KR20090014513A - Bonding film composition using phenoxy resin for semiconductor assembly and bonding film prepared therefrom - Google Patents

Abstract

An adhesive film for semiconductor assembly is provided to ensure the adhesive force between wafers or of a wafer and PCB, to improve the pick-up property with an adhesion layer due to the improvement of tensile modulus, and to minimize the bubbles generated in a die attach process due to a thermoplastic property. An adhesive film composition for semiconductor assembly comprises (a) phenoxy-based resin, (b) elastomeric resin containing a hydroxyl group or an epoxy group, (c) epoxy-based resin, (d) phenol type epoxy hardener or aromatic amine-based hardener, (e) at least one material selected from the group consisting of a latent catalytic curing agent and curing catalyst, (f) silane coupling agent and (g) filler.

Description

Bonding film composition and adhesive film for semiconductor assembly using phenoxy resin {BONDING FILM COMPOSITION USING PHENOXY RESIN FOR SEMICONDUCTOR ASSEMBLY AND BONDING FILM PREPARED THEREFROM}

The present invention relates to semiconductor assembly adhesive film compositions and adhesive films, and more specifically to semiconductor adhesive bonding and adhesive bonding films that can improve manufacturing processability and reliability when used in semiconductor assembly processes, including phenoxy clock resins. It is about.

Conventional pastes have been mainly used for the joining of semiconductor devices and device or supporting members. However, in recent years, semiconductor devices have been required to be miniaturized and refined according to the trend of miniaturization and large capacity. Many pastes, which have been used in recent years, have disadvantages such as abnormality during wire bonding due to protrusion or inclination of semiconductor devices, bubble generation, and difficulty in controlling the thickness. Therefore, in recent years, adhesive film is mainly used instead of the past paste.

Adhesive films used in semiconductor assembly are often used in conjunction with dicing films. The dicing film refers to a film which is used for fixing a semiconductor wafer in a dicing process in a series of semiconductor chip manufacturing processes. The dicing process is a process of cutting a semiconductor chip into individual chips, followed by the above-described dicing process, followed by an expansion process, a pick-up process, and a mounting process.

Such dicing film is usually formed by coating a UV-curable or general-curable adhesive on a base film of a vinyl chloride or polyolefin structure and adhering a cover film of PET material on top of it. On the other hand, the general method of using the adhesive film for the assembly of semiconductors is to attach the adhesive film to the semiconductor wafer, and then the dicing film having the same composition as the above is laminated on the dicing film after the cover film is removed. Along with fragmentation.

Recently, as a bonding agent for the assembly of semiconductors for die-bonding, the dicing film from which PET cover film has been removed and the adhesive film are laminated together to form a single film, and then the semiconductor wafer is attached on top of it and sculpted according to the dicing process. In this case, however, unlike the existing dicing film, which is intended only for dicing, the die and die-adhesive film must be dropped at the same time during the pick-up process. Difficulty is encountered, 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.

Recently, the semiconductor assembly process using dicing, die bonding, semiconductor, assembly, and adhesives is carried out after the wafer mounting process with dicing film on the wafer with the designed circuit at 50-80 ℃, followed by dicing process. The wafer is sculpted and die-bonded to stack chips in high temperature conditions. At this time, the adhesive layer should exhibit fluidity at high temperature to reduce the initial void size. In order to fix the stacked chip, an epoxy molding process is performed after a precure process for a predetermined time at 125 ° C to 175 ° C. Epoxy molding operation is typically carried out by applying an epoxy molding compound (EMC) at a high pressure at 150 ℃ to 200 ℃ condition when the voids present on the surface between the stacked chips can be completely removed to make a high reliability device.

In addition, the adhesive film for the assembly of semiconductors increases the content of the hardened portion in the adhesive composition in order to achieve high reliability, which reduces the tensile strength of the film and cuts it in the pre-cutting process to cut the film into a size suitable for the semiconductor wafer. Burr or chipping may occur during this chipping or sawing process, which is a semiconductor assembly process. In addition, after the pick-up process, the adhesive film is deformed due to the high adhesion strength with the adhesive, thereby reducing the pick-up success rate. In addition, due to the increase in modulus during the die attach process and the curing, the devices assembled at high temperature and high pressure are pressed during the epoxy molding compound (EMC) molding process, resulting in the rough surface of the PCB substrate. There is a problem that bubbles are generated and have a great adverse effect on reliability.

The embodiments of the present invention are intended to overcome the problems of the conventional techniques described above, and one object of the present invention is to include a diphenic film in the pick-up process by including a thermoplastic phenoxy resin having a cured or uncured adhesion promotion effect. It is to provide an adhesive film composition for a semiconductor assembly that can reduce the adhesion with the adhesive layer of the can increase the pickup success rate.

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

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-mentioned purposes is a phenoxy resin; Elastomer resins containing a hydroxyl group or an epoxy; Epoxy resins; Phenol type epoxy resins hardeners or amine type curing resins; At least one substance selected from the group consisting of latent catalyst type curing agents and curing catalysts; Silane coupling agent; And assembly of adhesive film for semiconductor assembly, which is characterized by containing fillers.

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

According to the embodiments of the present invention, the composition for semiconductor assembly adhesive film contains phenoxy resin, which reduces the adhesion with the PSA (adhesive layer) due to the rigidity of the film according to the excellent solid properties of the film at room temperature. In addition, due to the hard properties of the surface during the semiconductor fabrication process, the pick-up success rate between the adhesive layer and the adhesive layer is increased. On the other hand, since the change in the tack value is small, the adhesion force can be maintained during wafer mounting, and the die share value can be increased due to the increase in the curing speed. Due to the high fluidity at high temperature, the effect of filling the surface roughly during die attach process is excellent, minimizing bubbles generated and the effect of filling the rough surface such as PCB substrate is not only difficult, but also moisture penetration by external environment is difficult. Shear adhesion also increases, which has the effect of ensuring high reliability.

The following describes in more detail the embodiments of the present invention.

Embodiments of the present invention characterize semiconductor adhesive assembly film compositions comprising phenoxy resins. The semiconductor assembling adhesive film composition of the present invention is phenoxy resin; Elastomeric resins containing a hydroxyl group or an epoxy; Epoxy resins; Phenol type epoxy resin resin hardening agent or amine type hardening agent; At least one substance selected from the group consisting of latent catalyst type curing agents and curing catalysts; Silane coupling agent; And fillers.

The phenoxy resin used in the embodiments of the present invention contains an epoxy group or a hydroxyl group at both ends, and in the case of the epoxy group, the equivalent weight is very small compared to the molecular weight to participate in curing, but acts as a thermoplastic resin to impart fluidity at high temperature. In particular, the presence of more hydroxyl groups in the composition enhances the cure rate ("Application of Epoxy Resin to Electronics", latest edition, issued Nov. 26, 2003, pages 25-26). The resin contains a large amount of hydroxyl groups to increase the curing rate. Hydroxyl groups present in phenoxy have a high curing rate dependence, so the curing rate is important in the pre-cure process of fixing the stacked semiconductor chips, so that the curing rate of the adhesive film can be controlled by controlling the content of the phenoxy resin. The hardening residual rate can also be adjusted. In addition, due to the large amount of hydroxyl groups present in phenoxy, the hardness of the film is increased, but since the tack value is less than that of other general thermoplastic resins, it is possible to increase the adhesion between the wafer and wafer during wafer mounting. And the high hardness can improve the pickup. The phenphenoxy resin that can be used in the present invention is a resin which helps to form an adhesive film and promotes interfacial adhesion, and exhibits fluidity while controlling the curing rate. The softening point and glass transition temperature (Tg) in the range of 0 ° C. to 200 ° C. It is preferable to have a weight average molecular weight in the range of 200-1,000,000. When the phenoxy resin has a softening point and a weight average molecular weight within the above range, it is maintained at a solid state at room temperature to facilitate pickup by reducing the adhesive force with the pressure-sensitive adhesive during the pickup process, there is no decrease in tack value with increasing content Therefore, it is excellent in adhesion force with the wafer at the bottom during wafer mounting process, and fluidity at high temperature can be removed during die attach and epoxy molding process to remove bubbles generated at the interface during attach.

One example of the phenoxy resin used in the embodiments of the present invention may be represented by the following formula (1).

[Formula 1]

Where

R ₁ to R ₈ are each one or more selected from the group consisting of a hydrogen atom, a halogen group, an alkyl group having 1 to 5 carbon atoms, an aryl group having 1 to 5 carbon atoms, a cyclic aliphatic group having 6 to 15 carbon atoms, and a nitro group,

X ₁ is a member selected from the group consisting of a linear alkyl group having 0 to 5 carbon atoms, a branched alkyl group, a methylol group allyl, an allyl group, a substituted allyl group, a phenoxy group having 6 to 15 cyclic aliphatic groups and an alkoxycarbonyl group High,

Z is a hydroxyl group or an epoxy group,

n is an integer of 30 ms to 400 ms.

In Formula 1, Y ₁ represents hydroquinone, 2-bromohydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, 4,4′-dihydroxybiphenyl, bis (4-hydroxy It is 1 or more types chosen from the group which consists of an oxyphenyl) ether, a phenol group, a cresol group, a cresol novolak group, and a fullerene group, As a specific example of Y <_1> , 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-methylethylli Den) bis [2,6-di (1,1-dimethylethyl) phenol], 4,4 '-(1-methylethylidene) bis [2- (2-propenyl) phenol], 4,4' -Methylenebis [2- (2-propenyl) phenol], 3,3'-dimethyl [l, l'-biphenyl] -4,4'-diol, 3,3'-bis (2-propenyl) -[1,1'-biphenyl] -4,4'-diol, 4,4 '-(1-methylethylidene) bis [2- Tyl-6-hydroxymethylphenol], tetramethylolbisphenol 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'-methylene Bis (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'-methylenebis [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) bispe Nol, 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-fluorophenyl) 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-phenyl Phenol], 4,4'-butylidenebis [3-methyl-6- (1,1-dimethylethyl) phenol], 4-hydroxy-α- (4-hydroxyphenyl-α-methylbenzeneacetylenemethyl Ester, 4-hydroxy-α- (4- Hydroxyphenyl-α-methylbenzeneacetyleneethyl ester, 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-methyl Thilidene) 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-fluoro Rophenyl) 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'-(di Nimethylene) bis [2,6-difluorophenol], 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'-cyclohexylyl Denbisphenol, 4,4'-cyclohexylidenebis [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-methylethylidene)] bisphenol, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bis [2-meth -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-hydroxyphenyl) -1,1,3,3- Phenol skeletons, such as tetramethyldisiloxane, the silicone oligomer which has a p-hydroxyphenyl group at a sock end, and 2,2'- methylidene bisphenol, 2,2'- methyl ethylidene bisphenol, and 2,2'- ethylidene bisphenol The linear alkyl group, branched alkyl group, aryl group, methylol group, allyl group, etc. are introduce | transduced into the aromatic ring of. 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 1 to 50 parts by weight based on the entire adhesive film composition for semiconductor assembly, more preferably Is preferably 10 to 30 parts by weight. When the content of the phenoxy resin is more than 50 parts by weight, the tensile strength of the film may be significantly increased, resulting in a poor coating property of the film.

The elastomeric resins that can be used in the embodiments of the present invention are the rubber components necessary for the formation of film, which are rubbers containing hydroxyl groups or epoxy groups, and preferably have an average molecular weight in the range of 500 to 5,000,000. Examples of the elastomer resin include acrylonitrile, butadiene, styrene, acryl, isoprene, ethylene, and propylene. It is possible to use one or more selected from the group consisting of carbon-based, polyurethane-based, and silicone-based elastomers, but not limited to this. It is preferable that the content of the elastomer resin is 5 to 85 parts by weight relative to the entire semiconductor assembly adhesive film composition. When the content of the elastomer resin is less than 5 parts by weight, it is difficult to form a film, and when it exceeds 85 parts by weight, reliability may be lowered.

The epoch watch resin that may be used in the embodiments of the present invention is not particularly limited as long as it exhibits hardening and adhesive action, but considering the film's shape, it can be used as an epoxy in close proximity to a solid phase or a solid surface. Do.

The above-mentioned solid epoxy resins are not particularly limited, but examples thereof include bisphenol-based, phenolic novolac-based, cresol-novolac-based, polyfunctional epoxy and amine-substituted epoxy resins. Epoxy, substituted epoxy, naphthol epoxy and derivatives thereof. Such products currently marketed as epoxy resins include YD-017H, YD-020, YD020-L, YD-014, YD-014ER, YD-014K, YD-019K, YD-019, and YD. -017R, YD-017, YD-012, YD-011H, YD-011S, YD-011, YDF-2004, YDF-2001, etc.Phenol novolac (Phenol®novolac) is a Yucca Shell Epoxy Co., Ltd. 152, Epicoat 154, JPEPN-201, Dow Chemical's DN-483, Kukdo Chemical's YDPN-641, YDPN-638A80, YDPN-638, YDPN-637, YDPN-644, YDPN-631, etc. In the case of o-cresol novolac, 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., and EOCN-102S, EOCN-103S , EOCN -104S, EOCN-1012, EOCN-1025, EOCN-1027, YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704 from Japan Nippon Chemical, N-665-EXP, etc. Examples of bisphenol-based novolac epoxy include KBPN-110, KBPN-120, and KBPN-115 of Kukdo Chemical, and Yuka Shell Epoxy Co., Ltd., Epon® 1031S, Inc. Celsius, Hwasung Co., Ltd. "Detacol" EX-611, "Detacol" EX-614, "Detacol" EX-614B, "Detacol" EX-622, "Detacol" EX-512, "Detacol" EX-521, "Detacol" EX-421, "Detacol" EX -411, DETA COL EX-321, KEP-10200, KD-1012, EP-5100R, KD-1011, KDT-4400A70, KDT-4400, YH-434L, YH-434, YH-300, etc. As the amine-based epoxy resin, Yucca shell Epoxy Co., Ltd. Epicoat 604, Dokdo Chemical YH-434 of Mitsubishi Gas Corporation, TETRAD-X of Mitsubishi Gas Chemical Co., Ltd., ELT-120 of Sumitomo Chemical Co., Ltd., etc., and PT-810 of Cyclo Specialty Chemical Co., Ltd. Epoxy resins include ECL-4234, ERL-4299, ERL-4221, ERL-4206, and Naphthol-based epoxy resins.Epoxylon HP-4032, Epiclone HP-4032D, and Epiclone HP-4700. There are epiclones 4701, and these can be used alone or in combination of two or more.

In the embodiments of the present invention, the epoxy resin content is preferably 5 to 40 parts by weight based on the entire semiconductor assembly adhesive film composition. When the content of the epoxy resin is less than 5 parts by weight, the reliability is lowered due to lack of hardened parts, and when the content exceeds 40 parts by weight, the tensile strength of the film may drop.

As the phenolic epoxy resin curing agent that can be used in the embodiments of the present invention, it can be used without special limitation, which is normally used, but it is a compound having two or more phenolic hydroxyl groups in one molecule, and the anti-corrosive corrosion resistance of the phenolic anticorrosive phenols during absorption A, bisphenol, F, bisphenol, S-based curing agent, resin, and phenol phenol novolac resin, bisphenol A, novolak resin, cresol, novolac, xyloxy, biphenyl, etc. are preferable. Examples of such phenolic epoxy resin curing agents currently available on the market include simple phenolic curing agents such as H-1, H-4, HF-1M, HF-3M, HF-3M, and HF-4M. MEH-78004S, MEH-7800SS, MEH-7800S, MEH-7800H, MEH-7800H, MEH-7800HH, MEH-78003H, KOLON Petrochemical Co., Ltd. -F3065, MEH-7851SS, MEH-7851S, MEH7851M, MEH-7851H, MEH-78513H, MEH-78514H, and KP-F4500, triphenylmethyl-based methylated plastics of biphenyl. The MEH-7500, MEH-75003S, MEH-7500SS, MEH-7500S, MEH-7500H, etc. of the Plastic Industry Co., Ltd. can be used alone, or they can be used alone or in combination of two or more types. The content of the phenol-type epoxy resin curing agent is preferably 5 to 30 parts by weight based on the total adhesive film composition for semiconductor fabrication. The equivalent ratio of phenol to epoxy in the phenolic epoxy resin curing agent is preferably 0.8 to 1.3.

As the amine-type epoxy resin curing agent that can be used in the embodiments of the present invention, any of the amine-type epoxy resins that can be used can be used without particular limitation, but those represented by the following formulas (2) to (6) can be used as aromatic compounds having two or more amine groups in one molecule. Can be.

[Formula 2]

In the above formula,

X ₂ is a single bond or 1 selected from the group consisting of —CH ₂ —, —CH ₂ CH ₂ —, —O—, —SO ₂ —, —NHCO—, —C (CH ₃ ) ₂ —, or —CO— Paper,

R ₁ to R ₁₀ include at least one or more amine groups and are hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group.

[Formula 3]

In the above formula,

R ₁₁ to R ₁₈ 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.

[Formula 4]

In the above formula,

Z ₁ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a hydroxyl group,

R ₁₉ to R ₁₃ 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.

[Formula 5]

In the above formula,

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.

[Formula 6]

In the above formula,

X ₃ is 1 type selected from the group consisting of -CH _2- , -NH-, -SO _2- , -S-, or -O-,

R ₄₂ to R ₄₉ 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.

Representative examples of the amine-type epoxy resin curing agent of the formula (2) is 3,3'-diaminobenzidine (3,3'-diaminobenzidine), 4,4'-diaminodiphenyl methane (4,4'-diaminodiphenyl methane), 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'-bis [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-propylenediphenylketone (4,4'-diamino-3,3', 5,5'-tetra-n-propyldiphenylketone), 4,4'-diamino-3 , 3 ', 5,5'-tetraisopropyldiphenylketone (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 4,4'-diamino-3,3'5,5'-tetra-n-propyldiphenylmethane, 4,4'-diamino-3,3'5,5'-tetramethyldiphenyl Methane (4,4'-diamino-3,3'5,5'-tetramethyldiphenylmethane), 4,4'-diamino-3,3'5,5'-tet Isopropyldiphenylmethane (4,4'-diamino-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), 4,4'-diamino-3,5-dimethyl-3', 5'-diisopropyldiphenylmethane (4,4'-diamino-3,5-dimethyl -3 ', 5'-diisopropyldiphenylmethane), 4,4'-diamino-3,5-diethyl-3', 5'-diisopropyldi 4,4'-diamino-3,5-diethyl-3 ', 5'-diisopropyldiphenylmethane, 4,4'-diamino-3,5-diethyl-3', 5'-dibutyldiphenyl Methane (4,4'-diamino-3,5-diethyl-3 ', 5'-dibutyldiphenylmethane), 4,4'-diamino-3,5-diisopropyl-3', 5'-yabutylyaphenyl Methane (4,4'-diamino-3,5-diisopropyl-3 ', 5'-dibutyldiphenylmethane), 4,4'-diamino-3,3'-diisopropyl-5', 5'-dibutyldi Phenylmethane (4,4'-diamino-3,3'-diisopropyl-5 ', 5'-dibutyldiphenylmethane), 4,4'-diamino-3,3'-dimethyl-5', 5'-dibutyldi Phenylmethane (4,4'-diamino-3,3'-dimethyl-5 ', 5'-dibutyldiphenylmethane), 4,4'-diamino-3,3'-diethyl-5', 5'-dibutyl Diphenylmethane (4,4'-diamino-3,3'-diethyl-5 ', 5'-dibutyldiphenylmethane), 4,4'-diamino-3,3'-dimethyldiphenylmethane (4,4'- diamino-3,3'-dimethyldiphenylmethane), 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-dia Mino-3,3'-di-n-propyldiphenylmethane (4,4'-diamino-3,3'-di-n-propyldiphenylmethane), 4,4'-diami -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-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-triiso Propyldiphenylmethane (4,4'-diamino-3,3 ', 5-triisopropyldiphenylmethane), 4,4'-diamino-3,3', 5-tributyldiphenylmethane (4,4'-diamino- 3,3 ', 5-tributyldiphenylmethane), 4,4'-diamino-3-methyl-3'-ethyldiphenylmethane (4,4'-diamino-3-methyl-3'-ethyldiphenylmethane), 4,4 '-Diamino-3-methyl-3'-isopropyldiphenylmethane (4,4'-diamino-3-methyl-3'-isopropyldiphenylmethane), 4,4'-diamino-3-ethyl-3'- Isopropyldiphenylmethane (4,4'-diamino-3-ethyl-3'-iso propyldiphenylmethane), 4,4'-diamino-3-ethyl-3'-butyldiphenylmethane (4,4'-diamino-3-ethyl-, 3'-butyldiphenylmethane), 4,4'-diamino-3 -Isopropyl-3'-butyldiphenylmethane (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-bis (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'-tetra Methyldiphenylbenzanide (4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylbenzanilide), 4,4'-diamino-3,3', 5,5'-tetraethyldipheninbenzanyl Lead (4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylbenzanilide), 4,4'- Amino-3,3 ', 5,5'-tetra-n-propyldiphenylbenzanilide (4,4'-diamino-3,3', 5,5'-tetra-n-propyldiphenylbenzanilide), 4,4 '-Diamino-3,3', 5,5'-tetraisopropyldiphenylbenzanilide (4,4'-diamino-3,3 ', 5,5'-tetraisopropyldiphenylbenzanilide), 4,4'-amino -3,3 ', 5,5'-tetrabutyldiphenylbenzanilide (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-propyl 4,4'-diamino-3,3 ', 5,5'-tetra-n-propyldiphenylsulfone, 4,4'-diamino-3,3', 5,5'-tetraisopropyldi Phenylsulfone (4,4'-diamino-3,3 ', 5,5'-tetraisopropyldiphenylsulfone), 4,4'-diamino-3,3', 5,5'-tetramethyldiphenyl ether (4,4 '-diamino-3,3', 5,5'-tetramethyldiphenylether), 4,4'-diamino-3,3 ', 5,5'-tetra Diphenyl ether (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, 4,4'-diamino-2,2'-dimethylbibenzyl (4, 4'-diamino-2,2'-dimethylbibenzyl), 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4 '-Diaminodiphenylether (3,4'-diaminodiphenylether), 3,3'-diaminodiphenylmethane (3,3'-diaminodiphenylmethane), 3,4'-diaminodiphenylethane (3,4') -diaminodiphenylmethane), 2,2'-diamino-1,2-diphenylethane (2,2'-diamino-1,2-diphenylethane), or 4,4'-diamino-1,2-diphenylethane4,4 ' -diamino-1,2-diphenyletha ne, 2,4-diaminodiphenylamine, 4,4'-diaminooctafluorobiphenyl, o-dianisidine, and the like, and representative examples of Chemical Formula 3 include 1,5-diaminonaphthalene (1 , 5-diaminonaphthalene), 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, and the representative examples of Chemical Formula 4 are paraosaniline Representative examples of Formula 5 include 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, and 1,5-diaminoanthra 1,5-diaminoanthraquinone, 2,6-diaminoanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone 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-anthra quinone), and a representative example of Chemical Formula 6 is 3,7-diamino-2,8-dimethyldibenzothiophenesulfone

(3,7-diamino-2,8-dimethyldibenzothiophenesulfone), 2,7-diaminofluorene, 3,6-diaminocarbazole, and the like, and these Can be used alone or in combination of two or more.

In the embodiments of the present invention, the content of the amine-type epoxy resin hardener is preferably 5 to 30 parts by weight relative to the entire semiconductor assembly adhesive film composition. The equivalent ratio of the amine to the epoxy of the amine epoxy resin curing agent is preferably 0.3 to 1.5.

As a curing catalyst that can be used in the embodiments of the present invention, a phosphine or boron curing catalyst and an imidazole catalyst can be used. The phosphine-based curing catalysts that can be used in the embodiments of the present invention include triphenylphosphine, tri-o-tolylphosphine and tri-m-toylphosphine. 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, Diphenylphosphinostyrene(Diphenylphosphinous chloride), Tri-n-octylphosphine oxide, Diphenylphosphinyl hydroquinone, Tetrabutylphosphonium hydroxide, Tetrabutylphosphinium acetate Tetrabutylphosphonium acetate, Benzyltriphenylphosphonium hexafluoroantimonate, Tetraphenylphosphonium tetraphenylborate, Tetraphenylphosphonium tetra-p-toylborate , Benzyltriphenylphosphonium tetraphenylborate, benzyltriphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrafluoroborate, p-toyllphenylphosphonium tetra-p-toylborate (p-Tolyltriphenylphosphonium tetra-p-tolylborate) Triphenylphosphinetriphenyl Triphenylphosphine 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), and the boron curing catalyst is phenyl boronic acid, 4-methylphenyl boronic acid, 4-methoxyphenyl boronic acid, or 4-Methoxyphenyl boronic acid. , 4-trifluoromethoxyphenyl boronic acid, 4-tert-butoxyphenyl boronic acid, 3-fluoro-4-methoxyphenyl Boronic acid (3-Fluoro-4-methoxyphenyl boronic acid), Pyridine-triphenylborane, 2-ethyl-4-methylimidazolium tetraphenylborate (2-Ethyl-4-methyl imidazolium tetraphenylborate) , 1,8-diazabicyclo [5.4.0] Sen-7-tetraphenylborate (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- methylimidazole), 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole , 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Phenyl 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl imidazolium trimellitate, 1-cyanoethyl-2-phenyl Midazolium 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-diamino-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 addu ct), 2-methylimidazole isocyanuric acid adduct dihydrate, 2-phenyl-4,5-dihydroxymethylimidazole (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, 2,4-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-methacryloyloxyethyl-1,3,5-triazineisocyanuric acid derivative ( 2,4-diamino-6-methacryloyloxylethyl-1,3,5-triazine isocyanuric acid adduct ), 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole (1- (2-cyanoethyl) -2-ethyl-4-methylimidazole), 1-cyanoethyl-2-methyl Midazole (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-ethyl-4-methyl imidazoline ), 2-benzyl-4-methyl dimidazoline, 2-ethyl imidazoline, 2-phenylimidazole, 2 2-phenyl-4,5-dihydroxymethylimidazole, melamine, dicyandiamide, etc., which can be used alone or in two kinds. You can mix and use the above. In the present invention, the curing catalyst content is preferably 0.01 to 10 parts by weight relative to the entire semiconductor assembly adhesive film composition. More preferably, the content of the curing catalyst is preferably 0.01 to 5 parts by weight based on the whole adhesive film composition for semiconductor assembly. If it is more than that, the storage stability may be inferior.

In the present invention, the latent catalyst type curing agent physically or chemically includes a phosphine-based or boron-based curing catalyst in the phenol curing agent resin, and generally exhibits the same physical properties as the composition in which the phenol curing agent and the curing catalyst are mixed. A commercial example of this is MEH-7800C of Meihwa Plastics Industry.

In the present invention, a silane coupling agent can be used as a silane coupling agent, which has no special limitation and is commonly used as an adhesion promoter for enhancing the adhesion between the surface of inorganic materials such as silica and the resin of the adhesive film when the composition is blended. For example, 2- (3,4 epoxy cyclohexyl) -ethyltrimethoxysilane, 3-glycidoxycitrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidium Doxypropyltriethoxysilane, N-2 (aminoethyl) 3-amitopropylmethyldimethoxysilane, 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, merceto-containing 3-mercetopropylmethyldimethoxysilane, 3-mercetopropyltriethoxysilane, isocyanate-containing 3-isocyanatepropyltriethoxysilane You can demonstrate this, and you may marry alone or two or more. And it can be used.

In the present invention, the content of the silane coupling agent is preferably from 0.01 to 10 parts by weight relative to the entire semiconductor assembly adhesive film composition. When the content of the silane coupling agent exceeds 10 parts by weight, the adhesion may be lowered and the tensile strength of the film may be lowered.

The fillers that may be used in the present invention may use inorganic or organic fillers as needed. As inorganic fillers, metal powders such as gold powder, silver powder, copper powder and nickel can be used, and nonmetals such as alumina, magnesium hydroxide, magnesium hydroxide, magnesium carbonate, calcium silicate, magnesium silicate, magnesium oxide, calcium oxide and aluminum oxide. Aluminum nitride, silica, boron nitride, titanium dioxide, glass, iron oxide, ceramic, etc. can be used, and organic fillers such as carbon, rubber fillers, and polymers can be used. The shape and size of the filler are not particularly limited, but in general, inorganic fillers are preferably used in the form of spherical silica and amorphous silica, and the size of the filler is preferably in the range of 5 nm to 10 um. If the particles of the inorganic filler is more than 10um 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 to be used is preferably 0.1 to 60 parts by weight based on the entire semiconductor assembly adhesive film composition. In general, 0.1 to 30 parts by weight is preferable for the same chip bonding, and 10 to 60 parts by weight for other chip bonding. When the content of the filler exceeds 60 parts by weight, it is difficult to form the film, which may lower the tensile strength of the film.

Semiconductor assembly assembly adhesive film compositions of embodiments of the present invention may additionally contain organic solvents. The organic solvents lower the viscosity of the adhesive film composition for semiconductor assembly and facilitate the manufacture of the film. However, the organic solvent is not particularly limited, but is not particularly limited, but is not limited to toluene, xylene, propylene glycol, monomethyl ether acetate, benzene, methyl acetone, benzene, methyl acetone, and ethyl acetate. Hydrofuran, dimethylformaldehyde and cyclohexanone can be used.

In the embodiments of the present invention, the organic solvent includes, as a residual amount, excluding the contents of the remaining components in the entire composition of the semiconductor, the adhesive for the assembly, the adhesive film, and is preferably 5 to 85 parts by weight. The content of the organic solvent is determined by the viscosity of the composition. Usually it is possible to form a stable film at 20 to 60 parts by weight.

Semiconductor assembly assembly adhesive film compositions of the present invention may additionally contain an ionic clathrate to adsorb ionic impurities and to achieve insulation reliability during adsorption. Such ion trapping agents have no special restrictions, and, for example, triazine thiol compounds, zirconium zirconium, antimony bismuth, magnesium magnesium aluminum compounds, and the like. have.

It is preferable that the content of the ion trapping agent be 0.01 to 5 parts by weight relative to the entire semiconductor assembly adhesive film composition. When the ion trapping agent is excessive, it may become an impurity by itself and economic efficiency is low.

Another aspect of the present invention relates to semiconductor assembly adhesive films formed from the above-described semiconductor assembly assembly adhesive films. The use of semiconductors, adhesives, and assembly films for phenoxy resins allows the solid properties to be very good at room temperature, which favors pick-up with adhesive layers and increases fluidity at temperatures between 100 ° C and 130 ° C, such as PCBs or wafers. Its excellent effect of filling rough surfaces minimizes bubbles generated, which can provide adhesive films for assembling semiconductors that can achieve high adhesion and reliability.

Another aspect of the present invention relates to an adhesive for semiconductor assembly for dicing die bonding comprising the adhesive film for semiconductor assembly. The semiconductor assembly adhesive for dicing die bonding can minimize the generation of bubbles in the process of adhering the die adhesive film on the back surface of the semiconductor wafer.

Examples will be described in greater detail below with reference to the present invention. These examples are merely for the purpose of explanation and are not intended to limit the scope of protection of the present invention.

[Examples 1-1 to 1-4, Examples 2-1 to 2-4 and Comparative Examples 1 and 2]

After adding the components of 1L cylindrical flask containing high speed stirring rod and dispersing them at high speed at 4000rpm for 20 minutes, the composition was prepared. After filtration using 50μm capsule filter, the film was coated with 40μm thick adhesive film. After 20 min of drying at 60 ° C., 20 min of drying at 90 ° C., and then stored at room temperature for 1 day.

Example # 1-1

(a) Phenoxy Resin (PKHP, InChem Investment in Chemicals) 12 parts by weight,

(b) Epoxy-containing elastomers and resins (KLS-1045, manufactured by Fujikura Chemical), 170 parts by weight,

(c) Polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon-Gaku) 10 parts by weight, and epoxy resin made of cresol novolac and biphenyl (CER-1020, manufactured by Nippon Kayaku), 10 parts by weight

(d) Biphenyl-based phenol hardener (KPH-F4500, manufactured by Kolon Emulsifier) 12 parts by weight,

(e) 3 parts by weight of a phosphine-based curing catalyst (MEH-7800C, manufactured by Meihwa Industry) contained in a xylacyl phenol curing agent,

(f) imidazole-based cure catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate, part,

(g) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 0.7 parts by weight,

(h) Amorphous silica (R-972, manufactured by Daegu) 22 parts by weight.

Example 1-2

(a) Phenoxy resin (PKHP, InChem Investment in Chemicals) 24 parts by weight,

(b) Epoxy-containing elastomers and resins (KLS-1045, manufactured by Fujikura Chemical), 170 parts by weight,

(c) Polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon-Gaku) 10 parts by weight, and epoxy resin made of cresol novolac and biphenyl (CER-1020, manufactured by Nippon Kayaku), 10 parts by weight

(d) Biphenyl-based phenol hardener (KPH-F4500, manufactured by Kolon Emulsifier), 42 parts by weight,

(e) 3 parts by weight of a phosphine-based curing catalyst (MEH-7800C, manufactured by Meihwa Industry) contained in a xylacyl phenol curing agent,

(f) Imidazole-based curing catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate, part,

(g) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 0.7 parts by weight,

(h) Amorphous silica (R-972, manufactured by Daegu) 22 parts by weight.

Example 1-3

(a) Phenoxy resin (PKHP, InChem Investment in Chemicals) 36 parts by weight,

(b) Epoxy-containing elastomers and resins (KLS-1045, manufactured by Fujikura Chemical), 170 parts by weight,

(c) Polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon-Gaku) 10 parts by weight, and epoxy resin made of cresol novolac and biphenyl (CER-1020, manufactured by Nippon Kayaku), 10 parts by weight

(d) Biphenyl-based phenol hardener (KPH-F4500, manufactured by Kolon Emulsifier) 12 parts by weight,

(e) 3 parts by weight of a phosphine-based curing catalyst (MEH-7800C, manufactured by Meihwa Industry) contained in a xylac phenol curing agent,

(f) Imidazole-based curing catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate, part,

(g) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 0.7 parts by weight,

(h) Amorphous silica (R-972, manufactured by Daegu) 22 parts by weight.

Example 2-1

(a) Phenoxy Resin (PKHP, InChem Investment in Chemicals) 12 parts by weight,

(b) Epoxy-containing elastomers and resins (KLS-1045, manufactured by Fujikura Chemical), 170 parts by weight,

(c) Polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon-Gaku) 10 parts by weight, and epoxy resin made of cresol novolac and biphenyl (CER-1020, manufactured by Nippon Kayaku), 10 parts by weight

(d) aniline-based curing agent (1,5-diaminonaphthalene, manufactured by Tokyo Chemical Industry) 26 parts by weight,

(e) Imidazole-based curing catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate, part,

(f) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 0.7 parts by weight,

(g) Amorphous silica (R-972, manufactured by Daegu) 22 parts by weight.

Example 2-2

(a) Phenoxy resin (PKHP, InChem Investment in Chemicals) 24 parts by weight,

(b) Epoxy-containing elastomers and resins (KLS-1045, manufactured by Fujikura Chemical), 170 parts by weight,

(c) Polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon-Gaku) 10 parts by weight, and epoxy resin made of cresol novolac and biphenyl (CER-1020, manufactured by Nippon Kayaku), 10 parts by weight

(d) aniline-based curing agent (1,5-diaminonaphthalene, manufactured by Tokyo Chemical Industry) 26 parts by weight,

(e) Imidazole-based curing catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate, part,

(f) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 0.7 parts by weight,

(g) Amorphous silica (R-972, manufactured by Daegu) 22 parts by weight.

[Example 2-3]

(a) Phenoxy resin (PKHP, InChem Investment in Chemicals) 24 parts by weight,

(b) Epoxy-containing elastomers and resins (KLS-1045, manufactured by Fujikura Chemical), 170 parts by weight,

(c) Polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon-Gaku) 10 parts by weight, and epoxy resin made of cresol novolac and biphenyl (CER-1020, manufactured by Nippon Kayaku), 10 parts by weight

(d) aniline-based curing agent (1,5-diaminonaphthalene, manufactured by Tokyo Chemical Industry) 26 parts by weight,

(e) Imidazole-based curing catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate, part,

(f) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 0.7 parts by weight,

(g) Amorphous silica (R-972, manufactured by Daegu) 22 parts by weight.

[Comparative Examples # 1 and # 2]

The adhesive film was prepared by preparing the adhesive film composition without adding the phenoxy resin among the components of Examples 1-1 and 2-1.

Comparative Example 1

(a) Epoxy-containing elastomers and resins (KLS-1045, manufactured by Fujikura Chemical), 170 parts by weight,

(b) Polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon-Gaku) 10 parts by weight and epoxy resin consisting of cresol, novolac and biphenyl (CER-1020, manufactured by Nippon Kayaku), 10 parts by weight

(c) Biphenyl-based phenol hardener (KPH-F4500, manufactured by Kolon Emulsifier) 12 parts by weight,

(d) 3 parts by weight of a phosphine-based curing catalyst (MEH-7800C, manufactured by Meihwa Industry) contained in the xylacyl phenol curing agent,

(e) Imidazole-based curing catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate, part,

(f) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 0.7 parts by weight,

(g) Amorphous silica (R-972, manufactured by Daegu) 22 parts by weight.

[Comparative Example 2]

(a) Epoxy-containing elastomers and resins (KLS-1045, manufactured by Fujikura Chemical), 170 parts by weight,

(b) Polyfunctional epoxy resin (EPPN-501H, manufactured by Nippon-Gaku) 10 parts by weight and epoxy resin consisting of cresol, novolac and biphenyl (CER-1020, manufactured by Nippon Kayaku), 10 parts by weight

(c) aniline-based curing agent (1,5-diaminonaphthalene, manufactured by Tokyo Chemical Industry) 26 parts by weight,

(d) Imidazole-based curing catalyst (2MA-OK, 2,4-diamino-6- [2'-methylimidazoly- (1 ')]-ethyl-s-triazine isocyanuric acid adduct dihydrate, part,

(e) Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 0.7 parts by weight,

(f) Amorphous silica (R-972, manufactured by Daegu) 22 parts by weight.

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

The physical properties of the semiconductor assembly adhesive film prepared according to Examples 1-1 to 1-2, 2-3-1 and Comparative Examples 1 and 2 were evaluated as follows, and the results are shown in Table 1 below. . In addition, in order to estimate the pick-up success rate, the deviation of the 180-degree peel value between the adhesive layer and the pressure-sensitive adhesive layer (PSA) and the pressure-sensitive adhesive layer (PSA) before and after the UV irradiation is calculated from the results of Table 1. It is shown in Table 2.

(1) Fill value (between the adhesive layer and the adhesive layer): In order to measure the adhesion between the adhesive layer and the adhesive layer, each film was laminated with a dicing film at room temperature (25 ° C.) for 1 hour, after which the size was 15 mm X 180 ° Peel Strength was measured using a 70 mm rectangular film. The dicing film was manufactured by the company, and coated with a 10 um UV curable pressure sensitive adhesive on a 100 um polyolefin film. The tack value of the dicing film is 130 gf before ultraviolet curing and 20 gf after ultraviolet curing, respectively. In addition, in specimens made of stainless steel (SUS 304), the 180-degree peel value was 3000 dyne / mm before UV curing, and the peel value was 0.09 N / 25 mm after irradiation with energy of an ultraviolet lamp of 300 mJ / cm ² .

(2) Viscosity: In order to measure the viscosity of each film, each film was laminated in four layers at 60 ° C., and a circular cut was performed with a diameter of 8 mm. At this time, the thickness is about 200 ~ 240um. The viscosity measurement range was measured from 30 ° C to 100 ° C and the temperature raising condition was 5 ° C / min. Table 1 shows the Eta values at 100 and 125 ° C, which measure the flowability at the die attach temperature.

(3) Void: The 525um wafer, coated with a dioxide film, was cut to a size of 5mm x 5mm, and then laminated with the adhesive film at 60 ° C, leaving only the adhesive part and cutting it. Place a glass with a thickness of 155 um and a glass size of 18 mm x 18 mm on a hot plate with a temperature of 100 ° C, and squeeze a piece of laminated wafer with adhesive on it for 0.5 seconds, and then bubble it under a microscope at 125 degrees for 2 hours. After observation, the film was compressed for 15 seconds at a pressure of 200 psi at 175 degrees, and the bubble state was observed under a microscope. Thermocompression was performed using a CARVER instrument for 15 seconds at a pressure of 200 psi at 175 degrees.

(4) Die Shear Strength: Cut 525um thick wafer coated with a dioxide film into 5mm x 5mm size as shown in the figure below.Laminate at 60 degrees with adhesive film Left and cut. Place a wafer with a thickness of 525um and a size of 10mm x 10mm on a hotplate with a temperature of 120 degrees, 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, then 175 ℃ Fully cured for 4 hours at. As shown in FIG. 1, the measuring method measures die shares at 250 ° C. at a rate of 100 μm / sec.

5) Tack value measurement: Attach the specimen to the flat 10cm X 10cm plate made of stainless steel (SUS 304) using double-sided tape, and then use a hemispherical tack probe with a diameter of 4mm. Measured by. At this time, the probe contact time to the adhesive film was 20 seconds, and the rising and falling speed of the probe was 0.08 mm / sec.

6) Curing residual rate measurement: In order to measure the curing residual rate of each film, each film was cut into 10mm x 10mm, heated at 25 ° C to 125 ° C for 15 minutes, cured at 125 ° C for 1 hour, and then at 125 ° C to 25 ° C. Lower to 15 ° C. This process is called 1 cycle at 125 ° C. The hardening residual formula is as follows.

Cure retention rate (%) = (heating value of initial film / calorific value after 125 ℃ cycle) X 100

Table 1

As in the case shown in Table 1 above, in the case of the adhesive film manufactured by including the phenoxy resin (Examples 1 to 1 to 2-3 and 2-1 to 2-3), the phenoxy resin was not included (Comparative) For example, after the UV, the 180-degree fill value between the adhesive layer and the adhesive layer was reduced, and as the phenoxy resin content increased, the 180-degree peeling value decreased further. This is because the phenoxy resins contained in the film at room temperature exhibit high solid-state quality, and the higher the content, the greater the degree of firmness of the outer surface of the film.

This means that the semiconductor pick-up process reduces the adhesion to the adhesive layer, which can increase the pick-up success rate.

In addition, since the change in the decrease of the selection value is very small, as shown in the above Table 1, the adhesive force can be maintained during wafer mounting. In addition, as the phenoxy resin content increases, the hardening residual ratio decreases, and by using this, the hard modulus of the film laminated on several chips is reduced to reduce the elastic modulus, thereby completely removing voids remaining during the epoxy molding pressure. Can be.

Also, as in the case shown in Table 1 above, when the adhesive film is manufactured, including the phenoxy resin (Examples 1 to 1 to 1-3 and 2-1 to 2-3), do not include the phenoxy resin. The Die Shear Strength value was higher than the Comparative Examples 1 and 2. It can be seen that as the content of the phenoxy resin increases, the curing rate increases and the adhesion increases.

Also, as in the case shown in Table 1 above, when the adhesive film is manufactured, including the phenoxy resin (Examples 1 to 1 to 1-3 and 2-1 to 2-3), do not include the phenoxy resin. Compared with (Comparative Examples 1 and 2), it can be seen that the eta (Eta) value and the amount of bubbles generated which represent the viscosity at 100 ° C or 125 ° C, which are the temperatures in the die attach process, have decreased drastically. Resins that do not contain phenoxy resins exhibit very small viscosity changes from 100 ° C to 125 ° C, and have low flow rates, while air bubbles do not disappear, while the phenoxy resin content decreases and the bubble generation decreases. . In addition, even if the phenoxy content is increased, there is almost no change in the Eta value at 125 ° C. Therefore, increasing the fluidity on the chip to be assembled during the die attach process means that the suppression of bubble formation is, of course, excellent in wire permeability. do.

In the above, the preferred embodiments of the present invention have been described in detail with reference to the present invention, but they are merely exemplary and have a wide variety of variations and equivalents from those who have normal knowledge in the field of technology to which the present invention belongs. It will be appreciated that embodiments are possible. Therefore, the true technical protection scope of the present invention should be determined in accordance with the technical idea of the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure about the method of measuring the die share value of the adhesive film for semiconductor assembly by this invention.

Claims (17)

Phenoxy resins; Elastomer resins containing a hydroxyl group or an epoxy; Epoxy resins; Phenol type epoxy resin resins or aromatic amine curing agents; At least one material selected from the group consisting of latent catalytic type curing agents and curing catalysts; Silane coupling agent; And Semi-conductor assembly adhesive film composition characterized by the inclusion of fillers. According to claim 1, the above-mentioned phenoxy resin is represented by the following chemical formula 1, the semiconductor assembly assembly adhesive film composition: [Formula 1] 　

In the above formula, R ₁ to R ₈ are each one or more selected from the group consisting of a hydrogen atom, a halogen group, an alkyl group having 1 to 5 carbon atoms, an aryl group having 1 to 5 carbon atoms, a cyclic aliphatic group having 6 to 15 carbon atoms, and a nitro group, X ₁ is a member selected from the group consisting of a linear alkyl group having 0 to 5 carbon atoms, a branched alkyl group, a methylol group allyl, an allyl group, a substituted allyl group, a phenoxy group having 6 to 15 cyclic aliphatic groups and an alkoxycarbonyl group High, Z is a hydroxyl group or an epoxy group, n is an integer of 30 ms to 400 ms. 3. A compound according to claim 2, wherein Y ₁ represents hydroquinone, 2-bromohydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, 4,4'-dihydroxybiphenyl, bis It is at least 1 type selected from the group which consists of (4-hydroxyphenyl) ether, a phenol group, a cresol group, a cresol novolak group, and a styrene group, The adhesive film composition for semiconductor assembly. A semiconductor adhesive bonding film composition according to claim 1, wherein the aromatic amine-based curing agent is at least one member selected from the group represented by the following Chemical Formulas 2 to 6. [Formula 2]

In the above formula, X ₂ is a single bond or 1 selected from the group consisting of —CH ₂ —, —CH ₂ CH ₂ —, —O—, —SO ₂ —, —NHCO—, —C (CH ₃ ) ₂ —, or —CO— Paper, R ₁ to R ₁₀ are hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkoxy group containing at least one amine group. [Formula 3]

In the above formula, R ₁₁ to R ₁₈ 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. [Formula 4]

In the above formula, Z ₁ is one selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a hydroxyl group, R ₁₉ to R ₁₃ 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. [Formula 5]

Where 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. [Formula 6]

In the above formula, X ₃ is 1 type selected from the group consisting of -CH _2- , -NH-, -SO _2- , -S-, or -O-, R ₄₂ to R ₄₉ 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. The semiconductor adhesive bonding film composition according to claim 1, wherein the phenoxy resin has a softening point in the range of 0 ° C to 200 ° C, and has a weight average molecular weight in the range of 200 to 1,000,000. The adhesive composition for a semiconductor assembly according to claim 1, wherein the elastomer resin containing a hydroxyl group or an epoxy group is characterized by a weight average molecular weight in the range of 500 to 5,000,000. According to claim 1, the epoxy resins mentioned above are bisphenol epoxy, phenol phenol novolac epoxy, o-cresol epoxy resin, polyfunctional epoxy resin, amine epoxy epoxy substituted epoxy epoxy, etc. And "semiconductor" adhesive film compositions for assembling semiconductors, characterized by having at least one selected from the group consisting of derivatives thereof. According to claim 1, the above-mentioned phenolic epoxy resin curing agent is composed of one or more selected from the group consisting of phenol phenol novolak resins, xylox resins, bisphenol A novolak resins, and cresol-based novolak resins. Adhesive film composition. The semiconductor adhesive bonding film composition according to claim 1, wherein the curing catalyst is one or more selected from the group consisting of phosphine-based curing catalysts, boron-based curing catalysts, imidazole-based curing catalysts, and derivatives thereof. The adhesive film composition for assembling a semiconductor according to claim 1, wherein the silane coupling agent is an epoxy-containing silane or a mercapto-containing silane. The semiconductor filler assembly adhesive film composition of claim 1, wherein the filler is a spherical or amorphous metal or nonmetallic inorganic filler and has a size in the range of 5 nm to 10 um. The method of claim 1, wherein the "semiconductor" assembly "adhesion" film composition is "phenoxy resin" 1 to 60 parts by weight; 5 to 85 parts by weight of an elastomer resin containing a hydroxyl group or an epoxy group; 5 to 40 parts by weight of the epoxy clock resin; 5 to 30 parts by weight of the phenol type epoxy resin curing agent or the aromatic amine curing agent; 0.01 to 10 parts by weight of the curing catalyst; A silane coupling agent "0.01" to "10" parts by weight; And a filler comprising an adhesive film composition for semiconductor assembly, characterized in that it comprises from 0.1 to 60 parts by weight. The adhesive film composition for semiconductor assembly according to claim 12, wherein the phenolic epoxy resin curing agent has an epoxy / phenol curing agent ratio of 0.8 to 1.3, and the aromatic amine curing agent has an epoxy / aromatic amine curing agent ratio of 0.3 to 1.5. The semiconductor adhesive bonding film composition according to claim 1, wherein the semiconductor adhesive assembly film composition contains an additional 5 to 85 parts by weight of an organic solvent. According to claim 1, the adhesive film composition for semiconductor assembly is composed of 0.051 parts by weight of at least one ion complexing agent selected from the group consisting of triazine thiol compound, zirconium series, antimony bismuth series, and magnesium aluminum series compound. Bonding film compositions for semiconductor assembly, including those containing. An adhesive film for assembling a semiconductor, comprising the adhesive film composition for assembling a semiconductor according to claim 1 or 2. Adhesive for semiconductor assembly for dicing die-bonding containing the adhesive film for semiconductor assembly as described in Claim 16.

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