KR101788382B1 - Polymer resin having a chemical structure 1, adhesive film comprising the polymer resin, and semiconductive device connected by the adhesive film - Google Patents

Abstract

상기 화학식 1에서,
X와 Y 중 적어도 어느 하나는 치환되거나 비치환된, 다환 방향족 탄화수소 함유기이고, 다른 하나는 치환되거나 비치환된, C_{6 -30}의 방향족 혹은 지환족 함유기이고, n은 1 내지 50의 정수이다.The present invention relates to a polymer resin of formula (1), a process for producing the same, an adhesive film containing the same, and a semiconductor device connected by the adhesive film.
[Chemical Formula 1]

In Formula 1,
At least one of X and Y is a substituted or unsubstituted polycyclic aromatic hydrocarbon-containing group and the other is a substituted or unsubstituted C ₆ -C ₃₀ aromatic or alicyclic group, and n is an integer of 1 to 50 to be.

Description

Technical Field [0001] The present invention relates to a polymer resin of Chemical Formula 1, an adhesive film containing the same, and a semiconductor device connected by the adhesive film.

The present invention relates to a polymer resin of formula (1), a process for producing the same, an adhesive film containing the same, and a semiconductor device connected by the adhesive film.

In recent years, in the field of electronic packaging, various kinds of film-shaped adhesives capable of easily connecting such terminals have been proposed as IC chips A flexible printed wiring board (FPC), a glass substrate on which an IC chip and an ITO (Indium-Tin-Oxide) electrode circuit are formed, and the like.

In the adhesive film containing conductive particles in the resin composition as one of the film-shaped adhesives, the resin in the adhesive flows by heating and pressing to seal the gaps between the electrodes which face each other on the connection object, and at the same time, And filled between the electrodes to enable electrical connection.

Recently, as the size of a small-sized panel emphasizing portability is widespread, the space between the electrode and the electrode is narrowed. In the bonding, the connecting board expands due to the heat and pressure during bonding. After bonding, the connecting board shrinks again, So that a large amount of bubbles are generated and the filling effect of the adhesive is deteriorated. Accordingly, there is a demand for a new adhesive film which can withstand the expansion and contraction of the connecting board due to heat and pressure, and specifically has a harder physical property, a smaller bubble generating area at the time of pressing, and an excellent adhesive force.

Japan public 2009-161755

none

It is an object of the present invention to provide a polymer resin having a small area for bubble formation during compression and a high film-forming property at the time of film formation, as well as excellent flexibility, heat resistance and connection properties. Another object of the present invention is to provide an adhesive film which can be connected even at a low temperature connection temperature, excellent in adhesion and reliability, and a semiconductor device connected by the film.

In one embodiment of the present invention, a polymeric resin comprising the structure of Formula (1) is provided.

[Chemical Formula 1]

In Formula 1,

At least one of X and Y is a substituted or unsubstituted polycyclic aromatic hydrocarbon-containing group and the other is a substituted or unsubstituted C ₆ -C ₃₀ aromatic or alicyclic group, and n is an integer of 1 to 50 to be.

In another embodiment of the present invention, there is provided an adhesive film comprising a polymer resin having a unit of the above formula (1).

In yet another embodiment of the present invention,

Gwaneung crosslinking reaction comprises a polycyclic aromatic hydrocarbon group-containing monomer and an initiator having a composition, or crosslinking polycyclic aromatic hydrocarbon group-containing monomer and a crosslinkable functional group in the C _{6 -30} aromatic or alicyclic containing monomer and an initiator having a having a gwaneung ≪ / RTI >

There is provided a process for producing a polymer resin comprising the structure of the above formula (1), which comprises polymerizing the reaction composition.

Still another embodiment of the present invention provides a semiconductor device connected by the adhesive film disclosed in the present application.

The polymer resin and the adhesive film containing the polymer resin according to one embodiment of the present invention have a small bubble generating area upon compression and are excellent in film formability at the time of film formation, as well as excellent in fluidity and connection properties. Further, the adhesive film comprising the polymer resin according to one embodiment can be connected even at a low temperature connection temperature, and has excellent adhesive force and connection reliability.

1 shows a first embodiment of the present invention in which a first connected member 50 including a first electrode 70, a second connected member 60 including a second electrode 80, A semiconductor device (30) according to an example of the present invention, comprising an adhesive film (10) as described herein, which is located between two connected members and connects the first electrode and the second electrode via conductive particles Fig.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

According to one embodiment of the present invention, there is provided a polymer resin comprising the structure of Formula (1).

[Chemical Formula 1]

Wherein at least one of X and Y is a substituted or unsubstituted polycyclic aromatic hydrocarbon-containing group and the other is a substituted or unsubstituted C ₆ -C ₃₀ aromatic or alicyclic group, And is an integer of 1 to 50. In one example, both X and Y may be substituted or unsubstituted polycyclic aromatic hydrocarbon-containing groups. In another example, the polycyclic aromatic hydrocarbon-containing group in which one of X and Y is a substituted or unsubstituted polycyclic aromatic hydrocarbon-containing group may be a substituted or unsubstituted C ₆ -C ₃₀ aromatic or alicyclic-containing group.

The unit of the formula (1) may be 50 mol% or more, specifically 60 mol% or more, and more specifically 70 mol% or more in the polymer resin. When the polymer resin having the above-mentioned range is used, the bubble can be reduced and the adhesive force can be improved.

Unless defined otherwise herein, 'substituted' means that a hydrogen atom in the compound is replaced by a halogen atom (F, Br, Cl, I), a halogenated alkyl, a hydroxy group, an alkoxy group, a nitro group, a cyano group, A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ alkoxy group, to C ₂₀ alkenyl groups, C ₂ to C ₂₀ alkynyl groups, C ₆ to C ₃₀ aryl groups, C ₇ to C ₃₀ arylalkyl group, C ₁ to C ₂₀ alkoxy group, C ₁ to C ₂₀ heterocyclic group, C ₃ to C ₂₀ heteroaryl group, a C ₃ to C ₂₀ cycloalkyl group, a (meth) acrylate groups, C ₃ to C ₂₀ cycloalkyl alkenyl, C ₄ to C ₂₀ cycloalkyl alkynyl group, C ₂ to C ₂₀ heterocycloalkyl group, and combinations thereof ≪ / RTI >

In addition, unless otherwise defined herein, "hetero" means containing one to three heteroatoms selected from N, O, S, and P;

In the definition of Formula 1, a polycyclic aromatic hydrocarbon-containing group is a group formed by fusing two or more aromatic rings together to form a polycyclic aromatic ring. Examples thereof include a naphthalene group, an anthracene group, a phenanthrene group, A pyrene group, a quinoline group, an isoquinoline group, a quinoxaline group, an acridine group, a quinazoline group, or a phthalazine group.

In the definition of the above formula (1), the C _{6 -30} aromatic-containing group is an aromatic hydrocarbon ring-containing group having 6 to 30 carbon atoms, for example, an aromatic hydrocarbon ring may be present singly or two or more aromatic rings may be directly connected to each other, Or may be a residue connected by.

Specifically, the C _{6 -30} aromatic-containing group may be selected from the group consisting of the following formulas A1 to A7:

(A1)

;

;

(A2)

;

;

(A3)

;

;

(A4)

;

;

(A5)

;

;

[Formula A6]

; 및

; And

(A7)

.

.

In the above formulas A1 to A7, R ¹ to R ¹⁸ are each independently hydrogen or a substituted or unsubstituted halogen, halogenated alkyl, OH, C _{1 -6} alkyl, nitro, cyano, carbonyl, thiol or C ₆ and _-30 aryl, k, l, m, n , o, p, q, r, s, t, u, v, w, x, y and z are each independently an integer of 0 to 3. The substituents or linking groups of R ¹ to R ¹⁸ in the above formulas A1 to A7 may be substituted or linked to the position of ortho-, meth-, or para- with respect to each benzene ring.

The polymer resin containing the unit of the formula (1) may be obtained by condensing polycyclic aromatic hydrocarbon group-containing monomers having a crosslinkable functional group or by condensing a polycyclic aromatic hydrocarbon group-containing monomer having a crosslinkable functional group with a C _{6 -30} aromatic or alicyclic Group-containing monomers by condensation reaction.

In another embodiment of the present invention, there is provided a reaction composition comprising a polycyclic aromatic hydrocarbon group-containing monomer having a crosslinkable adhesion group and an initiator, or a reaction composition comprising a polycyclic aromatic hydrocarbon group-containing monomer having a crosslinkable adhesion group and a C _{6 -30} aromatic group having a crosslinkable functional group Or an alicyclic group-containing monomer and an initiator, and subjecting the reaction composition to a polymerization reaction. The present invention also provides a process for producing a polymer resin comprising a structure represented by the above formula (1).

More specifically, the polymer resin containing the unit represented by the formula (1) is obtained by introducing the monomers into a reactor in which nitrogen gas is refluxed, adding a solvent such as cyclohexanone, and maintaining the temperature of the reactor at 100 to 200 ° C, Followed by polymerization for 1 hour to 50 hours. The polymerization equivalent ratio of the polycyclic aromatic hydrocarbon group-containing monomer having a crosslinking compatibility group to the C _{6 -30} aromatic or alicyclic group-containing monomer having a crosslinkable functional group is 1: 9 to 9: 1, specifically 2: 8 to 8: 2 Lt; / RTI > The crosslinkable functional group is a reactive group capable of forming a crosslink by polymerization, and examples thereof include an epoxy group, a hydroxyl group, an acrylate group, and a carboxyl group.

The weight average molecular weight of the polymer resin having the unit represented by the formula (1) may be in the range of 1,000 to 500,000, and may be in the range of 2,000 to 200,000, more specifically 5,000 to 100,000. The above range can be advantageous in terms of film formability, flexibility, heat resistance, and the like. The glass transition temperature of the polymer resin having the unit represented by the formula (1) may be in the range of 80 캜 to 180 캜, specifically in the range of 100 캜 to 160 캜.

Examples of the reaction catalyst which can be used in the production of the polymer resin having the unit of the formula (1) include an amine type, an ammonium type or an imidazole type. Examples of the amine-based reaction catalyst include linear amines, aliphatic amines, modified aliphatic amines, aromatic amines, secondary amines, and tertiary amines, and specific examples thereof include benzyldimethylamine, triethanolamine, triethylenetetramine, Diethylenetriamine, triethylenamine, dimethylaminoethanol, and tri (dimethylaminomethyl) phenol.

Specific examples of the imidazole-based reaction catalyst include imidazole, isoimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, butylimidazole, 2- 2-methylimidazole, 2-undecenedimidazole, 1-vinyl-2-methylimidazole, 2-n-heptadecylimidazole, 2- 2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-heptadecylimidazole, Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-methylimidazole, adduct of imidazole and methylimidazole, adduct of imidazole and trimellitic acid, 2-n-heptadecyl-4-methylimidazole, phenyl Methylimidazole, benzylimidazole, 2-methyl-4,5-diphenylimidazole, 2,3,5-triphenylimidazole, 2-styrylimidazole, 1- Benzyl) -2-methylimidazole, 2- (2-hydroxy-4-t-butylphenyl) -4,5-diphenylimidazole, 2- Diphenylimidazole, 2- (3-hydroxyphenyl) -4,5-diphenylimidazole, 2- (p-dimethyl- Diphenylimidazole, di (4,5-diphenyl-2-imidazole) -benzene-1,4,2-naphthyl-4,5- 2-methylimidazole, 2-p-methoxystyrylimidazole, and the like, but are not limited thereto.

The reaction catalyst may be used in an amount of about 0.5 wt% to about 20 wt%, for example, about 1 wt% to about 15 wt%, or about 1 wt% to about 10 wt%, based on the total weight of the polymeric resin- % ≪ / RTI > by weight.

Hereinafter, an adhesive film according to an embodiment of the present invention will be described. This embodiment relates to an adhesive film comprising a polymer resin including the unit of the above formula (1). The adhesive film may further include a radical reactive substance and a radical reaction initiator, or a cationic polymerizable substance and a cationic polymerization initiator, in addition to the polymer resin having the unit of the formula (1). Specifically, the adhesive film may further include a cationic polymerizable substance and a cationic polymerization initiator. The polymer resin containing the unit of the formula (1) in the adhesive film may be contained in an amount of about 10% by weight to about 70% by weight, specifically 20% by weight to 60% by weight.

In one example, the adhesive film may comprise a polymeric resin having units of formula (I), a radical reactive material, and a radical reaction initiator. Examples of the radical reactive material include (meth) acrylate-based polymeric materials such as (meth) acrylate oligomers or (meth) acrylate-based monomers. Examples of the (meth) acrylate monomer include 6-hexanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ) Acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol (meth) acrylate, 2- hydroxyalkyl (meth) acryloylphosphate, 4-hydroxycyclohexyl (Meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylol ethane di (meth) acrylate, trimethylol propane di (meth) acrylate and the like. Examples of the (meth) acrylate oligomer include epoxy (meth) acrylate type epoxy resins having an intermediate molecular structure such as bisphenol such as 2-bromohydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AD, (4-hydroxyphenyl) ether and the like, and those having a skeleton such as an alkyl group, an aryl group, a methylol group, an allyl group, a cyclic aliphatic group, a halogen (such as tetrabromobisphenol A), a nitro group, and the like may be used. However, the (meth) acrylate oligomer is not limited thereto.

The radical reactive material may be contained in an amount of 10 to 40% by weight based on the solid content of the adhesive film. Within the above range, properties such as adhesion and appearance can be excellent, and reliability and stability can be obtained.

As examples of the radical reaction initiator, at least one of a photopolymerization initiator or a thermosetting reaction initiator may be used in combination. Examples of the photopolymerization type reaction initiator include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4-methyldiphenyl sulfide, isopropyl thioxanthone, diethyl thioxanthone, ethyl 4-diethylbenzoate, benzoin ether, Propyl ether, 2-hydroxy-2-methyl-1-phenylpropane-1-one, diethoxyacetophenone and the like can be used, but are not limited thereto. As the thermosetting type reaction initiator, a peroxide system and an azo system may be used, but the present invention is not limited thereto. As the peroxide system, benzoyl peroxide, lauryl peroxide, t-butyl peroxyl laurate, 1,1,3,3,4-methyl butyl peroxy-2-ethylhexanoate and the like can be used. Examples of azo compounds include azo compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis Azobis (2-methylbutylonitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2'- Azobis [N- (2-propenyl) -2-methylpropionimide], 2,2'-azobis Azobis (cyclohexane-1-carbonitrile), 1 - [(cyano-1-methylethyl) azo] formamide And the like, but are not limited thereto.

The radical reaction initiator may be contained in an amount of 0.5-10% by weight based on the solid content in the adhesive film. Within the above range, a sufficient reaction required for curing takes place, and excellent physical properties can be expected in adhesion strength, reliability, etc. after bonding through formation of an appropriate molecular weight.

In another example, the adhesive film may include a polymer resin having a unit of the above formula (1), a cationic polymerizable substance, and a cationic polymerization initiator.

As the cationic polymerizable substance, an epoxy resin, specifically, a thermosetting epoxy resin can be used. For example, an epoxy resin having an epoxy equivalent of about 90 g / eq to about 5000 g / eq and having two or more epoxy groups in the molecule Can be used. More specifically, it may include at least one epoxy resin selected from the group consisting of hydrogenated, bisphenol-type, novolak-type, glycidyl-type, aliphatic and alicyclic epoxy resins. For example, a bisphenol-type epoxy resin can be used. The cationic polymerizable material may be 10% to 50% by weight, specifically 15% to 45% by weight, based on the solids content of the adhesive film.

More specifically, a hydrogenated epoxy resin or a propylene oxide-based epoxy resin can be used. Use of a hydrogenated epoxy resin or a propylene oxide-based epoxy resin enables rapid curing at a low temperature and secures good stability.

The hydrogenated epoxy resin is specifically an alicyclic hydrogenated epoxy resin such as a hydrogenated bisphenol A type epoxy resin or a cycloaliphatic system. As the cycloaliphatic epoxy resin, resins having a structure such as alicyclic diepoxyacetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxyate, or vinylcyclohexene dioxide may be used. The hydrogenated bisphenol A type epoxy resin is generally obtained by using a hydrogenated bisphenol A derivative and epichlorohydrin, and may be a structure in which a double bond in a bisphenol A molecular structure is substituted with a hydrogen molecule.

The cationic polymerization initiator is not limited as long as it can catalyze the curing of the epoxy resin, and for example, sulfone, imidazole, isocyanate, amine, amide, phenol or acid anhydride curing agents can be used These may be used alone or in combination of two or more. The cationic polymerization initiator may be contained in an amount of 0.5-10% by weight based on the solid content in the adhesive film. Within the above range, a sufficient reaction required for curing takes place, and excellent physical properties can be expected in adhesion strength, reliability, etc. after bonding through formation of an appropriate molecular weight.

In another example, the adhesive film may further comprise conductive particles in addition to the components.

The conductive particles include, for example, metal particles including Au, Ag, Ni, Cu, and Pb, carbon particles, particles coated with a metal on the polymer resin, particles coated with a metal on a polymer resin, Etc. may be used. As the polymer resin, polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol and the like can be used, but the present invention is not limited thereto. Examples of the metal coating the polymer resin include, but are not limited to, Au, Ag, Ni, Cu, and Pb. Specifically, in the case of OLB (Outer Lead Bonding), since the adherend is an ITO (Indium Tin Oxide) glass surface, the core portion is made of a plastic material so that the ITO is not damaged by the pressure generated in the connection process of the anisotropic conductive film Metal particles such as Ni can be used to connect a PCB substrate. In the case of a PDP (Plasma Display Panel), a voltage applied to a circuit is very high, so that gold (Au) ). In the case of COG (Chip On Glass) or COF (Chip On Film) having a narrow pitch, insulated conductive particles coated with a thermoplastic resin on the surface of the conductive particles can be used. The conductive particles may include 5 to 40% by weight, and more preferably 7 to 30% by weight, based on the total weight of the adhesive film. Stable connection reliability can be ensured within the above range, and a low connection resistance can be exhibited.

In another example, the adhesive film may further include a binder resin in addition to the polymer resin having the unit of the formula (1). Examples of the binder resin that can be used include at least one selected from the group consisting of acrylonitrile-based, phenoxystyrene, butadiene-based, acrylate-based, urethane-based, polyamide-based, silicone-based and NBR (nitrilebutadiene rubber) But is not limited thereto. Alternatively, as the binder resin, an olefin resin, an acrylonitrile butadiene copolymer, a carboxyl terminal acrylonitrile butadiene copolymer, a polyimide resin, a polyester resin, a polyvinyl butyral resin, an ethylene-vinyl acetate copolymer, At least one of a styrene-butylene-styrene (SBS) resin, a styrene-ethylene-butylene-styrene (SEBS) resin, an epoxy resin or a phenoxy resin can be used.

The adhesive film may be an anisotropic conductive adhesive film in one example. The anisotropically conductive adhesive film may have a single-layer structure containing conductive particles, a polymer resin of Formula (1) and a cured portion, or a two-layer structure of a conductive layer containing conductive particles and an insulating resin layer containing no conductive particles. The composition of the conductive layer and the insulating resin layer may be the same only in the presence or absence of the conductive particles. Therefore, the conductive layer and the insulating resin layer in the above two-layer structure or more may independently include a polymer resin of the general formula (1). For example, the anisotropic conductive film may have a two-layer structure in which a conductive layer and an insulating resin layer are laminated or a three-layer structure in which a first insulating resin layer and a second insulating resin layer are laminated on both surfaces of the conductive layer, Layer structure in which a first insulating resin layer and a second insulating resin layer are laminated on both surfaces and a third insulating resin layer is laminated on any one of the insulating resin layers.

In the case of a two-layer structure, the thickness of the insulating resin layer may be larger than the thickness of the conductive layer, and specifically, the thickness of the insulating resin layer may be in the range of one to four times the thickness of the conductive layer. In this range, the insulating resin is sufficiently filled between adjacent circuits, so that good insulation and adhesion can be exhibited.

In the case of a three-layer structure, the thickness of the first insulating resin layer may be 2 占 퐉 or less, the thickness of the second insulating resin layer may be in a range of 7 占 퐉 to 18 占 퐉, and the thickness of the conductive layer may be 0.5 times To 2 times. More specifically, the thickness of the first insulating resin layer may be 1 占 퐉 or less, and the thickness of the second insulating resin layer may be in a range of 7 占 퐉 to 15 占 퐉.

The adhesive film comprising the polymer resin of Formula 1 according to the above-mentioned Examples was compressed at 90 ° C for 1 second, 1 MPa for pressure bonding and 130 ° C for 5 seconds and 3 MPa for final compression, Can be less than 20%. Specifically, the space portion bubble area may be 15% or less, more specifically 10% or less. Further, it is preferable that the adhesive film has an adhesive strength of 15 MPa or more, specifically 16 MPa or more after compression bonding at 90 ° C for 1 second, 1 MPa of pressure bonding and 130 ° C for 5 seconds and 3 MPa of final compression, May range from 17 MPa to 50 MPa.

Another example of the present invention also provides an adhesive film having a connection resistance of 5? Or less after reliability evaluation. Specifically, the connection resistance after the reliability evaluation may be 3 Ω or less, for example, 1 Ω or less, specifically 0.1 Ω or less. In this range, it is possible to maintain a low connection resistance while being able to be cured at a low temperature, thereby improving the connection reliability, and also there is an advantage that the storage stability can be maintained for a long period of time.

The method of measuring the connection resistance after the above reliability evaluation is not particularly limited, and a non-limiting example is as follows.

Five specimens were respectively prepared by pressurizing at 90 DEG C, 1.0 MPa for 1 second, and final compression at 130 DEG C and 3 MPa for 5 seconds. Each specimen was held at 85 DEG C and 85% relative humidity for reliability evaluation After storing the circuit connections in a high temperature and high humidity chamber for 500 hours, measure the resistance using the 4 point probe method. The resistance measuring device applies 1mA and the resistance is calculated by the measured voltage.

In one embodiment of the present invention,

A first connected member containing a first electrode;

A second connected member containing a second electrode; And

And a connecting film as described herein, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode.

In one aspect, the first and second connected members may be structurally similar in terms of material, thickness, dimension, and physical interconnectivity. The thickness of the first and second connected members is about 20 to 100 탆. In another aspect, the first connected member and the second connected member may not be structurally and functionally similar in terms of material, thickness, dimension, and physical interconnectivity. Examples of the first connected member and the second connected member include, but are not limited to, glass, printed circuit board (PCB), FPCB, COF, TCP, ITO glass and the like. The first electrode or the second electrode may be in the form of a protruding electrode or a planar electrode. In the case of the protruding electrode, the height H of the electrode, the width W, and the gap G between the electrode and the electrode exist, the height H of the electrode is about 2.50 μm to 10 μm, About 10 [mu] m to 90 [mu] m, and the gap (G) between the electrode and the electrode may range from about 10 [mu] m to 110 [mu] m. Preferably, the height H of the electrode is about 2.50 탆 to 9 탆, the width W of the electrode is about 5 탆 to 80 탆, and the gap G between the electrode and the electrode is about 5 탆 to 80 탆 .

For planar electrodes, the thickness may range from 500 to 1200 ANGSTROM.

As the first electrode or the second electrode, ITO, copper, silicon, IZO, or the like may be used, but the present invention is not limited thereto.

Preferably, the thickness of the planar electrode is 800 ANGSTROM to 1200 ANGSTROM, and the height of the protruding electrode is 6 to 10 mu m. At this time, if the thickness of the insulating layer is 4 탆 to 20 탆, sufficient adhesion can be exhibited. More preferably, the height of the planar electrode is 1000 占 and the height of the protruding electrode is 8 占 퐉, wherein the thickness of the insulating layer is 6 占 퐉 to 12 占 퐉.

Hereinafter, the present invention will be described in more detail by describing Production Examples, Examples, Comparative Examples and Experimental Examples. However, the following Production Examples, Examples, Comparative Examples and Experimental Examples are merely examples of the present invention, and the present invention should not be construed as being limited thereto.

Example

Manufacturing example

[Production Example 1 of Polymer Resin]

After dissolving 54 g of 2,2 '- (naphthalene-1,6-diylbis (oxy)) bis (methylene) dioxirane and 45.6 g of bisphenol A in PGMEA, 0.1 g of TBAB (TetraButylmmonium Bromide) was placed in a 100 ml round- Followed by stirring for 24 hours. The resultant was washed with methanol and water, and the resulting precipitate was dried to obtain Polymer Resin 1 (unit: 100 mol%, Tg: 116 ° C) having a unit of Mw of 20,000 and having the formula 1-1.

[Formula 1-1]

[Production Example 2 of Polymeric Resin]

After dissolving 54 g of 2,2 '- (naphthalene-1,6-diylbis (oxy)) bis (methylene) dioxirane and 32 g of naphthalene-2,3-diol in PGMEA, 0.1 g of TBAB was placed in a 100 ml round- Followed by stirring for 24 hours. After washing with methanol and water, the resulting precipitate was dried to obtain Polymer Resin 2 (100 mol% of units of Formula 1-2, Tg: 135 ° C) consisting of units of Formula 1-2 having Mw of 20,000.

[Formula 1-2]

[Production Example 3 of Polymeric Resin]

After dissolving 22.7 g of 2,2 '- (naphthalene-1,6-diylbis (oxy)) bis (methylene) dioxirane and 20.4 g of anthracene-9,10-diol in PGMEA, 0.1 g of TBAB was placed in a 100 ml round- C < / RTI > for 24 hours. The resultant was washed with methanol and water, and the resulting precipitate was dried to obtain Polymer Resin 3 (100 mol% of units of Formula 1-3, Tg: 142 DEG C) having units of Formula 1-3 at an Mw of 18,000.

[Formula 1-3]

[Production Example 4 of Polymer Resin]

105 g of 9,9'-bis (4-hydroxyphenyl) fluorene and 76.6 g of 2,2 '- (naphthalene-1,6-diylbis (oxy)) bis (methylene) dioxirane were dissolved in PGMEA and 0.5 g of TBAB And the mixture was stirred at 100 ° C for 24 hours. The resultant was washed with methanol and water, and the resulting precipitate was dried to obtain Polymer Resin 4 (100 mol% of units of Formula 1-4, Tg: 148 ° C) composed of units of Formulas 1-4 at a Mw of 20,000.

[Formula 1-4]

 [Production Example 5 of Polymeric Resin]

54 g of 9,9'-bis (4-hydroxyphenyl) fluorene and 31.5 g of DGEBA (Diglycidyl ether of bisphenol A) were dissolved in PGMEA and 0.09 g of TBAB was added to a 100 ml round-bottomed flask and stirred at 100 ° C for 24 hours. The resultant was washed with methanol and water, and the resulting precipitate was dried to obtain Polymer Resin 5 (100 mol% of Tg: 141 ° C) having a unit of Mw of 20,000 and having the formula (2).

(2)

Preparation of anisotropic conductive adhesive film

[Example 1] Single layer structure

Based on the solid weight of the entire film, a binder resin part serving as a matrix for film formation was prepared by mixing 45 wt% of the polymeric resin 1 obtained in Preparation Example 1 (dissolved in a volume ratio of 40 vol% to xylene / ethyl acetate in an azeotropic mixed solvent) 15 wt% of a propylene oxide-based epoxy resin (EP-4000S, Adeka, Japan), 15 wt% of a bisphenol A-based epoxy resin (JER834, Mitsubishi Chemical Co., Ltd.), 15 wt% of a thermosetting cationic curing agent (AUL-704, average particle diameter 4 μm, SEKISUI Co., Ltd., Japan) of 5% by weight, and 20% by weight of the conductive particles were mixed and then mixed to prepare an anisotropic conductive composition.

The anisotropic conductive composition was coated on a white release film, and the solvent was evaporated for 5 minutes in a drier at 70 캜 to produce a one-layer anisotropic conductive adhesive film having a thickness of 15 탆.

[Example 2] [Conductive layer production example 1]

Based on the solid weight of the entire film, a binder resin part serving as a matrix for film formation was prepared by mixing 45% by weight of the polymer resin 2 obtained in Preparation Example 2 (dissolved in 40% by volume of xylene / ethyl acetate in an azeotropic mixed solvent) 15 wt% of a propylene oxide-based epoxy resin (EP-4000S, Adeka, Japan), 15 wt% of a bisphenol A-based epoxy resin (JER834, Mitsubishi Chemical Co., Ltd.), 15 wt% of a thermosetting cationic curing agent (AUL-704, average particle size of 4 탆, SEKISUI, Japan) as a filler for imparting a conductive property, and then mixed to prepare a conductive layer composition Respectively.

The conductive layer composition was coated on a white release film, and the solvent was evaporated for 5 minutes in a drier at 70 ° C to obtain a 4 μm thick dried conductive layer film.

[Insulating resin layer production example 1]

Based on the solid weight of the entire film, a binder resin part serving as a matrix for film formation was prepared by mixing 45 wt% of the polymeric resin 1 obtained in Preparation Example 1 (dissolved in a volume ratio of 40 vol% to xylene / ethyl acetate in an azeotropic mixed solvent) 25 wt% of a propylene oxide-based epoxy resin (EP-4000S, Adeka, Japan), 25 wt% of a bisphenol A-based epoxy resin (JER834, Mitsubishi Chemical, Japan), 25 wt% of a thermosetting cationic curing agent , Sanshin Chemical Co., Ltd., Japan) were mixed to prepare an insulating resin layer composition.

The insulating resin layer composition was coated on a white release film and the solvent was evaporated in a drier at 70 캜 for 5 minutes to prepare an insulating resin layer containing no conductive particles having a thickness of 11 탆.

[Example 3]

In Example 2, an anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 2, except that the polymer resin 3 of Production Example 3 was used instead of the polymer resin 2 of Production Example 2 in the conductive layer Respectively.

[Example 4]

In Example 2, an anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 2, except that the polymer resin 4 of Production Example 4 was used instead of the polymer resin 2 of Production Example 2 in the conductive layer Respectively.

[Comparative Example 1]

The procedure of Example 1 was repeated except that the biphenyl fluorene resin FX-293 (manufactured by Shinil Chemical Co., Ltd.) was used instead of the polymer resin 1 of Production Example 1 in Example 1 to obtain a two-layer structure An anisotropic conductive adhesive film was produced.

[Comparative Example 2]

In Example 1, 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 of Production Example 5 was used instead of the polymer resin 1 of Production Example 1.

The components and the layer structures used in the production of the anisotropic conductive adhesive films of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 1.

Polymer resin Practice 1 common Practice 2 Practice 3 Practice 4 Comparison 1 Comparison 2 One-story structure Two-layer structure One-story structure One-story structure Insulating layer Conductive layer Polymer 1 45 45 - - - - - Polymer 2 - 45 - - - - Polymer 3 - - 45 - - - Polymer 4 - - - 45 - - Polymer 5 - - - - - 45 FX-293 45 Epoxy resin EP4000S 15 25 15 15 15 15 15 JER-834 15 25 15 15 15 15 15 Hardener Si-60L 5 5 5 5 5 5 5 Conductive particle AUL704F 20 20 20 20 20 20 Total 100 100 100 100 100 100 100 thickness 15um 11 μM 4um 4um 4um 15um 15um

Experimental Example

With respect to the anisotropically conductive adhesive films prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the space portion bubble area, the bonding strength, the initial connection resistance, and the connection resistance after the reliability evaluation were measured by the measurement method described below, Are shown in Table 2 below.

 [Space Bubble Area]

In order to evaluate the bubble generation area of the adhesive film, an IC chip (Samsung LSI) having a bump area of 1430 mu m and a glass substrate having an indium tin oxide circuit having a thickness of 5000 ANGSTROM (manufactured by Neoview Kolon) Respectively. The anisotropically conductive adhesive film thus prepared was placed on the organic substrate and pressed at 90 DEG C for 1 second at 1 MPa. After press-bonding, the specimens were pressed at 130 DEG C for 5 seconds and 3 MPa, and the bubble generation area in the specimen was measured by the following method. The bubble generation area was taken at 10 places of the interelectrode space using model name BX51 manufactured by OLYMPUS, and the area where the bubble was generated based on the space area (250 pitches in the lateral direction, 3 mm in length) between the electrodes was obtained and the average value The average value of the specimens was calculated.

[Adhesive strength]

Bond tester Dage Series-4000 was tested under the conditions of maximum load: 200 kgf and test speed: 50 mm / min. The specimen was pressurized at 90 ° C for 1 second and 1 MPa at 130 ° C for 5 seconds and 3 MPa. ) Was used to measure a total of 5 times for each specimen and averaged.

[Initial connection resistance]

The initial resistance was measured after press bonding at 90 DEG C for 1 second and 1 MPa, and after main compression at 130 DEG C for 5 seconds and 3 MPa.

[Connection resistance after reliability evaluation]

For reliability evaluation, the circuit connections of 5 samples for each sample were stored for 500 hours in a high temperature and high humidity chamber maintained at 85 DEG C and 85% relative humidity, and then the connection resistance was measured. After the initial and reliability evaluation, the connection resistance measurement is a 4-point probe method, which can use a resistance measuring device. The resistance between four points is measured by using four probes connected to the device. The resistance measuring device applies 1mA and the resistance is calculated by the measured voltage.

Example
One Example
2 Example
3 Example
4 Comparative Example
One Comparative Example
2 Space Bubble Area (%) 9 4 7 8 25 37 Adhesive strength (MPa) 20 22 22 18 12 18 Initial connection resistance
(Ω) 0.053 0.049 0.052 0.050 0.052 0.055 Connection resistance after reliability evaluation
(Ω) 0.057 0.055 0.054 0.055 0.069 0.203

As can be seen from the results of Table 2, the anisotropic conductive film containing the polymer resin of Formula 1 has a bubble-generating area of 10% or less at the time of compression and excellent in bonding strength and reliability even at a low temperature connection temperature, In Comparative Example 1 or Comparative Example 2 in which other polymer resin was used in place of the polymer resin of Comparative Example 1, unfavorable results were obtained in terms of the bubble area in the space, the bonding strength, and the connection resistance after reliability evaluation.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that such detail is solved by the person skilled in the art without departing from the scope of the invention. will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (22)

A polymer resin comprising the structure of formula (1).
[Chemical Formula 1]

In Formula 1,
At least one of X and Y is a substituted or unsubstituted polycyclic aromatic hydrocarbon-containing group and the other is a substituted or unsubstituted C ₆ -C ₃₀ aromatic or alicyclic group, And is an integer of 1 to 50. The process according to claim 1, wherein the polycyclic aromatic hydrocarbon-containing group is a naphthalene group, an anthracene group, a phenanthrene group, a pyrene group, a quinoline group, an isoquinoline group, a quinoxaline group, an acridine group, a quinazoline group, Polymer resin. The polymer resin according to claim 1, wherein the aromatic-containing group of C _{6 -30} is a residue in which the aromatic hydrocarbon ring is present singly or two or more aromatic rings are directly connected or connected by another linking group. 4. The polymer resin of claim 3, wherein the C _6-30 aromatic containing group is selected from the group consisting of the following formulas A1 to A7.
(A1)

;
(A2)

;
(A3)

;
(A4)

;
(A5)

;
[Formula A6]

; And
(A7)

.
In the general formula A1 to A7, R ¹ to R ¹⁸ are each independently hydrogen, substituted or unsubstituted, halogen, halogenated alkyl, OH, C _1-6 alkyl, nitro, cyano, carbonyl, thiol or C ₆ and _-30 aryl, k, l, m, n , o, p, q, r, s, t, u, v, w, x, y, and z are each independently an integer of 0 to 3. The method of claim 1 wherein the C _{6 -30} alicyclic containing group is an alicyclic hydrocarbon ring is present alone, or two or more alicyclic ring is connected directly or residues, polymeric resin connected by another connecting group. The polymer resin according to any one of claims 1 to 5, wherein the weight average molecular weight of the polymer resin is in the range of 1,000 to 500,000. The polymer resin according to any one of claims 1 to 5, wherein the polymer resin has a glass transition temperature of 80 to 180 占 폚. The method according to any one of claims 1 to 5, wherein the polymer resin contains a polycyclic aromatic hydrocarbon group-containing monomers having a crosslinkable functional group or a polycyclic aromatic hydrocarbon group-containing monomer having a crosslinkable functional group and a crosslinkable functional group Of a C _{6 -30} aromatic or alicyclic group-containing monomer. The polymer resin according to claim 8, wherein the polymerization equivalent ratio of the polycyclic aromatic hydrocarbon group-containing monomer having a crosslinkable functional group to the C _{6 -30} aromatic or alicyclic group-containing monomer having a crosslinkable functional group is 1: 9 to 9: 1. The polymer resin according to any one of claims 1 to 5, wherein the unit of the formula (1) is at least 50 mol% of the polymer resin. An adhesive film comprising the polymer resin according to any one of claims 1 to 5. The adhesive film according to claim 11, wherein the adhesive film has a space area bubble generation area of 20% or less under conditions of pressurization at 90 DEG C, 1 second, 1 MPa, and main compression at 130 DEG C for 5 seconds and 3 MPa. An adhesive film comprising a polymer resin having a unit of the formula (1), a conductive particle, a radical reactive substance and a radical reaction initiator, or a polymer resin having a unit of the formula (1), a conductive particle, a cationic polymerizable substance and a cationic polymerization initiator.
[Chemical Formula 1]

In Formula 1,
At least one of X and Y is a substituted or unsubstituted polycyclic aromatic hydrocarbon-containing group and the other is a substituted or unsubstituted C ₆ -C ₃₀ aromatic or alicyclic group, and n is an integer of 1 to 50 to be. The method according to claim 13,
10 to 70% by weight of a polymer resin having a unit of the formula (1)
5 to 40% by weight of conductive particles,
10% to 40% by weight of a radical reactive material, and
And 0.5 to 10% by weight of a radical reaction initiator. The method according to claim 13,
10 to 70% by weight of a polymer resin having a unit of the formula (1)
5 to 40% by weight of conductive particles,
10% to 50% by weight of a cationically polymerizable material, and
And 0.5% by weight to 10% by weight of a cationic polymerization initiator. The adhesive film according to any one of claims 13 to 15, wherein the adhesive film further comprises a binder resin in addition to the polymer resin of the formula (1). The adhesive film according to any one of claims 13 to 15, wherein the adhesive film has a structure of two or more layers including a conductive layer containing conductive particles and an insulating resin layer not containing conductive particles. A reaction composition comprising a polycyclic aromatic hydrocarbon group-containing monomer having a crosslinkable functional group and an initiator, or a reaction composition containing a polycyclic aromatic hydrocarbon group-containing monomer having a crosslinkable functional group and a C _{6 -30} aromatic or alicyclic group- ≪ / RTI >
Wherein the reaction composition is subjected to a crosslinking reaction.
[Chemical Formula 1]

In Formula 1,
At least one of X and Y is a substituted or unsubstituted polycyclic aromatic hydrocarbon group and the other is a substituted or unsubstituted aromatic or alicyclic group having _{6 to 30} carbon atoms and n is an integer of 1 to 50; 19. The method according to claim 18, wherein the crosslinkable reactor is an epoxy group, a hydroxyl group, an acrylate group, or a carboxyl group. 19. The process according to claim 18, wherein the crosslinking reaction comprises reacting the reaction composition for 1 hour to 50 hours while maintaining the reaction composition at 100 占 폚 to 200 占 폚. An adhesive film according to any one of claims 13 to 15, wherein the adhesive film is an anisotropic conductive adhesive film. A first connected member containing a first electrode;
A second connected member containing a second electrode; And
And an adhesive film according to any one of claims 13 to 15, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode. A semiconductor device.

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