KR100959746B1 - Adhesive film composition using phenoxy resin and ester-based thermoplastic resin for semiconductor assembly and bonding film therefrom - Google Patents

Abstract

The present invention relates to an adhesive film composition and an adhesive film for semiconductor assembly comprising a phenoxy resin and a polyester-based thermoplastic resin. According to the composition of the present invention, the tensile modulus before curing is improved to 30 Kgf / mm < 2 > or more to prevent sticking between the adhesives after the cutting process to the chip size, as well as to facilitate pick-up with the adhesive layer, and also during the die attach process. It is possible to provide an adhesive film for semiconductor assembly that can easily remove bubbles generated and ensure high reliability.

Adhesive film for semiconductor assembly, phenoxy resin, ester thermoplastic resin, epoxy group-containing elastomer resin, epoxy resin, phenolic or amine type curing agent, imidazole series curing catalyst, silane coupling agent, inorganic filler

Description

Adhesion film composition and adhesive film for semiconductor assembly using phenoxy resin and ester-based thermoplastic resin {ADHESIVE FILM COMPOSITION USING PHENOXY RESIN AND ESTER-BASED THERMOPLASTIC RESIN FOR SEMICONDUCTOR ASSEMBLY AND BONDING FILM THEREFROM}

The present invention relates to an adhesive film composition and an adhesive film for semiconductor assembly, and more particularly to a semiconductor assembly that can improve the manufacturing processability and reliability when used in the semiconductor assembly process, including phenoxy resin or polyester-based thermoplastic resin It relates to an adhesive film composition and an adhesive film.

Conventionally, silver paste has been mainly used for joining a semiconductor element and an element or support member, but according to the recent trend of miniaturization and large capacity of semiconductor elements, the support member used for this is also required to be miniaturized and refined. Silver paste, which has been widely used in recent years, has disadvantages such as abnormality during wire bonding, bubble generation, and difficulty in controlling thickness due to protrusion or inclination of semiconductor devices. Therefore, in recent years, the adhesive film is mainly used instead of silver paste.

Adhesive films used in semiconductor assembly are mainly used with dicing films. The dicing film refers to a film used to fix a semiconductor wafer in a dicing process in a series of semiconductor chip manufacturing processes. The dicing process is a process of cutting into individual chips from a semiconductor wafer, and an expand process, a pick-up process and a mounting process are performed successively to the dicing process.

Such a dicing film is usually composed of coating a UV-curable or general curable pressure-sensitive adhesive on a vinyl chloride or polyolefin base film and adhering a cover film of PET material thereon. On the other hand, the general use of the adhesive film for assembling semiconductor is attached to the semiconductor wafer (wafer), and the dicing film having the above configuration is applied to the dicing film from which the cover film is removed, followed by the dicing process To fragment.

Recently, as an adhesive for assembling a semiconductor for dicing die bonding, a dicing film from which a PET cover film has been removed and an adhesive film are laminated to each other to form a single film, and then a semiconductor wafer is attached thereon and fragmented according to a dicing process. In this case, however, unlike a dicing film intended only for dicing, the die and the die adhesive film must be simultaneously dropped during the pick-up process. There is a difficulty, and bubbles may occur due to the rough surface in the process of bonding the die-bonding film to the back surface of the semiconductor wafer. This causes voids between the chip and the interface after assembly, resulting in device defects in the reliability process.

In addition, in order to exhibit high reliability of the adhesive film for semiconductor assembly, the content of the cured portion in the adhesive composition is increased, which reduces the tensile strength of the film, thereby cutting the film to a size suitable for a semiconductor wafer. During the cutting or sawing to the chip size, which is a semiconductor assembly process, a burr or chipping phenomenon may occur. In addition, since the adhesive film is deformed due to the high adhesion force with the adhesive in the pick-up process, the pick-up success rate is decreased, and the epoxy molding compound (EMC) is increased due to the increase in modulus in the curing process after the die attach process. Pressing the device assembled at high temperature and high pressure during the molding process causes a problem that bubbles are generated due to the rough surface such as the PCB substrate, which greatly affects the reliability.

Examples for the implementation of the present invention is derived to overcome the problems of the prior art, one object of the present invention is to increase the tensile modulus (Tensile Modulus) before curing of the adhesive film, sawing process to chip size It is to provide an adhesive film composition for semiconductor assembly to reduce the occurrence of burr or chipping phenomenon in the process, and to prevent the adhesion between the adhesive during the pick-up process to improve the peeling force with the adhesive layer .

Another object of the present invention is to provide an adhesive film for semiconductor assembly formed from the adhesive film composition for semiconductor assembly.

Still another object of the present invention is to provide an adhesive for semiconductor assembly for dicing die bonding comprising the adhesive film for semiconductor assembly.

One aspect of the present invention for achieving the above object is (1) 2 to 15% by weight of phenoxy resin based on the total solids; (2) 10 to 30% by weight of the ester thermoplastic resin; (3) 30 to 60% by weight of an elastomer resin containing a hydroxyl group or an epoxy group; (4) 5 to 20% by weight of an epoxy resin; (5) 2 to 20% by weight of one or more resins selected from the group of phenolic resins or aromatic amine curing agent resins as curing agents for epoxy resins; (6) An adhesive film composition for semiconductor assembly comprising 0.01 to 5% by weight of at least one catalyst selected from the group consisting of phosphine, boron and imidazole curing catalysts.

Another aspect of the present invention for achieving the above object relates to a semiconductor assembly adhesive for dicing die bonding comprising an adhesive film for semiconductor assembly and the adhesive film for semiconductor assembly formed of the composition.

The adhesive film composition for semiconductor assembly of the embodiments of the present invention includes a phenoxy resin and an ester-based thermoplastic resin to increase the tensile modulus at room temperature to prevent sticking between the adhesives after cutting to the chip size (Sawing) The peeling force with the pressure-sensitive adhesive is reduced, so pick up is improved. In addition, due to the high fluidity at high temperature, the effect of filling the rough surface in the die bonding process is excellent, thereby minimizing bubbles generated during chip bonding at high temperature and filling the rough surface such as a printed circuit board (PCB). Due to the effect, it is difficult to penetrate the environmental factors such as water penetration by the external environment, and the shear adhesion is also increased, thereby securing a high reliability.

Hereinafter will be described in more detail with respect to embodiments of the present invention.

Embodiment of the present invention is characterized by an adhesive film composition for semiconductor assembly comprising a phenoxy resin and an ester-based thermoplastic resin.

The phenoxy clock resin that can be used in the embodiments of the present invention has a softening point and a glass transition temperature (Tg) in the range of 0 ° C to 200 ° C as a resin that helps to form an adhesive film and promote interfacial adhesion. Those having an average molecular weight in the range of 200 to 1,000,000 are mainly used. In the present invention, preferably, the softening point is in the range of 50 ° C to 100 ° C, and the weight average molecular weight is in the range of 10,000 to 100,000. When the phenoxy resin has a softening point and a weight average molecular weight within the above range, it maintains a solid state at room temperature to increase the tensile modulus to prevent sticking between the adhesives, and to facilitate the pickup by reducing the adhesive force with the adhesive during the pickup process In the die attach process, fluidity may be imparted at a high temperature to remove bubbles generated at an interface during die bonding.

In addition, the hydroxyl groups present in the phenoxy resin can control the rate of reaction such as epoxy and phenol or aromatic amines. In other words, the epoxy and curing agent reaction tends to increase the curing rate depending on the content of phenoxy. [Reference: Application of the latest version of epoxy resin to electronics, published November 26, 2003, author: 高 薄 一 弘, Publisher: Korean Institute of Technology and Information, Japan, page 25 ~ 26]. By using the phenoxy resin, the elastic modulus is controlled at high temperature and the thermoplastic effect is exerted, thereby reducing the elastic modulus due to the presence of the uncured portion in the epoxy molding compound (EMC) process in the semiconductor process. In addition, the thermoplastic phenoxy resin exhibits fluidity at a high temperature like a liquid, and thus has an excellent effect of filling a rough surface such as a PCB.

The phenoxy resin used in the embodiments of the present invention is represented by the following formula (1).

In Formula 1, n is defined in the molecular weight range and Y1 is a structure forming a skeleton in the phenoxy resin, hydroquinone, 2-bromohydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, 4 A skeleton of a 4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) ether, a phenol group, a cresol group, a cresol novolac group, a prorene group, and R1 to R8 represent a hydrogen atom, a halogen group or Alkyl group, aryl group, methylol group, allyl group, cyclic aliphatic group, nitro group, etc., X1 is a linear alkyl group, branched alkyl group, allyl group, substituted allyl group, cyclic aliphatic group, One or more selected from the phenoxy compounds introduced with the alkoxycarbonyl group may be used, but is not limited thereto.

Specific examples of Y1 include 2,2 '-(2-methylpropylidene) bis [2,4-dimethylphenol], 2,2'-methylidenebis [4-nonylphenol], 4,4'-(1 -Methylethylidene) bis [2- (1-methylethyl) phenol], 4,4 '-(1-methylethylidene) bis [2- (1,1-dimethylethyl) phenol], tetramethylbisphenol A, tetramethylbisphenol F,, 4,4 '-(1-methylethylidene) bis [2,6-di (1,1-dimethylethyl) phenol], 4,4'-(1-methylethylli Den) bis [2- (2-propenyl) phenol], 4,4'-methylenebis [2- (2-propenyl) phenol], 3,3'-dimethyl [1,1'-biphenyl]- 4,4'-diol, 3,3'-bis (2-propenyl)-[1,1'-biphenyl] -4,4'-diol, 4,4 '-(1-methylethylidene) Bis [2-methyl-6-hydroxymethylphenol], tetramethylol bisphenol A, 3,3 ', 5,5'-tetrakis (hydroxymethyl)-(1,1'-biphenyl) -4, 4'-diol, 4,4 '-(1-methylethylidene) bis [2-phenylphenol], 4,4'-(1-methylethylidene) bis [2-cyclohexylphenol], 4, 4'-methylenebis (2-cyclohexyl-5-methylphenol), 4,4 '-(1-methylpropylidene) bisphenol, 4,4'-(1 -Methylheptylidene) bisphenol, 4,4 '-(1-methyloctylidene) bisphenol, 4,4'-(1,3-dimethylbutylidene) bisphenol, 3,3 ', 5,5'- Tetramethyl- [1,1'-biphenyl] -4,4'-diol, 3,3 ', 5,5'-tetra-t-butyl- [1,1'-biphenyl] -4,4' -Diol, 4,4 '-(1-methylethylidene) bis [2- (1-phenylethyl) phenol], 4,4'-(2-ethylhexylidene) bisphenol, 4,4'-methylene Bis [2-methylphenol], 4,4 '-(2-methylpropylidene) bisphenol, 4,4'-propylidene bisphenol, 4,4'-(1-ethylpropylidene) bisphenol, 4,4'- Methylenebis [2,6-bis (1,1-dimethylethyl) phenol], 4,4 '-(3-methylbutylidene) bisphenol, 4,4'-(1-phenylethylidene) bisphenol, 4 , 4 '-(1-methylethylidene) bis [2- (1,1-methylpropyl) phenol], 4,4'-(phenylmethylene) bisphenol, 4,4 '-(diphenylmethylene) bisphenol, 4,4 '-[1- (4-nitrophenyl) ethylidene] bisphenol, 4,4'-[1- (4-aminophenyl) ethylidene] bisphenol, 4,4 '-[(4-bromophenyl Methylenebisphenol, 4,4 '-[(4-chlorophenyl) methylenebisphenol, 4,4'-[(4-ple Orophenyl) methylenebisphenol, 4,4 '-(2-methylpropylidene) bis [3-methyl-6- (1,1-dimethylethyl) phenol, 4,4'-(1-ethylpropylidene) bis [ 2-methylphenol], 4,4 '-(1-phenylethylidene) bis [2-methylphenol], 4,4'-(phenylmethylene) bis-2,3,5-trimethylphenol, 4,4 '-(1-phenylethylidene) bis [2- (1,1-dimethylethyl) phenol], 4,4'-(1-methylpropylidene) bis [2-cyclohexyl-5-methylphenol], 4,4 '-(1-phenylethylidene) bis [2-phenylphenol], 4,4'-butylidenebis [3-methyl-6- (1,1-dimethylethyl) phenol], 4- Hydroxy-α- (4-hydroxyphenyl-α-methylbenzeneacetylenemethylester, 4-hydroxy-α- (4-hydroxyphenyl-α-methylbenzeneacetyleneethylester, 4-hydroxy-α- (4-hydroxyphenyl) benzeneacetylenebutylester, tetrabromobisphenol A, tetrabromobisphenol F, tetrabromobisphenol AD, 4,4 '-(1-methylethylene) bis [2,6-dichlorophenol] , 4,4 '-(1-methylethylidene) bis [2-chlorophenol], 4,4- (1 -Methylethylidene) bis [2-chloro-6-methylphenol], 4,4'-methylenebis [2-fluorophenol], 4,4'-methylenebis [2,6-difluorophenol] , 4,4'-isopropylidenebis [2-fluorophenol], 3,3'-difluoro- [1,1'-diphenyl] -4,4'-diol, 3,3 ', 5 , 5'-tetrafluoro- [1,1'-biphenyl] -4,4'-diol, 4,4 '-(phenylmethylene) bis [2-fluorophenol], 4,4'-[( 4-fluorophenyl) methylenebis [2-fluorophenol], 4,4 '-(fluoromethylene) bis [2,6-difluorophenol], 4,4'-(4-fluorophenyl) Methylenebis [2,6-difluorophenol], 4,4 '-(diphenylmethylene) bis [2-fluorophenol], 4,4'-(diphenylmethylene) bis [2,6-difluoro Lophenol], 4,4 '-(1-methylethylene) bis [2-nitrophenol], 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol , 2,7-naphthalenediol, 4,4'-dihydroxydiphenylether, bis (4-hydroxyphenyl) methanone, 4,4'-cyclohexylidenebisphenol, 4,4'-cyclohexyl Denbis [2-methylphenol], 4,4'-cyclopentylidenebisphenol, 4,4'-cyclopentylidenebis [2-methylphenol], 4,4'-cyclohexylidene [2,6 -Dimethylphenol], 4,4'-cyclohexylidenebis [2- (1,1-dimethylethyl) phenol], 4,4'-cyclohexylidenebis [2-cyclohexylphenol], 4,4 '-(1,2-ethanediyl) bisphenol, 4,4'-cyclohexylidenebis [2-phenylphenol], 4,4'-[1,4-phenylenebis (1-methylethylidene) ] Bis [2-methylphenol], 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 4,4'-[1,4-phenylenebis (1-methyl Ethylidene)] bisphenol, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bis [2-methyl-6-hydroxymethylphenol], 4- [1- [4 -(4-hydroxy-3-methylphenyl) -4-methylcyclohexyl] -1-methylethyl] -2-methylphenol, 4- [1- (4-hydroxy-3,5-dimethylphenyl)- 4-methylcyclohexyl] -1-methylethyl] -2,6-dimethylphenol, 4,4 '-(1,2-ethanediyl) bis [2,6-di- (1,1-dimethylethyl) phenol ], 4,4 '-(dimethylsilylene) bisphenol, 1,3-bis (p-hydroxy) Phenyl) -1,1,3,3-tetramethyldisiloxane, silicone oligomers having p-hydroxyphenyl group at the terminal and 2,2'-methylidenebisphenol, 2,2'-methylethylidenebisphenol, 2 A linear alkyl group, a branched alkyl group, an aryl group, a methylol group, an allyl group, etc. are introduce | transduced into the aromatic ring of phenol skeletons, such as a 2'-ethylidene bisphenol. Specifically, 2,2'-methylidenebis [4-methylphenol], 2,2'-ethylidenebis [4-methylphenol], 2,2'-methylidenebis [4,6-dimethylphenol], 2,2 '-(1-methylethylidene) bis [4,6-dimethylphenol], 2,2'-(1-methylethylidene) bis [4-sec-butylphenol], 2,2 ' -Methylidenebis [6- (1,1-dimethylethyl) -4-methylphenol], 4,4 '-(1-methylethylidene) bis [2-methylphenol], 2,2'-ethylidene Bis [4,6-di (1,1-dimethylethyl) phenol], 2,2'-methylidenebis [3-methyl 4,6-di- (1,1-dimethylethyl) phenol], 2,2 '-Ethylidenebis [4- (1,1-dimethylethyl) phenol], 2,2'-methylidenebis (2,4-di-t-butyl-5-methylphenol), 2,2'-methyl Lidenebis (4-phenylphenol), 2,2'-methylidenebis [4-methyl-6-hydroxymethylphenol], 2,2'-methylenebis [6- (2-propenyl) phenol], and the like. have.

In the present invention, the phenoxy resin may be mixed in several kinds.

The content of the phenoxy resin in the composition of the present invention is preferably from 2 to 15% by weight, more preferably from 4 to 15% by weight based on the solids of the total composition. When the content of the phenoxy resin is more than 15% by weight, the tensile strength of the film is significantly increased and the liquid stability of the crude liquid may be reduced, resulting in poor coating properties, and less than 2% by weight has a disadvantage in that the tensile modulus is lowered. .

The ester-based thermoplastic resin usable in the embodiments of the present invention can improve tensile modulus as a resin which helps to form an adhesive film and promote interfacial adhesion, and increases fluidity after die bonding, thereby generating bubbles. It can be suppressed and eliminated. As for the ester thermoplastic resin suitable for this invention, it is preferable that glass transition temperature (Tg) is 30 degreeC or more and 80 degrees C or less.

The ester-based thermoplastic resin usable in the present invention may be represented by the following formula (2).

In Chemical Formula 2, R1 and R2 are polymerized from a carboxyl group having a bifunctional or higher functional group before polymerization including R1 and a diol before polymerization including R2, and a carboxyl group, a halogen group, a phenyl group, and a siloxane within a range that does not affect the overall polymer reaction. It may be substituted with one or more selected from the group consisting of an acid group, an alkoxy group, a hydroxy group, and an alkyl group, and n is 1 to 300.

The compound containing a carboxyl group having a bifunctional group or more prior to polymerization including R1 is preferably oxalic acid, succinic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1 , 5-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, diphenoxytene-4,4-dicarboxylic acid, diphenylsulfone Dicarboxylic acid, glycolic acid, para-oxybenzoic acid, para-oxyethoxybenzoic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, hexanedionic acid, butenedionic acid, trimellitic acid, trimesic acid Food acid, pyromellitic acid. The diol containing a hydroxyl group of at least bifunctional groups before polymerization including R 2 is preferably ethylene glycol, propylene glycol, isobutylene glycol, 2,6-dihydroxynaphthalene, octahydro-4,7- as alcohols. Methano-1H-indene-dimethanol, butanediol, neopentylglycol, hydroquinone, lesosinol, dihydroxyphenyl, naphthalenediol, dihydroxyphenylester, cyclohexanediol, 2,2-bis (4-hydride Hydroxyphenyl) propane, diethoxybisphenol A, pentaerythritol and a hydroxyl group of at least a bifunctional group substituted with alkyl, alkoxy or halogen.

The ester-based thermoplastic resin of Chemical Formula 2 is polymerized from a diol having a carboxyl group or more than a difunctional group and a hydroxyl group or more to form a structure that imparts fluidity and adhesion at a specific temperature of the ester resin. . The ester-based thermoplastic resin has a special property that the viscosity drops rapidly with temperature.

The content of the ester-based thermoplastic resin in the composition of the present invention is preferably 10 to 30% by weight, more preferably 10 to 25% by weight based on the solids of the total composition. When the content of the ester-based thermoplastic resin is more than 30% by weight, there is a disadvantage that the surface adhesion of the wafer is lowered, the reliability is lowered, the tensile modulus at room temperature is lowered below 10% by weight, bubbles well after die bonding There is a disadvantage that is not eliminated.

In the present invention, the total content of the phenoxy resin and the ester thermoplastic resin is preferably 20 to 45% by weight. Within the above range, the die shear strength is relatively excellent, and the pick-up characteristic is particularly excellent without the phenomenon of sticking between the adhesives. If the total content is less than 20% by weight, the room temperature modulus is low, which may cause adhesive sticking after the cutting process, and may cause a problem in pickup. If the content is more than 45% by weight, the elastomer resin content is low, resulting in a slight decrease in adhesive strength. Can be.

Elastomer resin (Elastromer) usable in the embodiments of the present invention is a rubber component required for film formation, it is a rubber containing a hydroxyl group or an epoxy group, it is preferred that the weight average molecular weight is in the range of 500 to 2,000,000. As the elastomer resin, for example, acrylonitrile, butadiene, styrene, acryl, isoprene, ethylene, propylene ), One or more selected from the group consisting of polyurethane-based and silicone-based elastomers may be used, but is not limited thereto. The content of the elastomer resin is preferably 30 to 60% by weight based on the total solids of the composition. When the content of the elastomer resin is less than 30% by weight, it is difficult to form a film, when the content of more than 60% by weight may reduce the reliability.

The epoxy resin that can be used in the embodiments of the present invention is not particularly limited as long as it exhibits curing and adhesive action. However, in consideration of the shape of the film, an epoxy resin having one or more functional groups is preferable as the solid phase or an epoxy near the solid phase. Do.

The solid epoxy resin is not particularly limited, but includes, for example, bisphenol-based, phenol novolac-based, o-cresol novolac-based, polyfunctional epoxy, amine-based epoxy, and heterocyclic rings. Epoxy, substituted epoxy, naphthol-based epoxy and derivatives thereof. Bisphenol-based products include YD-017H, YD-020, YD020-L, YD-014, YD-014ER, YD-013K, YD-019K, YD-019, and YD. -017R, YD-017, YD-012, YD-011H, YD-011S, YD-011, YDF-2004, YDF-2001, and the like.Phenol novolac-based coat coat of Yuka Shell Epoxy Co., Ltd. 152, Epicoat 154, EPPN-201 of Nippon Kayaku Co., Ltd., DN-483 of Dow Chemical, YDPN-641, YDPN-638A80, YDPN-638, YDPN-637, YDPN-644, YDPN-631 of Kukdo Chemical. , o-Cresol novolac system, YDCN-500-1P, YDCN-500-2P, YDCN-500-4P, YDCN-500-5P, YDCN-500-7P, YDCN-500-8P , YDCN-500-10P, YDCN-500-80P, YDCN-500-80PCA60, YDCN-500-80PBC60, YDCN-500-90P, YDCN-500-90PA75, etc. , EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, YDCN-701, YDCN-702, YDCN-703, YDCN-704 from Japan Dokdo Chemical Corporation N-665-EXP, and bisphenol-based novolac epoxy include KBPN-110, KBPN-120, KBPN-115, etc. of Kukdo Chemical, and Yuka Shell Epoxy Co., Ltd. Araldito 0163, Nata-Centigrade, Detacol EX-611, Detacol EX-614, Detacol EX-614B, Detacol EX-622, Detacol EX-512, Detacol EX-521, Deta Call EX-421, Detacall EX-411, Detacall EX-321, Kukdo Chemical EP-5200R, KD-1012, EP-5100R, KD-1011, KDT-4400A70, KDT-4400, YH-434L, YH- 434, YH-300 and the like.Amine epoxy resins include Yuka Shell Epoxy Epicoat 604, Dokdo Chemical Co., Ltd. YH-434, Mitsubishi Gas Chemical Co., Ltd., TETRAD-X, TETRAD-C, and Sumitomo Chemical Co., Ltd. Examples of the heterocyclic epoxy resin include PT-810 of CIBA Specialty Chemical Co., Ltd., and ERL-4234 and ERL-4299 of UCC. , ERL-4221, ERL-4206 and naphthol-based epoxy include Epiclonal HP-4032, Epiclone HP-4032D, Epiclone HP-4700, and Epiclone 4701 of Japan Ink Chem. More than a kind can be mixed and used.

In embodiments of the present invention, the content of the epoxy resin is preferably 5 to 20% by weight based on the total solids of the composition. When the content of the epoxy resin is less than 5% by weight, the reliability is lowered due to lack of hardened portion, and when the content of the epoxy resin is greater than 20% by weight, the tensile strength of the film is decreased. .

As the curing agent of the epoxy resin that can be used in the sphere examples of the present invention, typically, a phenol resin or an amine resin is preferable.

As the phenol resin that can be used in the embodiments of the present invention, those which are usually used may be used without particular limitation, but as the compound having two or more phenolic hydroxyl groups in one molecule, bisphenol A and bisphenol excellent in electrolytic corrosion resistance at the time of moisture absorption. F, bisphenol S-based curing agent resins and phenolic novolak resins, bisphenol A-based novolak resins or phenolic resins such as cresol novolac, xyloxi, biphenyl

Examples of products currently marketed as such phenol resins include H-1, H-4, HF-1M, HF-3M, HF-4M, HF-45, etc. of Meiwa Plastic Industry Co., Ltd. in the form of phenol novolac resins. MEPH-78004S, MEH-7800SS, MEH-7800S, MEH-7800M, MEH-7800H, MEH-7800HH, MEH-78003H, and KOLON Emulsion Co., Ltd. Phenyl-based Meihwa Plastic Industry Co., Ltd. MEH-7851SS, MEH-7851S, MEH7851M, MEH-7851H, MEH-78513H, MEH-78514H, KOLON Emulsion Co., Ltd. MEH-7500, MEH-75003S, MEH-7500SS, MEH-7500S, MEH-7500H, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The equivalent ratio of phenol to epoxy in the phenolic epoxy resin curing agent is preferably in the range of 0.5 to 1.5.

In the embodiments of the present invention, as the curing agent of the epoxy resin, it is also possible to use an amine resin containing activated hydrogen. In the present invention, an aromatic amine-based resin can be preferably used in consideration of the curing rate, physical properties after curing, and the like. Although what is normally used can be used as aromatic amine-type hardening | curing agent resin without a restriction | limiting in particular, It is represented by following formula (3) as an aromatic compound which has two or more amine groups in 1 molecule.

In Formula 3, X2 is absent or -CH _2- , -CH ₂ CH _2- , -O-, -SO _2- , -NHCO-, -C (CH ₃ ) _2- , or -CO-, R1 to R ₁₀ is hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkoxy group containing at least one amine group

R ₁₁ in Chemical Formula 4 To R ₁₈ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a cyanide group, a halogen group or an alkoxy group containing at least one or more amine groups.

In Formula 5, Z ₁ is hydrogen or an alkyl group or alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and R ₁₉ to R ₁₃ contain at least one amine group and hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and cyanide Group, halogen group or alkoxy group.

In Formula 6, R ₃₄ to R ₄₁ are hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a cyanide group, a halogen group, or an alkoxy group containing at least one amine group.

In Formula 7, X3 is -CH _2- , -NH-, or -SO _2- , -S-, -O-, and R ₄₂ to R ₄₉ contain at least one amine group, and hydrogen, 1 to 4 carbon atoms. Phosphorus alkyl group, hydroxyl group, cyanide group, halogen group or alkoxy group.

Representative examples of Formula 3 include 3,3'-diaminobenzidine, 4,4'-diaminodiphenyl methane, 4,4 'or 3 , 3'-diaminodiphenyl sulfone (4,4 'or 3,3'-diaminodiphenyl sulfone), para-phenylene diamine, 4,4'-diaminobenzophenone (4,4'- diaminobenzophenone, meta-phenylene diamine, meta-toluene diamine, 4,4'-diaminodiphenyl ether, 4,4 'or 3 , 3'-diaminobenzophenone (4,4 'or 3,3'-diaminobenzophenone), 1,4- or 1,3'-bis (4 or 3-aminocumyl) benzene (1,4' or 1, 3'-bis (4 or 3-aminocumyl) benzene, 1,4'-bis (4 or 3-aminophenoxy) benzene (1,4'-bis (4 or 3-aminophenoxy) benzene), 2,2 ' -Bis [4- (4 or 3-aminophenoxy) phenyl] propane (2,2'-bis] 4- (4 or 3-aminophenoxy) phenyl] propane, bis [4- (4 or 3-aminophenoxy Phenyl] sulfone (bis [4- (4 or 3-aminophenoxy) phenyl] sulfone, 2,2'-ratio [4- (4 or 3-aminophenoxy) phenyl] hexafluoropropane (2,2 '-[4- (4 or 3-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3' , 5,5'-tetrabutyldiphenylketone (4,4'-diamino-3,3 ', 5,5'-tetrabutyldiphenylketone), 4,4'-diamino-3,3', 5,5'- Tetraethyldiphenylketone (4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylketone), 4,4'-diamino-3,3', 5,5'-tetra-n-propylenedi Phenylketone (4,4'-diamino-3,3 ', 5,5'-tetra-n-propyldiphenylketone), 4,4'-diamino-3,3', 5,5'-tetraisopropyldiphenyl Ketone (4,4'-diamino-3,3 ', 5,5'-tetraisopropyldiphenylketone), 4,4'-diamino-3,3', 5,5'-tetramethyldiphenylketone (4,4 ' -diamino-3,3 ', 5,5'-tetramethyldiphenylketone), 4,4'-diamino-3,3'5,5'-tetra-n-propyldiphenmethane (4,4'-diamino-3 , 3'5,5'-tetra-n-propyldiphenylmethane), 4,4'-diamino-3,3'5,5'-tetramethyldiphenylmethane (4,4'-diamino-3,3'5 , 5'-tetramethyldiphenylmethane), 4,4'-diamino-3,3'5,5'-tetraisopropyldiphenylmethane (4,4'-di amino-3,3'5,5'-tetraisopropyldiphenylmethane), 4,4'-diamino-3,3'5,5'-tetraethyldiphenylmethane (4,4'-diamino-3,3'5, 5'-tetraethyldiphenylmethane), 4,4'-diamino-3,3'-dimethyl-5,5'-diethyldiphenylmethane (4,4'-diamino-3,3'-dimethyl-5,5 ' -diethyldiphenylmethane), 4,4'-diamino-3,3'-dimethyl-5,5'-diisopropyldiphenylmethane (4,4'-diamino-3,3'-dimethyl-5,5'- diisopropyldiphenylmethane), 4,4'-diamino-3,3'-diethyl-5,5'-diethyldiphenylmethane (4,4'-diamino-3,3'-diethyl-5,5'-diethyldiphenylmethane ), 4,4'-diamino-3,3'-diethyl-5,5'-diethyldiphenylmethane (4,4'-diamino-3,3'-diethyl-5,5'-diethyldiphenylmethane) 4,4'-diamino-3,5-dimethyl-3 ', 5'-diethyldiphenylmethane, 4,4'-diamino-3,5-dimethyl-3', 5'-diethyldiphenylmethane , 4'-diamino-3,5-dimethyl-3 ', 5'-diisopropyldiphenylmethane (4,4'-diamino-3,5-dimethyl-3', 5'-diisopropyldiphenylmethane), 4, 4'-diamino-3,5-diethyl-3 ', 5'-diisopropyldiphenylmethane (4,4'-diamino-3,5-diethyl-3', 5'-diisopropyldiphenylmethane), 4,4'-diamino-3,5-diethyl-3 ', 5'-dibutyldiphenylmethane (4,4'-diamino-3,5-diethyl-3', 5 '-dibutyldiphenylmethane), 4,4'-diamino-3,5-diisopropyl-3', 5'-yabutylyaphenylmethane (4,4'-diamino-3,5-diisopropyl-3 ', 5 '-dibutyldiphenylmethane), 4,4'-diamino-3,3'-diisopropyl-5', 5'-dibutyldiphenylmethane (4,4'-diamino-3,3'-diisopropyl-5 ' , 5'-dibutyldiphenylmethane), 4,4'-diamino-3,3'-dimethyl-5 ', 5'-dibutyldiphenylmethane (4,4'-diamino-3,3'-dimethyl-5' , 5'-dibutyldiphenylmethane), 4,4'-diamino-3,3'-diethyl-5 ', 5'-dibutyldiphenylmethane (4,4'-diamino-3,3'-diethyl-5 ', 5'-dibutyldiphenylmethane), 4,4'-diamino-3,3'-dimethyldiphenylmethane (4,4'-diamino-3,3'-dimethyldiphenylmethane), 4,4'-diamino-3 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diamino-3,3'-di-n-propyldiphenylmethane '-diamino-3,3'-di-n-propyldiphenylmethane), 4,4'-diamino-3,3'-diisopropyldiphenylmethane (4,4'-diamino-3,3'-diisopropyldiphenylmethane), 4,4'-diamino-3,3'-dibutyldiphenylmethane (4,4'-diamino-3,3'-dibutyldiphenylmethane), 4,4'-diamino-3,3 ', 5-trimethyldiphenylmethane, 4,4'-diamino-3,3', 5-triethyldiphenylmethane (4,4'-diamino-3,3 ', 5-triethyldiphenylmethane), 4,4'-diamino-3,3', 5-tri-n-propyldiphenylmethane (4 , 4'-diamino-3,3 ', 5-tri-n-propyldiphenylmethane), 4,4'-diamino-3,3', 5-triisopropyldiphenylmethane (4,4'-diamino-3 4,4'-diamino-3,3 ', 5-tributyldiphenylmethane 4,4'-diamino-3,3', 5-tributyldiphenylmethane '-Diamino-3-methyl-3'-ethyldiphenylmethane (4,4'-diamino-3-methyl-3'-ethyldiphenylmethane), 4,4'-diamino-3-methyl-3'-iso Propyldiphenylmethane (4,4'-diamino-3-methyl-3'-isopropyldiphenylmethane), 4,4'-diamino-3-ethyl-3'-isopropyldiphenylmethane (4,4'-diamino- 3-ethyl-3'-isopropyldiphenylmethane), 4,4'-diami 3-ethyl-3'-butyldiphenylmethane (4,4'-diamino-3-ethyl-, 3'-butyldiphenylmethane), 4,4'-diamino-3-isopropyl-3'-butyldiphenyl Methane (4,4'-diamino-3-isopropyl-3'-butyldiphenylmethane), 2,2-bis (4-amino-3,5-dimethylphenyl) propane (2,2-bis (4-amino-3, 5-dimethylphenyl) propane), 2,2-nonaqueous (4-amino-3,5-diethylphenyl) propane (2,2-bis (4-amino-3,5-diethylphenyl) propane), 2,2- Bis (4-amino-3,5-di-n-propylphenyl) propane (2,2-bis (4-amino-3,5-di-n-propylphenyl) propane), 2,2-bis (4- Amino-3,5-diisopropylphenyl) propane (2,2-bis (4-amino-3,5-diisopropylphenyl) propane), 2,2-bis (4-amino-3,5-dibutylphenyl) Propane (2,2-bis (4-amino-3,5-dibutylphenyl) propane), 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylbenzanalide (4,4 '-diamino-3,3', 5,5'-tetramethyldiphenylbenzanilide), 4,4'-diamino-3,3 ', 5,5'-tetraethyldipheninbenzanilide (4,4'-diamino-3 , 3 ', 5,5'-tetraethyldiphenylbenzanilide), 4,4'-diamino-3,3', 5,5'-tetra-n-pro Diphenylbenzanilide (4,4'-diamino-3,3 ', 5,5'-tetra-n-propyldiphenylbenzanilide), 4,4'-diamino-3,3', 5,5'-tetraiso Propyldiphenylbenzanilide (4,4'-diamino-3,3 ', 5,5'-tetraisopropyldiphenylbenzanilide), 4,4'-amino-3,3', 5,5'-tetrabutyldiphenylbenzanyl Lead (4,4'-diamino-3,3 ', 5,5'-tetrabutyldiphenylbenzanilide), 4,4'-diamino-3,3', 5,5'-tetramenyldiphenylsulfone (4,4 ' -diamino-3,3 ', 5,5'-tetramethyldiphenylsulfone), 4,4'-diamino-3,3', 5,5'-tetraethyldiphenylsulfone (4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylsulfone), 4,4'-diamino-3,3', 5,5'-tetra-n-propyldiphenylsulfone (4,4'-diamino-3,3 ', 5 , 5'-tetra-n-propyldiphenylsulfone), 4,4'-diamino-3,3 ', 5,5'-tetraisopropyldiphenylsulfone (4,4'-diamino-3,3', 5, 5'-tetraisopropyldiphenylsulfone), 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylether (4,4'-diamino-3,3', 5,5'-tetramethyldiphenylether), 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylether (4,4'-diamino-3,3', 5, 5'-tetraethyldiphenylether), 4,4'-diamino-3,3 ', 5,5'-tetra-n-propyldiphenylether (4,4'-diamino-3,3', 5,5'- tetra-n-propyldiphenylether), 4,4'-diamino-3,3 ', 5,5'-tetraisopropyldiphenylether (4,4'-diamino-3,3', 5,5'-tetraisopropyldiphenylether ), 4,4'-diamino-3,3 ', 5,5'-tetrabutyldiphenylether (4,4'-diamino-3,3', 5,5'-tetrabutyldiphenylether), 3,3 ' -Diaminobenzidine (3,3'-diaminobenzidine), 4,4'-diamino-2,2'-dimethylbibenzyl (4,4'-diamino-2,2'-dimethylbibenzyl), 3,3'- Diamino benzophenone (3,3'-diaminobenzophenone), 3,4-diaminobenzophenone, 3,4'-diaminodiphenylether (3,4'-diaminodiphenylether), 3, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diamino-1,2-diphenyl Ethane (2,2'-diamino-1,2-diphenylethane), or 4,4'-diamino-1,2-diphenylethane4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylamine, 4,4 '-D Minooctafluorobiphenyl, o-dianisidine and the like and representative examples of the formula (4) is 1,5-diaminonaphthalene (1,5-diaminonaphthalene), 1,8-diaminonaphthalene ( 1,8-diaminonaphthalene), 2,3-diaminonaphthalene (2,3-diaminonaphthalene) and the like, and a representative example of the formula (5) is paraosaniline (paraosaniline), a representative example of the formula 6 is 1,2 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 2,6-dia Minoanthraquinone (2,6-diaminoanthraquinone), 1,4-diamino-2,3-dichloroanthraquinone (1,4-diamino-2,3-dichloroanthraquinone), 1,4-diamino-2,3- Dicyano-9,10-anthraquinone (1,4-diamino-2,3-dicyano-9,10-anthraquinone), 1,4-diamino-4,8-dihydroxy-9,10-anthraquinone (1,4-diamino-4,8-dihydroxy-9,10-anthraquinone) and the like. Representative examples of 3,7-diamino-2,8-dimethyldibenzothiophenesulfone (3,7-diamino-2,8-dimethyldibenzothiophenesulfone), 2,7-diaminofluorene And 3,6-diaminocarbazole, and these may be used alone or in combination of two or more thereof.

As for the phenol resin or aromatic amine resin used as a hardening | curing agent of the said epoxy resin, it is good that the equivalence ratio with an epoxy resin is 0.5-1.5. Preferably, the equivalence ratio with respect to an epoxy resin uses 0.7 or more and 1.3 or less. If the equivalent ratio is less than 0.5 and more than 1.5, the content of the uncured product of the epoxy or the amine is increased, which lowers the thermal stability of the cured product and increases the water absorption.

In embodiments of the present invention comprises at least one or more of the curing agent phenolic resin or aromatic amine-based resin of the epoxy resin, the content is preferably 2 to 20% by weight based on the total solids of the composition. If more than 20% by weight, the modulus increases after curing, the bubble is not removed well, the reliability may be lowered, less than 2% by weight has a disadvantage of low adhesive strength after curing.

The composition according to the embodiment of the present invention includes a phosphine or boron-based curing catalyst and an imidazole-based catalyst.

The phosphine-based curing catalyst that can be used in the embodiments of the present invention is triphenylphosphine (Triphenylphosphine), tri-o-tolylphosphine (Tri-o-tolylphosphine), tri-m-toylphosphine (Tri-m- tolylphosphine), Tri-p-tolylphosphine, Tri-2,4-xylylphosphine, Tri-2, 5-xylphosphine , 5-xylylphosphine), tri-3, 5-xylphosphine (Tri-3, 5-xylylphosphine), tribenzylphosphine, tris (p-methoxyphenyl) phosphine (Tris (p-methoxyphenyl) phosphine, tris (p-tert-butoxyphenyl) phosphine (tris (p-tert-butoxyphenyl) phosphine), diphenylcyclohexylphosphine, tricyclophosphine (tricyclohexylphosphine), tributylphosphine ( Tributylphosphine), Tri-tert-butylphosphine, Tri-n-octylphosphine, Diphenylphosphinostyrene, Diphenylphosphinophosphate Diphenylphos phinouschloride, Tri-n-octylphosphine oxide, Diphenylphosphinyl hydroquinone, Tetrabutylphosphonium hydroxide, Tetrabutylphosphinium acetate acetate), benzyltriphenylphosphonium hexafluoroantimonate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, Benzyltriphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrafluoroborate, p-toyllphenylphosphonium tetra-p-toylborate, p-Tolyltriphenylphosphonium tetra-p-tolylborate Triphenyl phosphine triphenyl borane (Triphe nylphosphine triphenylborane), 1,2-bis (diphenylphosphino) ethane (1,2-Bis (diphenylphosphino) ethane), 1,3-bis (diphenylphosphino) propane (1,3-Bis (diphenylphosphino) propane ), 1,4-bis (diphenylphosphino) butane (1,4-Bis (diphenylphosphino) butane), 1,5-bis (diphenylphosphino) pentane (1,5-Bis (diphenylphosphino) pentane) Boron curing catalysts include phenyl boronic acid, 4-Methylphenyl boronic acid, 4-Methoxyphenyl boronic acid, 4- 4-Trifluoromethoxyphenyl boronic acid, 4-tert-Butoxyphenyl boronic acid, 3-fluoro-4-methoxyphenylboronic acid (3-Fluoro-4-methoxyphenyl boronic acid), Pyridine-triphenylborane, 2-Ethyl-4-methyl imidazolium tetraphenylborate, 1, 8-diazabicyclo [5.4.0] undecene-7-tet Phenylborate (1,8-Diazabicyclo [5.4.0] undecene-7-tetraphenylborate), 1,5-diazabicyclo [4.3.0] nonene-5-tetraphenylborate (1,5-Diazabicyclo [4.3.0] ] nonene-5-tetraphenylborate), lithium triphenyl (n-butyl) borate, etc. and imidazole catalysts include 2-methylimidazole, 2- 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole (2-phenylimidazole), 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2- Dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole (1-cyanoethyl-2-ethyl-4-methylimidazole), 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole ( One- cyanoethyl-2-phenylimidazole), 1-cyanoethyl-2-undecylimidazolium-trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate (1-cyanoethyl-2-phenylimidazolium-trimellitate), 2,4-diamino-6 [2'-methylimidazoyl- (1 ')-ethyl-s-triazine (2,4-diamino-6- [ 2'-methylimidazoly- (1 ')]-ethyl-s-triazine), 2,4-diamino-6- [2'-undecylimidazoyl- (1')]-ethyl-s-triazine ( 2,4-diamino-6- [2'-undecylimidazoly- (1 ')]-ethyl-s-triazine), 2,4-diamino-6- [2'-ethyl-4'-methylimidazoyl- (1 ')]-ethyl-s-triazine (2,4-diamino-6- [2'-ethyl-4'-methylimidazoly- (1')]-ethyl-s-triazine), 2,4-dia Mino-6- [2'-methylimidazoli- (1 ')]-ethyl-s-triazine isocyanuric acid derivative dihydrate (2,4-diamino-6- [2'-methylimidazoly- (1') )]-ethyl-s-triazine isocyanuric acid adduct dihydrate), 2-phenylimidazole isocyanuric acid adduct 2-methylimidazole isocyanuric acid adduct dihydrate, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole (2-phenyl-4-methyl-5-hydroxymethylimidazole), 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole (2, 3-dihyro-1H-pyrrolo [1,2-a] benzimidazole), 4,4'-methylenebis (2-ethyl-5-methylimidazole (4,4'-methylene bis (2-ethyl-5- methylimidazole), 2-methylimidazoline, 2-phenylimidazoline, 2-phenylimidazoline, 2,4-diamino-6-vinyl-1,3,5-triazine (2,4 -diamino-6-vinyl-1,3,5-triazine), 2,4-diamino-6-vinyl-1,3,5-triazineisocyanuric acid derivative (2,4-diamino-6-vinyl -1,3,5-triazine isocyanuric acid adduct), 2,4-diamino-6-meta atyloyloxyethyl-1,3,5-triazineisocyanuric acid derivative (2,4-diamino-6 -methacryloyloxylethyl-1,3,5-triazine isocyanuric acid adduct), 1- (2-sia Ethyl) -2-ethyl-4-methylimidazole (1- (2-cyanoethyl) -2-ethyl-4-methylimidazole), 1-cyanoethyl-2-methylimidazole (1-cyanoethyl-2- methylimidazole), 1- (2-cyanoethyl) 2-phenyl-4,5-di (cyanoethoxymethyl) imidazole (1- (2-cyanoethyl) 2-phenyl-4,5-di- (cyanoethoxymethyl ) imidazole), 1-acetyl-2-phenylhydrazine, 2-ethyl-4-methylimidazoline, 2-benzyl-4-methyl 2-imidazoline (2-benzyl-4-methyl dimidazoline), 2-ethyl imidazoline, 2-phenylimidazole, 2-phenyl-4,5-dihydride Hydroxymethylimidazole (2-phenyl-4,5-dihydroxymethylimidazole), melamine, dicyandiamide, etc. may be mentioned, and these can be used individually or in mixture of 2 or more types. In the present invention, the curing catalyst content is preferably 0.01 to 5% by weight based on the total solids of the composition. More preferably, the content of the curing catalyst is 0.01 to 3% by weight based on the whole adhesive film composition for semiconductor assembly. If it exceeds 5% by weight, the storage stability may be reduced.

In the present invention, there is no particular limitation as an adhesion promoter to enhance adhesion between the surface of an inorganic material such as silica and the resin of the adhesive film, and a silane coupling agent that is commonly used may be additionally used.

 For example, 2- (3,4 epoxy cyclohexyl) -ethyltrimethoxysilane, 3-glycidoxycitrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycid containing epoxy Doxypropyltriethoxysilane, N-2 (aminoethyl) 3-amitopropylmethyldimethoxysilane containing an amine group, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl ) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysil-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercetopropylmethyldimethoxysilane with merceto, 3-mercetopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane with isocyanate It can be illustrated and can be used individually or in mixture of 2 or more types.

In the present invention, the content of the silane coupling agent is preferably 0.01 to 7% by weight based on the entire adhesive film composition for semiconductor assembly. When the content of the silane coupling agent is greater than 7% by weight, the adhesion may be lowered and the tensile strength of the film may be lowered.

In the present invention, an inorganic or organic filler may be further used as necessary. As the inorganic filler, gold powder, silver powder, copper powder and nickel which are metal components may be used, and alumina, magnesium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, and oxide which are nonmetallic components Aluminum, aluminum nitride, silica, boron nitride, titanium dioxide, glass, iron oxide, ceramics, and the like can be used, and as the organic filler, carbon, rubber fillers, polymers, and the like can be used. The shape and size of the filler are not particularly limited, but in the inorganic filler, spherical silica and amorphous silica are mainly used, and the size thereof is preferably in the range of 5 nm to 10 μm. If the particle of the inorganic filler is 10㎛ or more there is a possibility of circuit damage due to collision with the semiconductor circuit.

In the embodiments of the present invention, the amount of the filler is preferably 0.1 to 50% by weight based on the total solids of the composition. In general, 0.1 to 30% by weight is preferable for the same chip adhesion, and 10 to 50% by weight for other chip adhesion. If it is more than 50% by weight, it is difficult to form a film, which may lower the tensile strength of the film.

The adhesive film composition for semiconductor assembly of embodiments of the present invention may further include an organic solvent. The organic solvent is to facilitate the film production by lowering the viscosity of the adhesive film composition for semiconductor assembly, but is not particularly limited, toluene, xylene, propylene glycol monomethyl ether acetate, benzene, acetone, methyl ethyl ketone, tetra Hydrofuran, dimethylformaldehyde, cyclohexanone and the like can be used.

In the embodiments of the present invention, the organic solvent is not particularly limited in content, and may be used in a range that does not affect the coating state of the composition after coating.

The composition according to the embodiment of the present invention preferably has a tensile modulus (Tensile Modulus) of 30 Kgf / mm 2 or more before curing. According to the composition of the present invention when the tensile modulus before curing of the adhesive film is 30Kgf / mm2 or more, it is possible to reduce the occurrence of burr or chipping phenomenon in the sawing process to the chip size, the adhesion between the adhesive The phenomenon may occur gradually, and the success rate may be improved during the pick-up process.

The composition may have a probe tack measurement value of 13 gf or less before curing. Since the probe tack measurement value of the adhesive film according to the composition may maintain a value of 13 gf or less, the adhesive force may be improved by preventing adhesion between the adhesives during the pick-up process. .

In addition, the composition is preferably an elastic modulus (Elastic Modulus) in the molding process of the epoxy molding compound (EMC-Epoxy Molding Compound) is 8MPa or less at the molding temperature. When the elastic modulus of the composition is 8 MPa or less, it can be easily removed by pressure to mold the remaining voids in the bonding process or the curing process.

Another aspect of the present invention relates to an adhesive film for semiconductor assembly formed from the adhesive film composition for semiconductor assembly. No special apparatus or equipment is required to form the adhesive film for semiconductor assembly using the composition of the present invention, and can be manufactured using any conventional manufacturing method known in the art to which the present invention pertains without limitation.

For example, after dissolving the composition of the present invention in the solvent and kneading sufficiently using a bead mill, it can be applied on a release-treated polyethylene terephthalate film and dried under heat to obtain an adhesive film having an appropriate coating thickness. have. It is preferable that it is 5-200 micrometers, and, as for the thickness of the said adhesive film, it is more preferable that it is 10-100 micrometers. Less than 5 μm is difficult to obtain sufficient adhesion, and more than 200 μm has little use, and it is difficult to remove the solvent used through coating and drying.

The present invention includes a dicing die bonding film comprising an adhesive film for semiconductor assembly.

The present invention provides a dicing die bonding film in which an adhesive layer and an adhesive film layer are sequentially stacked on a base film, wherein the adhesive film layer of the present invention provides an adhesive film of a dicing die bond film. .

The pressure-sensitive adhesive layer may be used a conventional pressure-sensitive adhesive composition.

It is preferable that the said base film has radiation permeability, and when applying the radiation curable adhesive which responds by ultraviolet irradiation, the base material with good light transmittance can be selected. Examples of the polymer that can be selected as such a substrate include homopolymers or copolymers of polyolefins such as polyethylene, polypropylene, propylene ethylene copolymers, ethylene ethyl acrylate copolymers, ethylene methyl acrylate copolymers, ethylene vinyl acetate copolymers, and polycarbonates. . Polymethyl methacrylate, polyvinyl chloride, polyurethane copolymers and the like can be used. The thickness of the base film is preferably 50 to 200 μm in consideration of tensile strength, elongation, radioactivity and the like.

By containing the adhesive film composition for semiconductor assembly comprising the phenoxy resin formed by the composition according to the present invention, since the solid property is very excellent at room temperature, the pick-up property with the adhesive layer is advantageous, and the fluidity is between 100 ° C and 130 ° C. Since it is possible to minimize the bubbles generated by increasing the effect of filling the rough surface such as a printed circuit board (PCB) or the wafer surface can provide an adhesive film for semiconductor assembly that can ensure high adhesion and reliability.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for illustrative purposes only and are not intended to limit the protection scope of the present invention.

[Examples 1 to 4 and Comparative Examples 1 to 4]

The following components were added to a 1 L cylindrical flask including a high speed stirring rod and dispersed at high speed at 4000 rpm for 20 minutes to prepare a composition, and then filtered using a 50 μm capsule filter and coated with an applicator to a thickness of 40 μm to form an adhesive film. It was prepared, and dried for 20 minutes at 60 ℃ 20 minutes at 90 ℃ and then stored at room temperature for 1 day.

Example 1

(a) Phenoxy resin (PKHP, manufactured by InChem Investment in Chemicals) 5g

(b) Ester Thermoplastic (UE-3350, Manufacturer: UNITIKA) 20g

(c) Epoxy-containing elastomer resin SG-P3TEA (15% solids) Manufacturer: Nagase Chemtex, Inc. 260g

(d) polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon Kayaku) 12 g

(e) Biphenyl phenol hardener (KPH-F4500, manufactured by Kolon Emulsifier) 10g

(f) Phosphine-based curing catalyst induced by xylactic phenol curing agent (MEH-7800C, manufactured by Meiwa Plastics) 2.5g

(g) Epoxy silane coupling agent (KBM-303, manufactured by Shinetsu) 1.5g

(h) 10 g of amorphous silica (R-972, Degussa)

(i) Solvent (cyclohexanone, manufactured by Samjeon Chemical) 100g

[Example 2]

(a) Phenoxy resin (E-4275, manufacturer: JER (Japan Epoxy Resin) 10g

(b) Ester thermoplastic resin (UE-3380, manufactured by UNITIKA) 25g

(c) Epoxy-containing elastomer resin (solid content 18%) (SG-800 H2, manufactured by Nagase Chemtex) 227.8 g

(d) Multifunctional epoxy resin (EOCN 102-S manufactured by Nippon Kayaku) 8g

(e) Xylac phenol curing agent (MEH-7800 4S manufactured by Meiwa Plastics) 5g

(f) Phosphine-based curing catalyst induced by xylactic phenol curing agent (MEH-7800C, manufactured by Meiwa Plastics) 2.5g

(g) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 1.5g

(h) amorphous silica (R-972, manufactured by Daegu) 7g

(i) Solvent (cyclohexanone, manufactured by Samjeon Chemical) 100g

Example 3

(a) Phenoxy resin (E-4275, manufacturer: JER (Japan Epoxy Resin) 10g

(b) Ester Thermoplastic (UE-3320, Manufacturer: UNITIKA) 30g

(c) Epoxy-containing elastomer resin (18% solids) (SG-800 H2, manufactured by Nagase Chemtextk) 212.2 g

(d) Multifunctional epoxy resin (EOCN 102-S manufactured by Nippon Kayaku) 8g

(e) aromatic amine curing agent (1,5-diaminonaphthalene, Tokyo Chemical Industry) 4g

(f) imidazole series curing catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate manufactured by Souk Chemical)

(g) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 1.8 g

(h) amorphous silica (R-972, manufactured by Daegu) 7g

(i) Solvent (cyclohexanone, manufactured by Samjeon Chemical) 100g

Example 4

(a) 10 g of phenoxy resin (PKHP, manufactured by InChem Investment in Chemicals)

(b) Ester Thermoplastic (UE-3380, Manufacturer: UNITIKA) 28g

(c) Epoxy-containing elastomer resin (solid content 15%) (SG-P3TEA, manufactured by Nagase Chemtextk) 260 g

(d) polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon Kayaku) 7 g

(e) Aromatic amine curing agent (1,5-diaminonaphthalene, Tokyo Chemical Industry) 3.5g

(f) imidazole series curing catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate manufactured by Souk Chemical)

(g) 1.5 g of epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.),

(h) amorphous silica (R-972, manufactured by Daegu) 10g

(i) Solvent (cyclohexanone, manufactured by Samjeon Chemical) 100g

 Comparative Example 1

(a) Phenoxy resin (PKHP, InChem Investment in Chemicals) 34.5g

(b) Ester Thermoplastic (UE-3380, Manufacturer: UNITIKA) 28g

(c) Epoxy-containing elastomer resin (18% solids) (SG-800 H2, manufactured by Nagase Chemtextk) 83.3 g

(d) polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon Kayaku) 8 g

(e) aromatic amine curing agent (1,5-diaminonaphthalene, Tokyo Chemical Industry) 4g

(e) imidazole series curing catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate manufactured by Souk Chemical) ,

(f) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 1.5 g,

(g) amorphous silica (R-972, manufactured by Daegu) 8g

(i) 200 g of solvent (cyclohexanone, manufactured by Samjeon Chemical)

Comparative Example 2

(a) Phenoxy resin (E-4275, manufacturer: JER (Japan Epoxy Resin) 20g

(b) Ester Thermoplastic (UE-3380, Manufacturer: UNITIKA) 31g

(c) Epoxy-containing elastomer resin (solid content 15%) (SG-P3TEA, manufactured by Nagase Chemtex) 166.7 g

(d) Multifunctional epoxy resin (EOCN 102-S manufactured by Nippon Kayaku) 8g

(e) Xylac phenol curing agent (MEH-7800 4S manufactured by Meiwa Plastics) 5g

(f) Phosphine-based curing catalyst induced by xylactic phenol curing agent (MEH-7800C, manufactured by Meiwa Plastics) 2.5g

(g) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 1.5g

(h) amorphous silica (R-972, manufactured by Daegu) 7g

(i) 200 g of solvent (cyclohexanone, manufactured by Samjeon Chemical)

Comparative Example 3

(a) Ester Thermoplastic (UE-3320, Manufacturer: UNITIKA) 15g

(b) Epoxy-containing elastomer resin (18% solids) (SG-800 H2, manufactured by Nagase Chemtex) 322.2 g

(c) Multifunctional epoxy resin (EOCN 102-S manufactured by Nippon Kayaku) 8g

(d) Xylac Phenolic Curing Agent (MEH-7800 4S, manufactured by Meiwa Plastics) 5g

(e) 2.5 g of phosphine-based curing catalyst induced by xylac phenol curing agent (MEH-7800C, manufactured by Meiwa Plastics)

(f) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 1.5g

(g) amorphous silica (R-972, manufactured by Daegu) 10g

(h) Solvent (cyclohexanone, manufactured by Samjeon Chemical) 70g

 [Comparative Example 4]

(a) Phenoxy resin (E-4275, manufacturer: JER (Japan Epoxy Resin) 19g

(b) Epoxy-containing elastomer resin (solid content 15%) (SG-P3TEA, manufactured by Nagase Chemtextk) 366.7 g

(c) polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon Kayaku) 8 g

(d) aromatic amine curing agent (1,5-diaminonaphthalene, Tokyo Chemical Industry) 4 g

(e) imidazole series curing catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate manufactured by Souk Chemical)

(f) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 2g

(g) amorphous silica (R-972, manufactured by Daegu) 10g

(i) Solvent (cyclohexanone, manufactured by Samjeon Chemical) 70g

<Evaluation of Physical Properties of Conductive Films Prepared in Examples and Comparative Examples>

The physical properties of the adhesive film for semiconductor assembly prepared by Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated as follows and the results are shown in Table 1 below.

(1) Void generation after wafer mounting: occurs when a pre-cut dicing die bonding film is laminated on an 8-inch wafer at a temperature of 65 ° C at a pressure of 0.3 MPa at a speed of 30 mm / s. Number of voids added. At this time, the voids were measured for the number of voids of 1 mm or more that can cause chipping during the cutting process.

(2) 180 degree peeling strength measurement (between adhesive layer and adhesive layer): In order to measure the peeling force between adhesive layer and adhesive layer, each film was laminated | stacked with dicing film at normal temperature (25 degreeC), and it left for 1 hour, and the Then, a rectangular film having a size of 25 mm (width) x 70 mm (length) was made, and 180 ° Peel Strength was measured using an Instron tester. At this time, the peeling rate was measured at 300 mm / min. The dicing film was produced by the company, and a 10 μm ultraviolet curable pressure sensitive adhesive was coated on a 100 μm polyolefin film. The tack value of the dicing film is 70 gf before ultraviolet curing and 3 gf after ultraviolet curing, respectively. In the specimen of stainless steel (SUS 304), the 180-degree peel strength was 1.2 N / 25 mm before UV curing.

(3) Bubble measurement after die bonding: A 525 탆 thick wafer coated with a dioxide film was cut into 5 mm x 5 mm size, laminated with an adhesive film at 60 ° C, and cut with only the adhesive part left. . The glass plate having a thickness of 155 μm and a size of 18 mm × 18 mm was placed on a hot plate having a temperature of 100 ° C., and the wafer lamination of the adhesive-laminated wafer was die bonded with a force of 100 gf for 0.5 seconds, and then the bubble state was observed under a microscope. After completion of bubble observation, the sample was cured at 125 ° C. for 2 hours, and then the bubble state was observed under a microscope. Thereafter, the mixture was further cured at 125 ° C. for 2 hours, and then pressed for 15 seconds at a pressure of 200 psi at 175 degrees to observe the bubble state under a microscope. The thermocompression was carried out for 15 seconds at a pressure of 200 psi at 175 degrees using a CARVER instrument.

(4) Die Shear Strength: A 525㎛ thick wafer coated with a dioxide film is cut into 5mm x 5mm size as shown in the figure below, and then laminated and bonded at 60 degrees with an adhesive film. The cut was made leaving only parts. Place a wafer with a thickness of 525 µm and a size of 10mm x 10mm on a hotplate with a temperature of 120 ° C, attach a piece of wafer with adhesive lamination on it, compress it with 500gf force for 20 seconds, and cure at 125 ℃ for 2 hours, and then 175 Fully cured at 4 ° C. for 4 hours. The measurement measured die shear strength at 250 ° C. at a rate of 100 μm / sec.

(5) Tensile Modulus Measurement: A tensile modulus is measured using an Instron tester as shown in Fig. 2, by making a specimen having a thickness of 40 μm. At this time, measure using 100N load cell, and fix both ends of specimen to tensile tester. The measurement speed was measured at 100 mm / min.

(6) Tack measurement: Tack is measured using a tack tester (Model name: TopTack 2000A). The specimens are prepared in a size of 20 mm (width) x 80 mm (length) and placed on a table at 30 ° C. The probe size is 3/8 inch, the applied pressure is 200gf, the dwell time is 20s after the pressure is applied, the separation speed is 0.08mm / s and the load cell is 1.0 Measured at Kgf.

(7) Pick up Evaluation: After picking up using a die bonder (Die Bonder, model name: SDB-10M, manufacturer: Samsung Electronics), the measurement results are shown in Table 1 below. The thickness of the wafer was 80 μm, the chip size was cut into 10 mm × 10 mm, and after UV curing, the extending length was 5 mm, and the pin height was picked up at 0.4 mm. . Pick up force was 100 gf and pick up time was measured at 300 ms.

(8) Evaluation of Inter-Adhesion Solidification: In order to evaluate the inter-adhesion fixation after standing after chipping (Sawing) process, it was allowed to stand for 24 hr after expanding with a stretching length of 5 mm in a die bonder without UV curing. . Pick-up was evaluated after UV curing after standing.

As shown through Table 1, in the case of the adhesive film prepared by adjusting the content of the phenoxy resin and the ester-based thermoplastic resin (Examples 1 to 4) otherwise die shear strength than (Comparative Examples 1 to 4) Was excellent, and the pick-up characteristic was excellent without the adhesiveness between the adhesives. This is because the phenoxy resin or ester-based thermoplastic resin contained in the film state at room temperature exhibits a solid phase property and the tensile modulus increases as the content increases. This means that the pick-up success rate can be increased because it prevents the adhesion between the adhesives in the semiconductor pickup process and reduces the adhesion of the adhesive layer.

In addition, as shown in Table 1, when the content of the phenoxy resin is less than 15% by weight voids in the mounting process, the generated voids may cause chipping (Chipping) in the cutting (Sawing) process. In addition, when the total content of the phenoxy and ester-based thermoplastic resin is more than 45% by weight, high temperature stability is lowered and die shear strength is lowered to 5 Kgf or less, thereby causing a problem in reliability.

In addition, as shown in Table 1, when the total content of the phenoxy resin or the ester-based thermoplastic resin is less than 20% by weight, bubbles are often generated during die bonding, the room temperature modulus is lowered, and the adhesiveness between the adhesives is severe, resulting in poor pickup characteristics. There is a problem.

Although the present invention has been described in detail with reference to preferred embodiments of the present invention, these are merely exemplary, and those skilled in the art to which the present invention pertains have various modifications and equivalents therefrom. It will be appreciated that embodiments are possible. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

Claims (13)

Based on total solids (1) 2 to 15 weight percent of phenoxy resin; (2) 10 to 30% by weight of the ester thermoplastic resin; (3) 30 to 60% by weight of an elastomer resin containing a hydroxyl group or an epoxy group; (4) 5 to 20% by weight of an epoxy resin; (5) 2 to 20% by weight of at least one resin selected from the group of phenolic resin curing agents or aromatic amine curing agent resins as curing agents for epoxy resins; (6) 0.01 to 5% by weight of at least one catalyst selected from the group consisting of phosphine, boron and imidazole curing catalysts: Adhesive film composition for semiconductor assembly comprising a. The adhesive film composition for semiconductor assembly according to claim 1, wherein the softening point of the phenoxy resin is 50 to 100 ° C and the weight average molecular weight is in the range of 10,000 to 100,000. The adhesive film composition for semiconductor assembly according to claim 1, wherein the total content of the phenoxy resin and the ester thermoplastic resin is 20 to 45 wt%. The adhesive film composition for semiconductor assembly according to claim 1, wherein a glass transition temperature (Tg) of the ester-based thermoplastic resin is 30 ° C to 80 ° C. The adhesive film composition for semiconductor assembly according to claim 1, wherein the phenol resin or aromatic amine resin used as a curing agent for the epoxy resin has an equivalent ratio with the epoxy resin of 0.5 to 1.5. The adhesive film composition of claim 1, wherein the composition has a tensile modulus before curing of 30 Kgf / mm 2 or more. The adhesive film composition of claim 1, wherein the composition of the probe tack before curing is 13 gf or less. The adhesive film composition of claim 1, wherein the composition has an elastic modulus of 8 MPa or less at 175 ° C after curing in a molding process step. The adhesive film composition for semiconductor assembly according to claim 1, wherein the composition further comprises 0.01 to 7% by weight of a silane coupling agent. According to claim 1, wherein the composition further comprises a filler of 0.1 to 50% by weight based on the total solids, and the adhesive film composition for semiconductor assembly, characterized in that the particle size of the filler ranges from 5nm to 10㎛. An adhesive film for semiconductor assembly, characterized in that formed with the adhesive composition for semiconductor assembly according to any one of claims 1 to 10. 12. The adhesive film for semiconductor assembly according to claim 11, wherein the semiconductor adhesive film adheres a printed circuit board (PCB) and a single crystal silicon die. A dicing die bond film comprising the adhesive film for semiconductor assembly of claim 11.