 centipoise at a temperature of 100 ° C or less.

According to still another aspect of the present invention, a display device connected by the adhesive film is provided.

The polymer resin and the adhesive film containing the same according to the embodiments of the present invention not only have excellent heat resistance and flowability, but also exhibit high film formability when forming a film, and have superior flexibility, flowability, and heat resistance. Sex and connection nature. Further, the adhesive film containing a polymer resin according to an embodiment of the present invention can achieve connection even at a low connection temperature and exhibit excellent storage stability, adhesion strength, and reliability.

Embodiments of the present invention will be described in detail below. However, the examples are provided to illustrate and not to limit the invention. The invention is defined only by the scope of the accompanying claims.

One embodiment of the present invention provides a polymer resin having a unit represented by Formula 1 or Formula 2: [Formula 1] ; [Formula 2] Wherein X ₁ and X ₂ are each a difunctional epoxy compound-derived unit or a liquid crystal original compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has a crosslinking functional group; Y ₁ and Y _{2 is} each a difunctional epoxy compound-derived unit, and each of Z ₁ and Z ₂ is a liquid crystal original compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has a crosslinking functional group, Or each of Y ₁ and Y ₂ is a liquid crystal original compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has a crosslinking functional group, and each of Z ₁ and Z ₂ is a difunctional epoxy The compound-derived unit; and n ₁ , n ₂ , m ₁ and m ₂ each independently represent an integer from 1 to 10.

The polymer resin for forming a film represented by Formula 1 or Formula 2 has high film formability while exhibiting improved properties in terms of flexibility, heat resistance, adhesion strength, and storage stability.

The term "substituted" as used herein, unless otherwise defined, means that a hydrogen atom in a compound is substituted with a substituent selected from a halogen atom (F, Br, Cl or I), a haloalkyl group, a hydroxyl group, an alkoxy group. , nitro, cyano, amine, azide, sulfhydryl, fluorenyl, hydrazono, carbonyl, amine mercapto, thiol, ester, carboxyl or its salts, sulfonyl or a salt thereof, a phosphate group or a salt thereof, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₂ to C ₂₀ alkynyl group, a C ₆ to C ₃₀ aryl group, a C ₇ to C ₃₀ aralkyl group, C ₁ to C ₂₀ alkoxy, C ₁ to C ₂₀ heteroalkyl, C ₃ to C ₂₀ heteroarylalkyl, C ₃ to C ₂₀ cycloalkyl, (meth) acrylate group, C ₃ to C ₂₀ Cycloalkenyl, C ₄ to C ₂₀ cycloalkynyl, C ₂ to C ₂₀ heterocycloalkyl, and combinations thereof.

Further, unless otherwise defined, the term "hetero" means that the compound contains one to three heteroatoms selected from N, O, S, and P.

In Formula 1 or Formula 2, the difunctional epoxy compound may be a substituted or unsubstituted difunctional bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol AD epoxy compound or a bisphenol S epoxy Compound. Specifically, the difunctional epoxy compound may be a bisphenol A epoxy compound or a bisphenol F epoxy compound.

In Formula 1 or Formula 2, a liquid crystal original compound containing at least two aromatic or alicyclic compounds and having a crosslinking functional group means an aromatic ring or an alicyclic ring having at least two linked in one direction. A liquid crystalline raw compound having a cross-linking functional group and being substituted or unsubstituted and having a rod-like or dish-like structure. The crosslinking functional group is a functional group capable of reacting with an epoxy group to form a crosslinked structure, such as a hydroxyl group, an epoxy group, an acrylate group or a carboxyl group, more specifically a hydroxyl group.

Examples of the liquid crystal raw compound-derived unit may include the following formulas A1 to A7: [Formula A1] , [Formula A2] , [Formula A3] , [Formula A4] , [Formula A5] , [Formula A6] And [Formula A7] Wherein R ₁ to R ₂₄ are each independently hydrogen, fluoro, alkyl, thiol, methylthio, nitro or an alcohol, amine or carboxylic acid having from 0 to 20 alkyl or hydrogen, and at opposite ends The linking group can include an ether linkage or an ester linkage.

Another example of a liquid crystal raw compound may include a compound having the following structure and having a crosslinking functional group at an opposite end, in which at least two aromatic hydrocarbons are bonded to a fused ring or at least two aromatic rings are directly linked or Connected via a linking group.

The polymer resin having a unit represented by Formula 1 or Formula 2 may be a difunctional epoxy compound, a phenyl fluorene compound having a cross-linking functional group or a naphthyl fluorene compound, and containing an aromatic or alicyclic compound and having an intersection It is prepared by a condensation reaction of a bifunctional liquid crystal original compound. The crosslinking functional group may be a functional group capable of reacting with an epoxy group or other crosslinking functional group to form a crosslinked structure, such as a hydroxyl group, an epoxy group, an acrylate group or a carboxyl group, more specifically a hydroxyl group or Epoxy group. Specifically, a polymer resin having a unit represented by Formula 1 or Formula 2 can be produced by placing the above compound in a reactor while refluxing nitrogen, adding a solvent (for example, cyclohexanone), and adding The catalyst is reacted and polymerization is carried out for 1 hour to 50 hours while maintaining the reactor at a temperature of from 100 ° C to 200 ° C. The polymerization equivalent ratio of the phenylhydrazine compound or the naphthylquinone compound having a crosslinking functional group to the liquid crystal original compound having a crosslinking functional group may be from 1:5 to 5:1, specifically from 1:4 to 3:1. Further, the polymerization equivalent ratio of the phenylfluorene compound or the naphthylquinone compound having a crosslinking functional group to the difunctional epoxy compound may be from 1:5 to 5:1, specifically from 1:4 to 3:1. The phenyl fluorene compound or naphthyl fluorene compound having a crosslinking functional group may be 9,9-bis(4-hydroxyphenyl)fluorene or 9,9-bis ( 6-hydroxy-2-naphthylfluorene (6-hydroxy-2-naphthyl) fluorene).

The polymer resin having a unit represented by Formula 1 or Formula 2 may have a weight average molecular weight of 1,000 to 500,000, specifically, 2,000 to 200,000, and more specifically 10,000 to 100,000. Within this range, the polymer resin can contribute to film formability, flexibility, and heat resistance. The polymer resin having a unit represented by Formula 1 or Formula 2 may have a glass transition temperature of from 95 ° C to 180 ° C, specifically from 100 ° C to 150 ° C. The polymer resin may be contained in the adhesive film in an amount of 10% (10% by weight) to 50% by weight, specifically 15% by weight to 40% by weight, based on the solid content.

The reaction catalyst for preparing the polymer resin having a unit represented by Formula 1 or Formula 2 may be, for example, an amine reaction catalyst or an imidazole reaction catalyst. The amine reaction catalyst may include a linear amine, a fatty amine, a modified aliphatic amine, an aromatic amine, a secondary amine, and a tertiary amine, and specific examples thereof may include benzyldimethylamine, triethanolamine, triethylenetetramine, Diethylenetriamine, triethylamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, and the like.

Examples of the imidazole reaction catalyst may include imidazole, isoimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, butylimidazole, 2-heptadecenyl- 4-methylimidazole, 2-undecenyl imidazole, 1-vinyl-2-methylimidazole, 2-n-heptadecylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-benzene Imidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4- Addition of methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-nonylaminoethyl-2-methylimidazole, imidazole and methylimidazole , an adduct of imidazole and trimellitic acid, 2-n-heptadecyl-4-methylimidazole, phenylimidazole, benzylimidazole, 2-methyl-4,5-diphenylimidazole, 2, 3,5-triphenylimidazole, 2-styrylimidazole, 1-(dodecylbenzyl)-2-methylimidazole, 2-(2-hydroxy-4-t-butylphenyl)-4 , 5-diphenylimidazole, 2-(2-methoxyphenyl)-4,5-diphenylimidazole, 2-(3-hydroxyphenyl)-4,5-diphenylimidazole, 2- (p-dimethyl-aminophenyl)-4,5-diphenylimidazole, 2-(2-hydroxyphenyl)-4,5-diphenylimidazole, bis (4,5 -diphenyl-2-imidazolyl)-benzene-1,4,2-naphthyl-4,5-diphenylimidazole, 1-benzyl-2-methylimidazole, and 2-p-methoxystyryl Imidazole, but not limited to this.

The amount of the reaction catalyst used may be from about 0.5% by weight to about 20% by weight, for example from about 1% by weight to about 15% by weight or about 1% by weight, based on the total of the polymer resin used to form the composition. Up to about 10% by weight.

An adhesive film according to an embodiment of the present invention will be explained below. This embodiment relates to an adhesive film comprising the above polymer resin having a unit represented by Formula 1 or Formula 2. The adhesive film may further comprise a radical reactive material, a radical reaction initiator, and conductive particles, or may further comprise a cationic polymerizable material, cationic polymerization, in addition to the polymer resin having a unit represented by Formula 1 or Formula 2. Starting agent and conductive particles. Specifically, the adhesive film may further comprise conductive particles, a cationic polymerizable material, and a cationic polymerization initiator.

In one embodiment, the adhesive film may include a polymer resin having a unit represented by Formula 1 or Formula 2, conductive particles, a radical reactive material, and a radical reaction initiator. Examples of the radical reactive material may include a (meth) acrylate polymerizable material such as a (meth) acrylate oligomer or a (meth) acrylate monomer. Examples of the (meth) acrylate monomer may include monohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 1,4-butanediol (meth)acrylate (meth)acrylate), 2-hydroxyalkyl(meth)acryloyl phosphate, 4-hydroxycyclohexyl(meth) Acrylate), neopentyl glycol mono(meth)acrylate, trimethylolethane di(meth)acrylate, and trihydroxyl Methylpropane di(meth)acrylate, but not limited to this. Examples of the (meth) acrylate oligomer may include: an epoxy (meth) acrylate oligomer having an intermediate molecular structure backbone selected from the group consisting of 2-bromo hydroquinone, resorcin, Catechol, bisphenol (for example, bisphenol A, bisphenol F, bisphenol AD, and bisphenol S), 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)ether (bis ( 4-hydroxyphenyl)ether); and (meth)acrylate oligomers having an alkyl group, an aryl group, a hydroxymethyl group, an allyl group, an alicyclic group, a halogen group (tetrabromobisphenol A), or a nitro group Things, but not limited to them.

The radically reactive material may be contained in the adhesive film in an amount of 10% by weight to 40% by weight, for example, 10% by weight to 30% by weight, based on the solid content. Within this range, the film can then have excellent physical properties (e.g., strength and appearance) and stability after reliability testing.

Examples of the radical reaction initiator may include a photopolymerization initiator or a thermosetting initiator which may be used in combination of one or more. The photopolymerization initiator may include benzophenone, methyl o-benzoylbenzoate, 4-benzopyrene-4-methyldiphenyl sulfide (4-benzoyl). -4-methyldiphenyl sulfide), isopropylthioxanthone, diethylthioxanthone, ethyl 4-diethylbenzoate, benzoin ether ), benzoin propyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and diethoxy Diethoxy acetophenone, but not limited to this. The thermosetting initiator may include, but is not limited to, a peroxide initiator and an azo initiator. The peroxide initiator may include benzoyl peroxide, lauryl peroxide, lauroyl peroxide, and t-butyl peroxylaurate. And 1,1,3,3-4,4-methylbutylperoxy-2-ethylhexanoate, but not limited thereto. The azo initiator may include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). ), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(N-cyclohexyl) -2-methylpropionamide (2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2-azobis(2,4-dimethylvaleronitrile) (2,2- Azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis[N -(2-propenyl)-2-methylpropionamide] (2,2'-azobis[N-(2-propenyl)-2-methylpropionamide]), 2,2'-azobis(N-butyl (2,2'-azobis(N-butyl-2-methylpropionamide), 1,1'-azobis(cyclohexane-1-carbonitrile) (1,1' -azobis(cyclohexane-1-carbonitrile) and 1-[(cyano-1-methylethyl)azo]amide, but not only Limited to this.

The radical reaction initiator may be contained in the adhesive film in an amount of from 0.5% by weight to 10% by weight, for example from 1% by weight to 8% by weight, based on the solid content. Within this range, sufficient curing can occur and it is expected that the film will have a sufficient molecular weight to exhibit excellent physical properties in terms of adhesion strength and reliability after bonding.

In another embodiment, the adhesive film may include a polymer resin having a unit represented by Formula 1 or Formula 2, a cationic polymerizable material, conductive particles, and a cationic polymerization initiator.

Examples of the cationically polymerizable material may include an epoxy resin, specifically a thermosetting epoxy resin. For example, an epoxy resin having an epoxy equivalent weight of from about 90 grams per equivalent (g/eq) to about 5,000 grams per equivalent and comprising at least two epoxy groups can be used. More specifically, the cationically polymerizable material may include at least one epoxy resin selected from the group consisting of hydrogenated epoxy resins, bisphenol type epoxy resins, novolac-type epoxy resins, shrinkage Glycidyl-type epoxy resin, aliphatic epoxy resin and cycloaliphatic epoxy resin. The cationically polymerizable material may be contained in the adhesive film in an amount of 10% by weight to 50% by weight, specifically 15% by weight to 45% by weight, more specifically 15% by weight to 35% by weight, based on the solid content.

More specifically, a hydrogenated epoxy resin or an oxypropylene-based epoxy resin can be used. Hydrogenated epoxy resins or propylene oxide based epoxy resins allow for rapid curing at low temperatures while ensuring satisfactory stability.

Specifically, the hydrogenated epoxy resin comprises a hydrogenated bisphenol A epoxy resin or an alicyclic hydrogenated epoxy resin such as a cycloaliphatic epoxy resin. The cycloaliphatic epoxy resin may include an alicyclic diepoxy acetal, an alicyclic diepoxy adipate, an alicyclic diepoxycarboxylate (alicyclic). Diepoxy carboxylate), a resin such as vinylcyclohexene dioxide. In general, a hydrogenated bisphenol A epoxy resin can be obtained using a hydrogenated bisphenol A derivative and epichlorohydrin and has a structure in which a double bond in a molecular structure of bisphenol A is substituted with a hydrogen molecule.

Examples of the hydrogenated bisphenol A epoxy resin may include a hydrogenated bisphenol A epoxy monomer represented by the following formula 3 or a hydrogenated bisphenol A epoxy oligomer represented by the following formula 4. [Formula 3] [Formula 4] In Formula 4, n is from 0.1 to 13.

Specifically, a hydrogenated epoxy resin having an epoxy equivalent weight of from 150 g/eq to 1,200 g/eq and a viscosity of from 900 cps/25 ° C to 12,000 cps/25 ° C can be used.

Any cationic polymerization initiator may be used as the cationic polymerization initiator as long as the cationic polymerization initiator can accelerate the curing of the epoxy resin, for example, ruthenium which can be used singly or as a mixture thereof can be used. Imidazole, isocyanate, amine, guanamine, phenol or anhydride curing agent.

The conductive particles may include: metal particles including Au, Ag, Ni, Cu, and Pb; carbon particles; particles obtained by coating a polymer resin with a metal; particles obtained by coating a polymer resin with a metal The surface is subjected to insulation treatment to obtain particles and the like. The polymer resin may include polyethylene, polypropylene, polyester, polystyrene, and polyvinyl alcohol, but is not limited thereto. The metal used for coating the polymer resin may include, but is not limited to, Au, Ag, Ni, Cu, and Pb. Specifically, in Outer Lead Bonding (OLB), since the bonding body is an indium tin oxide (ITO) glass surface, conductive particles having a plastic core portion can be used to avoid anisotropy. The pressure applied during the joining of the conductive film damages the ITO. In order to connect a printed circuit board (PCB), metal particles such as Ni particles may be used. For a plasma display panel (PDP), since extremely high voltage is applied to the circuit, conductive particles obtained by plating metal particles (for example, Ni particles) with gold (Au) can be used. For chip on glass (COG) or chip on film (COF) having a narrow pitch, insulating conductive particles obtained by coating the surface of the conductive particles with a thermoplastic resin can be used. Conductive particles may be included in the adhesive film in an amount of 10% by weight to 40% by weight, 15% by weight to 35% by weight, for example, 15% by weight to 25% by weight.

In still another embodiment, in addition to the polymer resin having the unit represented by Formula 1 or Formula 2, the adhesive film may further contain a binder resin. Examples of the binder resin may include at least one selected from the group consisting of acrylonitrile resin, phenoxy resin, butadiene resin, acrylate resin, urethane resin, polyamine Resins, anthrone resins, and nitrile butadiene rubber (NBR) resins, but are not limited thereto. Alternatively, the binder resin may include at least one of an olefin resin, an acrylonitrile butadiene copolymer, a carboxyl terminated acrylonitrile butadiene copolymer, and a polyfluorene. Imine resin, polyester resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, styrene-butadiene-styrene (SBS) resin, styrene-ethylene/butyl Styrene-ethylene/butylene-styrene (SEBS) resin, epoxy resin, and phenoxy resin.

In some embodiments, the adhesive film can be an anisotropic conductive adhesive film. The anisotropic conductive adhesive film may have a single layer structure or a structure including at least two layers including conductive particles, a polymer resin represented by Formula 1 or Formula 2, and a curing system, and the at least The structure of the two layers includes a conductive layer containing conductive particles and an insulating resin layer containing no conductive particles. The conductive layer and the insulating resin layer may have the same composition except for the presence or absence of conductive particles. Therefore, in the structure including at least two layers, the conductive layer and the insulating resin layer may independently include the polymer resin represented by Formula 1 or Formula 2. For example, the anisotropic conductive film may have a two-layer structure in which a conductive layer and an insulating resin layer are stacked, a three-layer structure in which a first insulating resin layer and a second insulating resin layer are stacked on opposite surfaces of the conductive layer, Or a four-layer structure in which the first insulating resin layer and the second insulating resin layer are stacked on the opposite surfaces of the conductive layer and the third insulating resin layer is stacked on any of the first and second insulating resin layers.

In the two-layer structure, the thickness of the insulating resin layer may be greater than the thickness of the conductive layer. Specifically, the thickness of the insulating resin layer may be one to four times the thickness of the conductive layer. Within this range, the insulating resin sufficiently fills the gap between adjacent circuits, and thus the film can exhibit satisfactory insulating properties and bonding properties.

In the three-layer structure, the first insulating layer may have a thickness of 2 micrometers or less, the second insulating layer may have a thickness of 7 micrometers to 18 micrometers, and the thickness of the conductive layer may be 0.5 of the diameter of the conductive particles. Doubled to 2 times. More specifically, the first insulating layer may have a thickness of 1 micrometer or less, and the second insulating layer may have a thickness of 7 micrometers to 15 micrometers.

The adhesive film comprising the polymer resin represented by Formula 1 or Formula 2 according to the above embodiment has a minimum melt viscosity of 1,000 to 40,000 centipoise at a temperature of 100 ° C or less. Accordingly, one embodiment provides an adhesive film having a minimum melt viscosity of from 1,000 centipoise to 40,000 centipoise at a temperature of 100 ° C or less. The minimum melt viscosity within this range can facilitate initial compression properties and indentation uniformity. In particular, the minimum melt viscosity may range from 1,000 centipoise to 20,000 centipoise, for example from 1,000 centipoise to 10,000 centipoise. The minimum melt viscosity was measured by the following method.

The film was measured at a temperature of 30 ° C to 180 ° C using ARES G2 (TA Instruments) at a heating rate of 10 ° C / min, a strain of 5%, and a frequency of 1 rad / sec at 100 ° C. Whether there is a minimum melt viscosity and a value of the minimum melt viscosity at a temperature of less than 100 °C. Here, parallel plates and disposable aluminum plates having a diameter of 8 mm were used.

As measured by differential scanning calorimetry (DSC) and calculated according to Equation 1, the film may have a heat change ratio of 30% or less: heat change ratio (%) = [(T ₀ - T ₁ ) / T ₀ ] × 100 --- (1) wherein T ₀ is measured by DSC at a heating rate of 10 ° C / min in a temperature range from -50 ° C to 250 ° C The initial heat of the film, and T ₁ is taken at a heating rate of 10 ° C / min in a temperature range from -50 ° C to 250 ° C after being placed at 25 ° C for 70 hours. The heat of the film that is measured by the DSC. Specifically, the heat change ratio may be 20% or less.

The rate of heat change can be measured by any of the usual methods used in the art. The heat change ratio can be measured by the following exemplary method. In this method, after dividing an anisotropic conductive film according to one embodiment into a sample, a differential scanning calorimeter (for example, model Q20 (TA Instruments)) is used at 25 ° C at 10 ° C. The initial heat (T ₀ ) of the sample was measured at a heating rate of /min at a temperature ranging from -50 ° C to 250 ° C. Next, the sample was placed at 25 ° C for 70 hours, and then the heat (T ₁ ) of the sample was measured in the same manner. The rate of change in heat is calculated according to Equation 1. When the heat change ratio is in the above range, the film is then provided with satisfactory storage stability, which prevents a decrease in the strength of the subsequent or an increase in the connection resistance.

Yet another embodiment of the present invention provides an adhesive film having a connection resistance of 5 ohms (Ω) or less than 5 ohms after the reliability test. Specifically, the adhesive film may have a connection resistance of 3 ohms or less after the reliability test. Within this range, the adhesive film can be cured at a low temperature while maintaining a low connection resistance, thereby improving connection reliability and maintaining storage stability for long-term use.

The connection resistance after the reliability test can be measured by the following method, but is not limited to the method.

Five samples of each adhesive film were prepared by the following methods: primary compression at 60 ° C, 1.0 million Pascals (MPa) and 1 second, and primary compression at 130 ° C, 60 MPa and 5 seconds. The connection was carried out under conditions, and then subjected to a reliability test by placing in a high temperature and high humidity chamber at 85 ° C and 85% relative humidity for 500 hours, and then measuring the resistance using a four-point probe method. The resistance meter applies a current of 1 mA and measures the voltage at the current, thereby calculating the resistance.

The adhesive film according to an embodiment of the present invention may have 5% or less in the compressed portion after preliminary compression for 1 second to 3 seconds at 55 ° C to 70 ° C and 1 million Pascals to 3 MPa Pascals. The area of the bubble, and exhibits a uniform indentation after a primary compression of 1 to 5 seconds at 120 ° C to 140 ° C and 50 MPa to 80 MPa.

1 is a cross-sectional view of a display device 30 in accordance with one embodiment of the present invention. The display device 30 includes: a first connection member 50 including a first electrode 70; a second connection member 60 including a second electrode 80; and an adhesive film 10 according to the present invention, the adhesive film 10 being disposed on the first connection The first electrode 70 and the second electrode 80 are connected between the member 50 and the second connection 60 member via the conductive particles 3.

In some embodiments, the first connecting member and the second connecting member may be structurally similar in terms of material, thickness, size, and physical interconnectivity. The first connecting member and the second connecting member have a thickness of from about 20 microns to about 100 microns. In other embodiments, the first connecting member and the second connecting member may be structurally and functionally different in terms of material, thickness, size, and physical interconnectivity. Examples of the first connecting member or the second connecting member may include glass, a printed circuit board, a flexible printed circuit board (FPCB), a film flip chip, a tape carrier package (TCP), and oxidation. Indium tin glass, but not limited to this. The first electrode or the second electrode may be a protruding electrode or a planar electrode. When the first electrode or the second electrode is a protruding electrode, the electrode has a height (H) and a width (W) and has a gap (G) between the electrode and the other electrode, wherein the height (H) of the electrode is about 2.50 microns to about 10 microns, the width (W) of the electrodes is from about 10 microns to about 90 microns, and the gap (G) between the electrodes is from about 10 microns to about 110 microns. Preferably, the height (H) of the electrode is from about 2.50 microns to about 9 microns, the width (W) of the electrode is from about 5 microns to about 80 microns, and the gap (G) between the electrodes is about 5 Micron to about 80 microns.

When the first electrode or the second electrode is a planar electrode, the electrode may have a thickness of 500 angstroms to 1,200 angstroms.

The first electrode or the second electrode may be indium tin oxide, copper, anthrone or indium zinc oxide (IZO), but is not limited thereto.

Preferably, the planar electrode has a thickness of 800 angstroms to 1,200 angstroms and the protruding electrode has a height of 6 micrometers to 10 micrometers. Here, when the insulating layer has a thickness of 4 μm to 20 μm, the film may exhibit sufficient bonding strength. More preferably, the planar electrode has a thickness of 1,000 angstroms and the protruding electrode has a height of 8 micrometers to 10 micrometers, in which case the insulating layer has a thickness of 6 micrometers to 12 micrometers.

Next, the present invention will be explained in more detail with reference to Preparation Examples, Examples, Comparative Examples, and Experimental Examples. However, it is to be understood that the examples are provided for illustration only and are not intended to limit the invention in any way. Example Preparation Example [Preparation Example 1 of Polymer Resin]

In a 500 ml round bottom separable flask with a stirrer, 64.5 g of 4,4'-bisphenol (4,4'-biphenol) and 35 g of 9,9'-bis(4-hydroxyphenyl)indole (9,9'-bis(4-hydroxyphenyl)fluorene) was dissolved in 120 ml of cyclohexanone, then 186.5 g of YD-128 was added as epoxy resin and 0.18 g of 2E4MZ was used as the imidazole catalyst and kept in a nitrogen atmosphere. The reaction was carried out at 145 ° C for 5 hours, whereby a polymer resin 1 (weight average molecular weight of 48,400 and glass transition temperature of 103 ° C) was obtained. [Preparation Example 2 of Polymer Resin]

In addition to using 55.9 g of 4,4'-bisphenol and 70 g of 9,9'-bis(4-hydroxyphenyl)fluorene instead of 64.5 g of 4,4'-bisphenol and 35 g of 9,9'-bis (4- Polymer resin 2 (weight average molecular weight: 47,600, glass transition temperature: 125 ° C) was polymerized in the same manner as in Preparation Example 1, except for hydroxyphenyl) hydrazine. [Preparation Example 3 of Polymer Resin]

In addition to using 32.7 grams of 4,4'-bisphenol and 105.1 grams of 9,9'-bis(4-hydroxyphenyl)anthracene instead of 64.5 grams of 4,4'-bisphenol and 35 grams of 9,9'-bis (4- Polymer resin 3 (weight average molecular weight: 47,000, glass transition temperature: 130 ° C) was polymerized in the same manner as in Production Example 1, except for hydroxyphenyl)fluorene. [Preparation Example 4 of Polymer Resin]

In addition to using 18.6 g of 4,4'-bisphenol and 140.2 g of 9,9'-bis(4-hydroxyphenyl)fluorene instead of 64.5 g of 4,4'-bisphenol and 35 g of 9,9'-bis (4- Polymer resin 4 (weight average molecular weight: 42,600, glass transition temperature: 140 ° C) was polymerized in the same manner as in Preparation Example 1, except for hydroxyphenyl)fluorene. [Preparation Example 5 of Polymer Resin]

Polymer resin 5 (weight average molecular weight: 48,600, glass transition temperature: 113 ° C) in the same manner as in Preparation Example 1, except that 65 g of 2,3-dihydroxynaphthalene was used instead of 64.5 g of 4,4'-bisphenol. ) Perform polymerization. [Preparation Example 6 of Polymer Resin]

In addition to using 64.5 g of 4,4'-bisphenol and 45.1 g of 9,9'-bis(6-hydroxy-2-naphthyl) anthracene instead of 64.5 g of 4,4'-bisphenol and 35 g of 9,9'-double Polymer resin 6 (weight average molecular weight: 29,200, glass transition temperature: 95 ° C) was polymerized in the same manner as in Preparation Example 1, except for (4-hydroxyphenyl)fluorene. [Preparation Example 7 of Polymer Resin]

Polymerization was carried out in the same manner as in Preparation Example 1, except that 93.2 g of 4,4'-bisphenol was used instead of 64.5 g of 4,4'-bisphenol and 35 g of 9,9'-bis(4-hydroxyphenyl)fluorene. Polymer 7 (having a weight average molecular weight of 50,200 and a glass transition temperature of 93 ° C) was polymerized.

The polymerization equivalent ratios of the polymer resins prepared in Preparation Examples 1 to 7 are shown in Table 1. Table 1 Fabrication of an anisotropic conductive adhesive film [Preparation Example 1 of Conductive Layer]

20% by weight of the polymer resin 1 obtained in Preparation Example 1 as a binder resin system serving as a film-forming substrate was dissolved in an equivalent amount of propylene glycol monomethyl ether acetate as a solvent, based on the total weight of the solid film. (propylene glycol monomethyl ether acetate, PGMEA), and then as a curing system, 30% by weight of hydrogenated epoxy resin (YX8000, epoxy equivalent of 205, viscosity of 1800 millipoise (mPs)), as a cationic polymerization catalyst 5% by weight of benzyl (4-hydroxyphenyl)methylphosphonium hexafluorophosphate, 4% by weight of R972 as nano cerium oxide, 1% by weight of KBM403 as a decane coupling agent, and as 40% by weight of insulating conductive particles (AUL-704 available from Sekisu Co., Ltd., Japan, having an average particle diameter of 4 μm) of an anisotropic conductive film-conductive filler were mixed, thereby preparing a conductive layer composition.

The conductive layer composition was applied to a white release film, and then the solvent was volatilized in a drier at 60 ° C for 5 minutes, thereby obtaining a dried conductive layer of 6 μm thick. [Preparation Example 1 of Insulating Resin Layer]

A 12 μm thick insulating resin layer containing no conductive particles was produced in the same manner as in Production Example 1 of the conductive layer except that the conductive particles were not used. [Example 1]

An anisotropic conductive adhesive film having a two-layer structure was fabricated by stacking and laminating the conductive layer obtained in Preparation Example 1 of the conductive layer and the insulating resin layer obtained in Preparation Example 1 of the insulating resin layer. [Example 2]

An anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1 except that the polymer resin 2 prepared in Preparation Example 2 was used instead of the polymer resin 1 prepared in Preparation Example 1. [Example 3]

An anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1 except that the polymer resin 3 prepared in Preparation Example 3 was used instead of the polymer resin 1 prepared in Preparation Example 1. [Example 4]

An anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1 except that the polymer resin 4 prepared in Preparation Example 4 was used instead of the polymer resin 1 prepared in Preparation Example 1. [Example 5]

An anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1 except that the polymer resin 5 prepared in Preparation Example 5 was used instead of the polymer resin 1 prepared in Preparation Example 1. [Example 6]

An anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1 except that the polymer resin 6 prepared in Preparation Example 6 was used instead of the polymer resin 1 prepared in Preparation Example 1. [Comparative Example 1]

Anisotropic conductivity having a two-layer structure was produced in the same manner as in Example 1 except that PKHH (manufactured by International Chemicals (InChem)) as a phenoxy resin was used instead of the polymer resin 1 prepared in Preparation Example 1. membrane. [Comparative Example 2]

Anisotropic conductivity having a two-layer structure was produced in the same manner as in Example 1 except that FX-293 (manufactured by Nippon Steel Chemical Co., Ltd.) as an anthracene resin was used instead of the polymer resin 1 prepared in Preparation Example 1. Then the film. [Comparative Example 3]

An anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1 except that the polymer resin 7 prepared in Preparation Example 7 was used instead of the polymer resin 1 prepared in Preparation Example 1. Experimental example

The preliminary compression properties of the anisotropic conductive adhesive film manufactured in Examples 1 to 6 and Comparative Example 1 to Comparative Example 3, the indentation uniformity after bonding, the initial connection resistance, after the reliability test were evaluated by the following methods Connection resistance, heat change ratio, adhesion strength, and minimum melt viscosity. The evaluation results are shown in Table 2. [Preliminary compression properties]

In order to evaluate the preliminary compression properties of the anisotropic conductive adhesive film, an integrated circuit (IC) wafer having a bump region of 1,430 μm (manufactured by Samsung LSI) and including a thickness of 5,000 angstroms were used. A glass substrate of an ITO circuit (manufactured by NeoView Kolon) was used as a binder material. Each of the prepared anisotropic conductive adhesive films was placed on a glass substrate and initially compressed at 60 ° C under a condition of 1 megaPascal for 1 second. After the preliminary compression, the release film was removed, and then observed with a microscope (manufactured by Olympus Corporation) to check whether or not bubbles were present between the terminals. In terms of the ratio of the bubble region to the compressed portion in the three observed positions, 0% to less than 5% represents an excellent image (O), 6% to less than 10% represents a good image (∆), and 10% or more. % represents a bad image (X). [Indentation uniformity after bonding]

Each sample was fabricated by performing main compression for 5 seconds at 130 ° C, 60 MPa after preliminary compression, and the samples were visually observed to determine indentation uniformity. Specifically, when the indentation on the opposite side of the driver integrated circuit is as clear as the indentation at the center portion, the result is determined to be a uniform indentation and the result is rated as good (O). This result was evaluated as uneven (X) when the indentation on the opposite side of the driver integrated circuit was not clear or blurred compared to the indentation at the central portion. [heat change ratio]

The initial heat (T ₀ ) of each of the adhesive films was measured by differential scanning calorimetry (DSC) at a heating rate of 10 ° C / min from a temperature range of -50 ° C to 250 ° C, and was After being placed at 25 ° C for 70 hours, the heat (T ₁ ) of the adhesive film was measured by DSC at a heating rate of 10 ° C / minute in a temperature range from -50 ° C to 250 ° C. The ratio of heat change of 20% or less is rated as excellent (O), 30% or less, and the ratio of heat change is rated as good (∆), and the ratio of heat change of more than 30% is rated as bad ( X). [Continue strength]

Using a joint tester (Dage Series - 4000), with a maximum load of 200 kg force and a test speed of 100 μm/sec, the initial compression was performed for 1 second at 60 ° C, 1 MPa Pascal and Each sample obtained by mainly compressing for 5 seconds at 130 ° C and 60 MPa Pascal was subjected to at least three measurements. The adhesion strength of 10 megapascals or more than 10 megapascals is rated as ◎, the adhesion strength of 5 megapascals to 10 megapascals is evaluated as O, and the adhesion strength of 1 megapascals to 5 megapascals is evaluated as ∆, and the case where the energy is not measured and the strength is evaluated as X. [Initial connection resistance]

Each of the adhesive films was initially compressed at 60 ° C, 1 MPa Pascal for 1 second and mainly compressed at 130 ° C, 60 MPa Pascal for 5 seconds, and the initial resistance of each of the adhesive films was evaluated. The initial resistance of 0.1 ohm or less was rated as good (O), the initial resistance of 0.1 ohm to 0.2 ohm was evaluated as ∆, and the initial resistance greater than 0.2 ohm was rated as X. [Connection resistance after reliability test]

The reliability of the five circuit-connected products of each sample was placed in a high-temperature and high-humidity chamber at 85 ° C and 85% relative humidity for 500 hours, and then the connection resistance was measured. The connection resistance was defined as reliable. Connection resistance after sex test. The connection resistance of 5 ohms or less was rated as good (O), and the connection resistance of more than 5 ohms was rated as bad (X). The initial connection resistance and the connection resistance after the reliability test were measured using a four-point probe method in which the resistance between the four points was measured using a four-probe connected to the resistance meter using a resistance meter. The resistance meter applies a current of 1 mA and measures the voltage at the current, thereby calculating the resistance. [minimum melt viscosity]

The minimum melt viscosity was measured in the following manner.

Each of the adhesive films was measured at 100 ° C to 180 ° C in a temperature range of 30 ° C to 180 ° C using ARES G2 (TA Instruments) at a heating rate of 10 ° C / min, a strain of 5%, and a frequency of 1 rad / sec. Whether there is a minimum melt viscosity and a value of the minimum melt viscosity at a temperature of C or less than 100 °C. Here, parallel plates and disposable aluminum plates having a diameter of 8 mm were used.

The measured minimum melt viscosity of 1,000 centipoise to 3,000 centipoise is rated as ◎, and the measured minimum melt viscosity of greater than 3,000 centipoise to 10,000 centipoise is evaluated as O, and the measured is greater than 10,000 The minimum melt viscosity of centipoise is rated as ∆, while the minimum melt viscosity occurring above 100 °C is rated as X. Table 2

While the invention has been described with respect to the embodiments of the present invention, it is understood that these embodiments and features are not intended to limit the invention. Therefore, the scope and spirit of the invention should be limited only by the scope of the appended claims and their equivalents.

3‧‧‧Electrical particles
10‧‧‧Next film
30‧‧‧Display device
50‧‧‧First connecting member
60‧‧‧Second connection member
70‧‧‧First electrode
80‧‧‧second electrode

1 is a cross-sectional view of a display device 30 including a first connection member 50 having a first electrode 70, a second connection member 60 having a second electrode 80, and a configuration in accordance with an embodiment of the present invention. An adhesive film connecting the first connecting member and the second connecting member to connect the first electrode and the second electrode.

3‧‧‧Electrical particles

10‧‧‧Next film

30‧‧‧Display device

50‧‧‧First connecting member

60‧‧‧Second connection member

70‧‧‧First electrode

80‧‧‧second electrode

Claims (18)

A polymer resin having a unit represented by Formula 1 or Formula 2: [Formula 1] ; [Formula 2] Wherein X ₁ and X ₂ are each a difunctional epoxy compound-derived unit or a liquid crystal original compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has a crosslinking functional group; Y ₁ and Y _{2 is} each a difunctional epoxy compound-derived unit, and each of Z ₁ and Z ₂ is a liquid crystal original compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has a crosslinking functional group, Or each of Y ₁ and Y ₂ is a liquid crystal original compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has a crosslinking functional group, and each of Z ₁ and Z ₂ is a difunctional epoxy The compound-derived unit; and n ₁ , n ₂ , m ₁ and m ₂ each independently represent an integer from 1 to 10. The polymer resin according to claim 1, wherein the difunctional epoxy compound-derived unit is a self-bifunctional bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol AD epoxy compound or a double A unit derived from a phenol S epoxy compound. The polymer resin according to claim 1, wherein the liquid crystal raw compound-derived unit comprises at least one selected from the group consisting of Formula A1 to Formula A7: [Formula A1] , [Formula A2] , [Formula A3] , [Formula A4] , [Formula A5] , [Formula A6] And [Formula A7] Wherein R ₁ to R ₂₄ are each independently hydrogen, fluoro, alkyl, thiol, methylthio, nitro or an alcohol, amine or carboxylic acid having from 0 to 20 alkyl or hydrogen, and at opposite ends Linking groups include ether linkages or ester linkages. The polymer resin according to any one of claims 1 to 3, wherein the polymer resin has a weight average molecular weight of 1,000 to 500,000. The polymer resin according to any one of claims 1 to 3, wherein the polymer resin has a glass transition temperature of from 95 ° C to 180 ° C. The polymer resin according to any one of claims 1 to 3, wherein the polymer resin is a bifunctional epoxy compound, a phenyl fluorene compound having a crosslinking functional group or a naphthyl group. It is prepared by a condensation reaction of a ruthenium compound and a liquid crystal original compound containing an aromatic or alicyclic compound and having a crosslinking functional group. The polymer resin according to claim 6, wherein the phenyl fluorene compound having the crosslinking functional group or the naphthyl fluorene compound is the liquid crystal original compound having the crosslinking functional group. The polymerization equivalent ratio is from 1:5 to 5:1. The polymer resin according to claim 6, wherein the phenyl fluorene compound having the crosslinking functional group or the naphthyl fluorene compound has a polymerization equivalent ratio to the difunctional epoxy compound of 1 : 5 to 5:1. An adhesive film comprising the polymer resin according to any one of claims 1 to 3. The adhesive film according to claim 9, wherein the adhesive film has a minimum melt viscosity of 1,000 to 40,000 centipoise at a temperature of 100 ° C or less. An adhesive film comprising a polymer resin having a unit represented by Formula 1 or Formula 2, a radical reaction material, a radical reaction initiator, and conductive particles, or comprising the unit having Formula 1 or Formula 2 The polymer resin, cationic polymerizable material, cationic polymerization initiator, and conductive particles: [Formula 1] ; [Formula 2] Wherein X ₁ and X ₂ are each a difunctional epoxy compound-derived unit or a liquid crystal original compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has a crosslinking functional group; Y ₁ and Y _{2 is} each a difunctional epoxy compound-derived unit, and each of Z ₁ and Z ₂ is a liquid crystal original compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has a crosslinking functional group, Or each of Y ₁ and Y ₂ is a liquid crystal original compound-derived unit, wherein the liquid crystal raw compound contains at least two aromatic or alicyclic compounds and has a crosslinking functional group, and each of Z ₁ and Z ₂ is a difunctional epoxy The compound-derived unit; and n ₁ , n ₂ , m ₁ and m ₂ each independently represent an integer from 1 to 10. The adhesive film according to claim 11, wherein the adhesive film comprises 10% by weight to 50% by weight of the polymer resin having the unit represented by Formula 1 or Formula 2, 10% by weight to 50% by weight of the radical reactive material, 0.5% by weight to 1% by weight of the radical reaction initiator, and 10% by weight to 40% by weight of the conductive particles. The adhesive film according to claim 11, wherein the adhesive film comprises 10% by weight to 50% by weight of the polymer resin having the unit represented by Formula 1 or Formula 2, 10% by weight to 50% by weight of the cationically polymerizable material, 0.5% by weight to 10% by weight of the cationic polymerization initiator, and 10% by weight to 40% by weight of the conductive particles. The adhesive film according to any one of claims 11 to 13, wherein the adhesive film has a structure of at least two layers, and the structure of the at least two layers includes a conductive layer containing conductive particles and An insulating resin layer containing no conductive particles. The adhesive film of claim 11, wherein the adhesive film has a minimum melt viscosity of from 1,000 centipoise to 40,000 centipoise at a temperature of 100 ° C or less. The adhesive film according to any one of claims 11 to 13, wherein the film is 30% or less as measured by differential scanning calorimetry (DSC) and calculated according to Equation 1. 30% heat change ratio: [Equation 1] Heat change ratio (%) = [(T ₀ - T ₁ ) / T ₀ ] × 100, where T ₀ is in the temperature range from -50 ° C to 250 ° C The initial heat of the adhesive film measured by differential scanning calorimetry at a heating rate of 10 ° C/min, and T ₁ is 70 ° after being placed at 25 ° C, at -50 ° The heat of the adhesive film measured by the differential scanning calorimetry at a heating rate of 10 ° C / min in a temperature range of C to 250 ° C. The adhesive film according to any one of claims 9 to 11, wherein the adhesive film is an anisotropic conductive adhesive film. A display device comprising: a first connecting member including a first electrode; a second connecting member including a second electrode; and the following according to any one of claims 9 and 11 to 13 a film disposed between the first connecting member and the second connecting member and connecting the first electrode and the second electrode.