JP2001168113A - Adhesive composition for semiconductor element and semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition for a semiconductor element whose reflow crack resistance is excellent by relaxing a thermal stress in a series of semiconductor device manufacturing processes, and to provide a semiconductor deice whose connection reliability is excellent and which is manufactured by using the adhesive composition. SOLUTION: This adhesive composition for a semiconductor element is constituted of polymer obtained by meta thesis polymerization whose elasticity in a room temperature is 1.5 GPa or less and whose average molecular weight rages from 5,000 to 500,000 and thermal hardening resin or optical hardening resin. Also, this is a semiconductor device mounted through adhesive members using the adhesive composition for the semiconductor elements on a substrate for loading.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition for a semiconductor element used for bonding a semiconductor element to a substrate for mounting a semiconductor element, and a semiconductor element mounted on the substrate for mounting a semiconductor element via the adhesive composition. The present invention relates to a semiconductor device.

[0002]

2. Description of the Related Art As semiconductor devices and packages are becoming lighter and thinner, the mounting density is high and low in addition to the method of mounting semiconductor devices on a lead frame as represented by a LOC (Lead On Chip) package. 2. Description of the Related Art A bare chip mounting of a semiconductor element on a mounting substrate such as a printed wiring board, which can be expected to be costly, and a semiconductor package using an organic substrate have been put to practical use. An epoxy resin, a polyimide resin, or the like has been used as an adhesive between the semiconductor element and the mounting board used in these packages. When these packages are mounted, reflow soldering for heating the entire substrate with infrared rays or the like is used, and the packages are heated to a high temperature of 200 ° C. or more. At this time, the moisture remaining inside the package is vaporized, and the stress generated due to the vaporization of the moisture cannot be alleviated by the adhesive, causing cracks (reflow cracks). The reflow crack significantly reduces the reliability of the semiconductor device, and is a serious technical problem. Further, in addition to moisture, there is a serious problem that stress is generated between the substrate and the element due to a difference in thermal expansion coefficient between the mounting substrate and the semiconductor element due to heating and cooling, and the element is separated. As a method for solving such a problem, a method of packing the semiconductor device in a moisture-proof package and opening it just before surface mounting, or drying the semiconductor device at 100 ° C. for 24 hours just before surface mounting, and then mounting Have been proposed. From the viewpoint of improving the adhesive, for example, an adhesive containing a moisture adsorbent (Japanese Patent Application Laid-Open No. 6-118227) has been proposed.

[0003]

However, the method of performing moisture-proof packing and drying of a semiconductor device requires a long manufacturing process and a high manufacturing cost. In the method using an adhesive proposed in Japanese Patent Application Laid-Open No. 6-118227, the problem of reflow cracks due to moisture still remains because the adsorbent that has absorbed moisture is present in the adhesive. An object of the present invention is to solve the problems of the prior art, to provide an adhesive composition for a semiconductor element excellent in reflow crack resistance by relaxing thermal stress generated in a series of semiconductor device manufacturing steps, and to provide the adhesive composition. An object of the present invention is to provide a semiconductor device manufactured by using the semiconductor device and having excellent connection reliability.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a method for manufacturing a room temperature (25
And a curing agent comprising a polymer obtained by metathesis polymerization having a modulus of elasticity of 1.5 GPa or less at ℃) and a number average molecular weight of 5,000 to 500,000, and a curing agent. Adhesive composition. The present invention also relates to an adhesive composition, wherein the polymer is a polymer obtained by metathesis polymerization of a cyclic olefin or a polymer obtained by further hydrogenating the polymer. Further, the present invention provides
It is a preferable adhesive composition when the polymer is a copolymer of a cycloalkene derivative and a norbornene derivative. Further, the present invention provides a semiconductor device mounted on a mounting substrate via an adhesive member using the adhesive composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer obtained by the metathesis polymerization used in the present invention is a thermoplastic polymer and has a storage elastic modulus of 25 ° C. at room temperature as measured with a dynamic viscoelasticity measuring device. Is 1.5 GPa or less, preferably 1.0 GPa or less. The elastic modulus of the thermoplastic polymer is prepared, for example, by preparing a film having a thickness of 50 μm and using a dynamic viscoelasticity measuring device RSAII manufactured by Rheometrics Scientific Co., Ltd. C. to 150.degree. C.). If the elastic modulus at room temperature of the thermoplastic polymer is higher than 1.5 GPa, the stress generated between the semiconductor element and the mounting substrate cannot be relaxed, which causes a reflow crack, which is not preferable. In consideration of the film-forming properties, the number average molecular weight of the present polymer is 5,000 to
500,000, preferably 20,000 to 10
It is 0000. Further, the glass transition temperature of the thermoplastic polymer is preferably 100 ° C. or lower, and more preferably −20 to 60 ° C.

The polymer used in the present invention includes, for example,
Examples include a polymer obtained by metathesis polymerization of a cyclic olefin or a polymer obtained by further hydrogenating this polymer.
The cyclic olefin is not particularly limited as long as it is capable of metathesis polymerization, but has a strain in the norbornene-based derivative (monomer) such as substituted or unsubstituted norbornene, dicyclopentadiene, dihydrodicyclopentadiene, and the like. Cycloalkene derivatives (monomers) are preferably used. These monomers can be used alone or in combination of two or more.

The norbornene derivatives (monomers) include norbornene, norbornadiene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidene norbornene, butylnorbornene, 5-acetyl-2-norbornene, dimethyl-5-norbornene-2,3-diene. Carboxylate, N-hydroxy-5-
Norbornene-2,3-dicarboximide, 5-norbornene-2-carbonitrile, 5-norbornene-2
-Carboxaldehyde, 5-norbornene-2,3-
Dicarboxylic acid monomethyl ester, 5-norbornene-
2,3-dicarboxylic acid dimethyl ester, 5-norbornene-2,3-dicarboxylic acid diethyl ester, 5-norbornene-2,3-dicarboxylic acid di-n-butyl ester, 5-norbornene-2,3-dicarboxylic acid dicyclohexyl Esters, 5-norbornene-2,3-dicarboxylic acid dibenzyl ester, 5-norbornene-2,
3-dicarboxylic anhydride, 3,6-epoxy-1,2,2
Bicycles such as 3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2-methanol, 6-triethoxysilyl-2-norbornene, 5-norbornen-2-ol Tricyclic norbornenes such as norbornene, dicyclopentadiene (a dimer of cyclopentadiene), dihydrodicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, etc., tetracyclododecene, methyltetracyclododecene, dimethylcyclotetrad Examples include tetracyclic norbornenes such as decene, and pentacyclic or higher norbornenes such as tricyclopentadiene (trimer of cyclopentadiene) and tetracyclopentadiene (tetramer of cyclopentadiene). A compound having two or more norbornene groups, for example, tetracyclododecadiene, symmetric tricyclopentadiene, or the like can also be used.

Cycloalkene derivatives (monomers) include cyclobutene, cyclopentene, cyclooctene,
Cyclododecene, 1,5-cyclooctadiene, 1,
3,5,7-cyclooctatetraene, 1,5,7-cyclododecatriene, 5,6-epoxy-1-cyclooctene, 3,4-epoxy-1-cyclooctene, 5-
Methoxy-1-cyclooctene, 5-bromo-1-cyclooctene, 5-isopropoxy-1-cyclooctene, 5-formyl-1-cyclooctene, 5-methoxy-1-cyclooctene, ethylcyclooct-1- Ene-5-carboxylate, (trimethylsilyl) cyclooct-1-ene-5-carboxylate, tetrahydroindene, methyltetrahydroindene, indene,
Acenaphthylenyl and the like. The above compounds are
It can be used alone or as a mixture of a plurality of monomers. When a plurality of monomers are used, a random copolymer or a block copolymer can be polymerized.

As a metathesis polymerization catalyst for polymerizing the above-mentioned monomer, a conventionally known polymerization method can be used. For example, Encyclopedia of Polymer Science and En
gineering, 9, 634-668 (HF Mark, NM Bikal
es, CG Overberger, edited by G. Menges, 1987, John Wiley
& Sons), transition metal compounds such as tungsten, molybdenum, rhenium, titanium, ruthenium, rhenium and iridium. When these catalysts are used, the polymerization efficiency can be drastically increased by adding a cocatalyst such as alkylaluminum. In addition, Macromolecules, p. 23, p. 3534 (1990) and Or
Tungsten, molybdenum and ruthenium carbene complexes described in ganometallics, 16, p. 3867 (1997) can be used.

[0010] The metathesis polymerization is usually carried out in the presence of a solvent. The polymerization solvent is not particularly limited as long as it does not reduce the activity of the catalyst. For example, toluene, acetone, benzene, xylene, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, N-methylpyrrolidone, γ-butyrolactone, N, N-dimethyl Formamide, N, N-dimethylacetamide, dimethylsulfoxide, ethyl acetate, methyl acetate, n-butyl acetate, chloroform, methylene chloride, 1,2-dichloroethane, n-pentane, cyclopentane, cyclopentene, n-hexane, cyclohexane, cyclohexene ,
Examples thereof include n-heptane, cycloheptane, n-octane, cyclooctane, and diethyl ether, and the monomer concentration is 1 to 80% by weight, preferably 5 to 30% by weight.

The polymer obtained by the metathesis polymerization is as follows:
The polymer may contain carbon and carbon double bonds in the polymer main chain, and the polymer may be hydrogenated with hydrogen gas or the like.
The hydrogenation reaction catalyst and reaction conditions can be determined by known methods. For example, a catalyst, palladium, nickel, a supported heterogeneous catalyst such as ruthenium, titanium, nickel, a Ziegler comprising a combination of a metal compound such as cobalt and an alkylaluminum derivative as described in Vol. 33, page 566 (1991). A homogeneous catalyst such as a type catalyst, a ruthenium complex, a rhodium complex, and a rhenium complex is used. The reaction conditions are temperature 0
At 200 ° C., the hydrogen pressure is 9.8 to 9807 KPa (0.1 to 1).
00Kg / cm ² ) preferably at a temperature of 25 to 150 ° C and a hydrogen pressure of 49 to 4903 KPa (0.5 to 50 Kg / c)
m ² ). Basically, this reaction is preferably performed in a state where the polymer is dissolved in a solvent. As a solvent to be used, toluene, acetone, benzene, xylene, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, N-methylpyrrolidone, γ-
Butyrolactone, N, N-dimethylformamide, N, N
N-dimethylacetamide, dimethylsulfoxide, ethyl acetate, methyl acetate, n-butyl acetate, chloroform, methylene chloride, 1,2-dichloroethane, n-pentane, cyclopentane, cyclopentene, n-hexane, cyclohexane, cyclohexene, n-heptane ,
Examples thereof include cycloheptane, cycloheptene, n-octane, cyclooctane, cyclooctene, and diethyl ether. The polymer concentration is 1 to 80% by weight, preferably 1 to 80% by weight.
30% by weight.

The curable resin (curing agent) used in combination with the polymer obtained by metathesis polymerization in the present invention is a commonly used curable resin (curing agent) that is cured by heat or light. The curable resin that is cured by heat is not particularly limited as long as it gives a three-dimensional cured product by heating.For example, a combination of a curing catalyst and an epoxy resin, a phenol resin, a bismaleimide resin, a cyanate resin, an oxetane derivative, or the like is used. No. These are 1 to 100 parts by weight, preferably 5 to 70 parts by weight, based on 100 parts by weight of the polymer obtained by the metathesis polymerization.

Curable resin (curing agent) that is cured by light
The compound is not particularly limited as long as it gives a three-dimensional cured product by irradiation with active energy rays, but the compound itself is cured by light irradiation, such as an azide compound, a chalcone compound, and a light represented by a cinnamic acid compound. Curable compounds. Further, in the presence of a photo-radical generator, monofunctional and difunctional or higher (meth) acrylate compounds, unsaturated polyesters, maleimide compounds, vinyl compounds represented by styrene and N-vinyl-2-pyrrolidone, allyl compounds and the like. No. Further, in the presence of a photoacid generator, it can be used in combination with a compound having one or more functional groups such as epoxy, oxetane and vinyl ether groups in the molecule. These are 1 to 100 parts by weight, preferably 5 to 70 parts by weight, based on 100 parts by weight of the polymer obtained by the metathesis polymerization. The curable resin (curing agent)
In addition to the method of curing only by heating and light irradiation,
Curing may be performed by a combination of heating and light irradiation.

The adhesive composition of the present invention may contain a filler, a glass fiber, a glass mat, a coloring agent, an antioxidant, a weathering agent, a flame retardant, and the like, if necessary.

The fillers used in the present invention include, for example, silver, alumina, titanium oxide, zircon oxide, antimony oxide, zinc oxide, magnesium oxide, aluminum oxide, magnesium hydroxide, aluminum hydroxide, calcium carbonate, Inorganic fillers such as talc, kaolin clay, mica, nepheline sinite, silica, silica gel, fused silica, synthetic silicic acid, quartz powder, quartzite powder, silicate earth, barium sulfate, calcium sulfate, pumice powder, glass balun, whisker, wood Examples include powder, resin beads such as polyester, polystyrene, acrylic resin, and urea resin, and organic fillers such as carbon fiber and carbon black. These may be used in combination of two or more. The amount of these fillers can be appropriately determined depending on the physical properties of the polymer, the viscosity of the resin solution, and the like, and is usually 0.1 to 300 parts by weight based on 100 parts by weight of the polymer obtained by the metathesis polymerization.
Parts by weight.

The filler used in the present invention may be subjected to a surface treatment, and the silane coupling agent for the surface treatment is usually Y _n SiX _4-n (Y has a functional group and is bonded to Si. X is a monovalent group having hydrolyzability and bonded to Si, and n represents 1 to 4). Y above
Examples of the functional group therein include groups such as vinyl, amino, methacryloxy, cyano, carbamate, sulfonyl azide, urea, styryl, chloromethyl, ammonium salt, and alcohol. X includes groups such as chloro, bromo, methoxy, ethoxy, methoxyethoxy and the like.

Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N, N-dimethylaminophenyltriethoxysilane, trimethoxysilylbenzoic acid, chloromethylphenethyltrimethoxysilane, 2-styrylethyl Liethoxysilane, aminoethylaminomethylphenethyltrimethoxysilane, γ-
Chlorophenyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, allyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3
-Aminopropyltrimethoxysilane, bis (2-hydroxyethyl) aminopropyltriethoxysilane, bis {3- (triethoxysilyl) propyl} amine, bis {3- (triethoxysilyl) propyl} ethylenediamine, 2-chloroethyl Triethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-cyanopropyltriethoxysilane,
N, N-diethyl-3-aminopropyltrimethoxysilane, N, N-diethylaminophenyltriethoxysilane, 1- (dimethylchlorosilyl) -2- (chloromethylphenyl) ethane, isocyanatopropyltriethoxysilane, mercaptoethyl Triethoxysilane, methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, N-methylaminopropyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride, -Trichlorosilyl-2- (chloromethylphenyl) ethane, β-trichlorosilyl-4-ethylpyridine, triethoxysilylpropylethylcarbamate, N- (triethoxysilylpropyl) urea, 1-
Trimethoxysilyl-2- (aminomethyl) phenylethane, 1-trimethoxysilyl-2- (chloromethyl)
Phenylethane, 2- (trimethoxysilyl) ethylphenylsulfonyl azide, trimethoxysilylpropyldiethylenetriamine, p-aminophenyltrimethoxysilane, 2-styrylethyltrimethoxysilane, aminoethylmethylphenethyltrimethoxysilane, 6-
Examples thereof include triethoxysilyl-2-norbornene and derivatives thereof, and these can be used as a mixture.

When the silane coupling agent itself is in a liquid state, it can be used as it is as a treatment liquid used for treating the surface of the filler, but it is usually used as a solution of water or an organic solvent. Is preferred.

The organic solvent is not particularly limited as long as it can dissolve the silane coupling agent and other components. In addition to alcohols such as methanol, ethanol, propyl alcohol and isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, dimethylformamide, N-methyl-2-pyrrolidone, methyl cellosolve, ethyl cellosolve, dioxane, tetrahydrofuran, Ethylene glycol dimethyl ether or the like is used, and these may be used as a mixture of two or more types including water.

The concentration of the silane coupling agent in the treatment solution is 0.001 to 10% by weight, preferably 0.01 to 10% by weight.
~ 5% by weight. When the amount is less than 0.001% by weight, the effect of improving the adhesive force at the interface between the resin and the filler is small, and when the amount is more than 10% by weight, it is economically undesirable. The temperature and time of the treatment are not particularly limited, but are usually 0 to 100.
C., 0.5 to 10 minutes, preferably 20 to 50 ° C., 5 seconds to 3 minutes.

Examples of the coloring agent include inorganic pigments such as titanium dioxide, cobalt blue and cadmium yellow, and organic pigments such as carbon black, aniline black, phthalocyanine and quinacdrine.

The antioxidant is not particularly restricted but includes, for example, phenolic antioxidants, phosphorus-based antioxidants, amine-based antioxidants, and stell-based antioxidants. In particular, hindered phenol derivatives of phenolic antioxidants are desirable, and 2,6-di-t-butyl-
4-methylphenol, 4,4'-methylenebis-
(2,6-di-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-
4-hydroxyphenyl) propionate], 1,6-
Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-
Bis (n-octylthio) -6- (4-hydroxy-3,
5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis- [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-
Di-t-butyl-4-hydroxyphenylpropionate], octadecyl- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t -Butyl-4-hydroxyhydroxycinnamamide), 3,5-di-t-butyl-
4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris
(3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, isooctyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like. Other than these, Adecastab series (manufactured by Asahi Denka Kogyo Co., Ltd.) and Sumilizer series (manufactured by Sumitomo Chemical Co., Ltd.) can be mentioned. These antioxidants are used in an amount of 0.01 to 30 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer obtained by the metathesis polymerization.

Examples of the weather resistance imparting agent include an ultraviolet absorber and a light stabilizer. Examples of the ultraviolet absorber include salicylic acid-based ultraviolet absorbers such as phenyl salicylate and pt-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4, Benzophenone-based ultraviolet absorbers such as 4'-dimethoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-
Amylphenyl) benzotriazole ultraviolet absorbers such as benzotriazole, 2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, ethyl-2-
And cyanoacrylate-based ultraviolet absorbers such as cyano-3,3'-diphenylacrylate. These may be used alone or in combination of two or more.

As a light stabilizer, bis (2,2,6,6-
Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,2 Hindered amine light stabilizers such as 6,6-tetramethylpiperidine polycondensate are exemplified. These may be used alone or in combination of two or more, and may be used in combination with an ultraviolet absorber.

As the flame retardant, hexabromobenzene,
Tetrabromobisphenol A, decabromodiphenyl oxide, tribromophenol, dibromophenyl glycidyl ether, perchloropentacyclodecane,
Halogen compounds such as heptate derivatives are used alone or in combination of two or more. Further, a non-halogen compound such as a phosphoric acid compound such as tris (dichloropropyl) phosphate and tris (dibromopropyl) phosphate and a boric acid compound can be used. Further, examples of the auxiliary flame retardant include antimony trioxide, iron oxide, aluminum hydride and the like. When these are used in combination with the flame retardant, the flame retardant effect is further enhanced. The flame retardant is usually used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the metathesis polymer, and an auxiliary flame retardant such as antimony trioxide is used in an amount of 1 to 15 parts by weight. Hydrates such as aluminum hydroxide and magnesium hydroxide can also be used as fillers for flame retardancy. It is preferable to use these additives in an amount of 10 to 30 parts by weight based on 100 parts by weight of the polymer obtained by the metathesis polymerization.

The adhesive composition of the present invention may be a composition obtained by blending a resin such as polyimide, polyester, polyethylene, rubber-based elastomer, acrylic resin, methacrylic resin and vinyl resin in addition to the above. These are usually polymers 1 obtained by the metathesis polymerization of the present invention.
It is preferable to add 10 to 100 parts by weight to 00 parts by weight.

The adhesive member using the adhesive composition of the present invention is preferably used as a solvent-free paste containing no volatile components such as a solvent, but if necessary, used as a paste dissolved in a solvent. can do. Further, the present adhesive composition can be formed into a film on one or both sides of a substrate such as polyimide, polyester, or polyvinylidene fluoride and used as an adhesive member. The adhesive member is first formed on a support member such as a wiring board for mounting a semiconductor element by a dispensing method, a stamping method, a screen printing method, a thermocompression bonding method, and the like. The semiconductor element and the supporting member are bonded by heating and curing using a heating device such as a drying machine, a heat block, a hot plate, or the like, whereby a semiconductor device can be obtained.

[0028]

The present invention will be described below in more detail with reference to examples. (Synthesis of polymer by metathesis polymerization) 10.00 g of 5-norbornene-2,3-dimethyl ester (47.6 m
mol) and 7.863 g (71.4 mmol) of cyclooctene were dissolved in 160 g of toluene, and heated to 60 ° C. under a nitrogen atmosphere. To this solution was added bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride (Str
326 mg (0.4 mmol)
Was dissolved in 3.7 g of toluene. Thereafter, the mixture was stirred at 60 ° C. for 2 hours under a nitrogen atmosphere. After this,
After cooling to room temperature, the reaction solution was slowly added to 2 liters of methanol, and the pale black polymer was removed by suction filtration and dried under reduced pressure. When the weight after drying was measured, 17.0 g (yield 95.2% by weight) of a polymer was obtained. This polymer is dissolved in tetrahydrofuran and GPC
As a result of analysis, the number average molecular weight was 36,000 (in terms of polystyrene). The polymer was dissolved again in toluene, cast on a support, and the solvent was removed.
m film, manufactured by Rheometrics Scientific Co., Ltd., dynamic viscoelasticity measuring device RSAII (tensile mode, frequency 10 Hz, 5 ° C./min heating rate, −40
To 150 ° C).
Was 290 MPa (0.29 GPa).

(Preparation of Adhesive Film) Polymer 10
0 parts by weight was dissolved in 185.7 parts by weight of cyclopentanone to prepare a polymer solution A. Separately, bisphenol A type epoxy resin (epoxy equivalent 20
0, manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epicoat 828) 8.8 parts by weight, 4,4 ′-[1- [4- [1- (4
-Hydroxyphenyl) -1-methylethyl] phenyl]
[Ethylidene] bisphenol (manufactured by Honshu Chemical Co., Ltd., trade name: TrisP-PA) 6.2 parts by weight and triphenylphosphine (Tokyo Kasei Kogyo Co., Ltd.) 0.3 parts by weight were dissolved in cyclopentanone 28.4 parts by weight. A curing agent solution B was prepared, and a polymer solution A was added thereto to obtain an adhesive composition. The above adhesive composition is applied using an applicator onto a 50 μm thick Upilex S (a product of Ube Industries, Ltd., trade name, polyimide resin film), dried at 85 ° C. for 15 minutes, and the adhesive is applied to one side. A film with the composition was made.
Next, the adhesive composition was similarly applied to the back surface, and 90
The adhesive composition was dried at 15 ° C. for 15 minutes and at 120 ° C. for 60 minutes to form a three-layer double-sided adhesive film adhesive member having a film thickness of 50 μm on each side.

(Package Reliability Test) A package reliability test was performed on the above-mentioned adhesive member. As a method of evaluating the reliability test, the reflow crack resistance of a sample obtained by bonding a semiconductor chip and a printed wiring board with an adhesive member is considered.
The PCT (pressure cooker) test was applied. At this time, one side of the adhesive member was applied to the printed wiring board at a pressure of 0.98M.
Pa (10 Kg / cm ² ), temperature 160 ° C., time 5 seconds, and the other surface was applied to the semiconductor chip at a pressure of 0.79.
It was pasted under the conditions of MPa (8 kg / cm ² ), temperature of 160 ° C. and time of 3 seconds. Thereafter, the sample was heated at 150 ° C. for 1 hour to prepare a sample.

The reflow crack resistance was evaluated by passing the sample through an IR reflow furnace set at a maximum temperature of the sample surface of 240 ° C. and maintaining this temperature for 5 seconds, and then cooling the sample to room temperature. Observation was performed. As a result, no crack occurred in all six samples using the present adhesive composition.

In the PCT test, a sample exposed to 168 hours at 121 ° C. and 2 atm was heated at 120 ° C. for 2 hours, cooled to room temperature, and cracks in the sample were observed. As a result, as in the evaluation of the reflow crack resistance, no crack occurred in all six samples using the present adhesive composition.

[0033]

According to the present invention, the elastic modulus at room temperature (25 ° C.) of the present invention is 1.5 GPa or less and the number average molecular weight is 5,000 to 5
An adhesive composition comprising a polymer obtained by metathesis polymerization of 00000 and a curable resin (curing agent) has a low storage elastic modulus, is excellent in stress relaxation, and has a polymer obtained by metathesis polymerization. Has a low moisture absorption property, so that it absorbs a small amount of moisture and reduces stress generated without generating molding stress or thermal stress, so that it is possible to provide an adhesive composition having excellent reflow crack resistance. In the used semiconductor device, connection reliability is greatly improved.

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Claims (5)

[Claims] 1. A semiconductor comprising a polymer obtained by metathesis polymerization having an elastic modulus at room temperature of 1.5 GPa or less and a number average molecular weight of 5,000 to 500,000, and a thermosetting resin or a photocurable resin. An adhesive composition for a device. 2. A polymer 100 obtained by metathesis polymerization.
Thermosetting resin or photocurable resin 1 to 10 parts by weight
The adhesive composition for a semiconductor device according to claim 1, wherein 0 part by weight is blended. 3. The adhesive composition for a semiconductor element according to claim 1, wherein the polymer is a polymer obtained by metathesis polymerization of a cyclic olefin or a polymer obtained by further hydrogenating the polymer. . 4. The adhesive composition for a semiconductor element according to claim 1, wherein the polymer is a copolymer of a cycloalkene derivative and a norbornene derivative. 5. A semiconductor device in which a semiconductor element is mounted on a mounting substrate via an adhesive member using the adhesive composition for a semiconductor element according to claim 1.