JP2001049221A - Adhesive composition for electronic component and adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition for electronic components which has an excellent temperature-cycle resistance and therefore improves the ply separation caused by repetitive temperature change, which is a problem observed in adbesives used for semiconductor devices such as BGA, CSP, etc., and an adhesive sheet. SOLUTION: An adhesive composition essentially comprises (a) an epoxy resin, (b) an epoxy hardener and (c) an elastic body. Here, the ratios of the dynamic elastic moduli at -50 deg.C, 50 deg.C and 150 deg.C affer heating the cured adhesive composition at 150 deg.C for 250 hr, to the elastic moduli at the corresponding temperatures before the heat treatment, are all within the range of from 0.1 to 10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to various electronic components,
More particularly, the present invention relates to an adhesive composition and an adhesive sheet suitable for a semiconductor device having a structure in which an IC chip is laminated on an IC substrate composed of an insulator layer and a conductive circuit, and particularly to an adhesive composition for bonding an IC chip or a heat sink. To glue
More specifically, the present invention relates to an adhesive composition for bonding an IC chip to an IC substrate, an IC chip to a heat sink, or a heat sink to an IC substrate.

[0002]

2. Description of the Related Art With the rapid spread of portable personal computers and portable telephones, electronic devices are required to be further reduced in size, thickness, and multifunctionality. In order to fulfill this demand, miniaturization and high integration of electronic components are indispensable. However, high-density mounting technology for electronic components is also required. IC packages, which form the core of recent electronic components, have Q
FP (Quad Flat Package) and SOP (Small Outline P
ackage), but recently, BGA (Ball Grid Allay) and CSP (Chip Size Pac)
Kage) has attracted attention as an IC package capable of high-density mounting.

[0003] The BGA and CSP have solder balls as external connection terminals provided on the back surface of the package in a plane lattice.
Electrodes of an IC (semiconductor integrated circuit) are connected to electrodes of a printed circuit board via an IC substrate which is a circuit wiring pattern conversion substrate. Plastic B depending on the type of IC substrate
GA (hereinafter abbreviated as P-BGA), ceramic BGA
(Hereinafter abbreviated as C-BGA), tape BGA (hereinafter, referred to as C-BGA).
Abbreviated as T-BGA. ), Enhanced B
GA (hereinafter abbreviated as E-BGA) has been developed.
Until recently, P-BGA, which can use wire bonding technology in QFP, was the mainstream, but TAB (Tape)
T-BGA using Automated Bonding technology is becoming mainstream because it can be further densified (increased number of pins) and has excellent heat dissipation. CSP is BGA
Are further miniaturized and densified, and are called micro BGA and fine pitch BGA. In particular, the CSP is a package having excellent electrical characteristics such as low impedance and high frequency response due to its structure.

FIG. 1 is a sectional view showing an example of a fine pitch BGA. An IC substrate provided with an insulating film 4 which is an insulator layer on which a conductor circuit such as a wiring 3 is formed is laminated on an IC chip 6 via an adhesive 7, and the IC chip 6 The wiring 3 is connected to the wiring 3 formed on one surface of the insulating film 4 via a gold wire 9 and further electrically connected to the outside by the solder ball 1. FIG.
1 shows a cross-sectional view of an example of a BGA. The insulating film 4 having the wiring 3 is laminated on the IC chip 6 via the adhesive 7, and the IC chip 6 is connected to the wiring 3 formed on one surface of the insulating film 4 via the electrode 5. And electrically connected to the outside by solder balls 1. There is also a semiconductor device having a configuration in which an IC chip is bonded to a heat sink with an adhesive.

[0005]

Incidentally, a polyimide film is usually used for the insulating film 4. The polyimide has a linear expansion coefficient of 20 to 30 ppm, whereas the IC chip has a linear expansion coefficient of 5 ppm. The linear expansion coefficient of the copper material usually used for the heat sink is 14 to 18 pp.
m. That is, there is a great difference in the linear expansion coefficient between the IC chip and the IC substrate (polyimide film) or the heat sink. The temperature of the IC package is room temperature when not driven, but becomes 100 ° C or more due to heat generation of the IC during driving.
The IC package is exposed to a temperature cycle from room temperature to high temperature (100 ° C. or higher). At that time, IC substrate and IC chip,
Stress was generated due to the difference in thermal expansion coefficient between the IC chip and the heat sink. Conventionally, as an adhesive for bonding between them, a thermosetting adhesive is generally inexpensive and excellent in workability, electrical characteristics and heat resistance, and specifically epoxy resin / epoxy curing agent / Adhesives typified by NBR (acrylonitrile-butadiene copolymer) have been used. However, since this NBR has a diene bond, it gradually loses elasticity at a high temperature. When temperature changes from room temperature to a high temperature are repeated, delamination of an adherend may occur due to a generated stress.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and improves delamination due to repeated temperature changes, which is a problem of conventional adhesives used for semiconductor devices such as BGA and CSP. That is, an object of the present invention is to provide an adhesive composition for electronic parts and an adhesive sheet having excellent temperature cycle resistance.

[0007]

The adhesive composition for electronic parts of the present invention is an adhesive composition containing (a) an epoxy resin, (b) an epoxy curing agent, and (c) an elastic body as essential components. The cured adhesive composition is cured at 150 ° C. for 250
The ratio of the dynamic elastic modulus at each temperature of −50 ° C., 50 ° C., and 150 ° C. after the heat treatment left for a time to the elastic modulus at each corresponding temperature before the heat treatment is in a range of 0.1 to 10. It is characterized by being in. At that time, as the elastic body,
A polymer having an ester bond is desirable, and a polymer having a functional group having reactivity with an epoxy resin or an epoxy curing agent is desirable. The adhesive composition for electronic parts of the present invention is an IC comprising an insulator layer and a conductor circuit.
It is suitable for a semiconductor device having a structure in which an IC chip is laminated on a circuit surface of a substrate for use or a back surface thereof, and particularly suitable for bonding the IC chip or a heat sink. In the adhesive sheet for electronic components of the present invention, the adhesive composition for electronic components is formed on at least one surface of a support.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The adhesive composition of the present invention is a curable adhesive composition containing (a) an epoxy resin, (b) an epoxy curing agent, and (c) an elastic body as essential components. The components used in the adhesive composition of the present invention will be described.

[(A) Epoxy resin] Epoxy resin is a resin having two or more oxirane rings in the molecule, for example, glycidyl ether, glycidyl ester, glycidylamine, linear aliphatic epoxide, alicyclic resin. A resin having any structure such as epoxide may be used, and a single resin or a combination of two or more resins may be used. Specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether,
Glycidyl ethers such as resorcinol diglycidyl ether, brominated bisphenol A diglycidyl ether, fluorinated bisphenol A diglycidyl ether, phenol novolac glycidyl ether, cresol novolac glycidyl ether, brominated novolac glycidyl ether, and hexahydrophthalic acid diglycidyl ester Glycidyl esters such as diglycidyl phthalate and diglycidyl dimer, glycidyl amines such as triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane and tetraglycidyl meta-xylene diamine, and linear aliphatic epoxy resins such as epoxidized soybean oil. Sites, 3,4-epoxy-6-methylcyclohexylmethylcarboxylate, 3,4-
Alicyclic epoxies such as epoxycyclohexylmethyl carboxylate are exemplified.

[0010] Of these, bisphenol type epoxy resins are particularly preferred because they are inexpensive, and bisphenol A type is particularly preferably used. The epoxy equivalent of the epoxy resin is preferably 4000 or less, more preferably 1 or less.
Epoxy equivalents of 50-2000. If the epoxy equivalent is larger than 4000, the elasticity of the cured product becomes low, and the adhesive strength decreases. The epoxy resin preferably used in the present invention is specifically manufactured by Yuka Shell Epoxy Co., Ltd .: trade name; Epicoat 806, 828, 1001, manufactured by Asahi Denka Kogyo Co., Ltd .: trade name; EP-4100G, EP4400, EP
-4901, manufactured by Nippon Kayaku Co., Ltd .: Trade name; EOCN102
S, 103S, 104S, 1020, EPPN501H
And the like. Use of a halogenated epoxy, particularly a brominated epoxy, is an effective means for imparting flame retardancy. Specific examples of the brominated epoxy include Yuka Shell Epoxy Co., Ltd .: trade name; Epicoat 50
45, 5046, 5050, Nippon Kayaku: Brand name; BR
EN-S, BREN-105, BREN-301 and the like.

[(B) Epoxy curing agent] An epoxy curing agent refers to a chemical substance which reacts with an epoxy resin to form a three-dimensional network structure, and includes aromatic polyamines, aliphatic polyamines,
Polyamides, acid anhydrides, phenol derivatives, polymercaptans, tertiary amines, Lewis acid complexes and the like are used. Specifically, 4,4'-diaminodiphenylmethane, 4,4 '
-Diaminodiphenyl ether, diaminodiphenylsulfone, diaminodiphenylsulfide, m-phenylenediamine, 2,4-toluylenediamine, m-toluylenediamine, o-toluylenediamine, metaxylylenediamine, metaaminobenzylamine, benzidine, 4 -Chloro-O-phenylenediamine, bis (3,
Aromatic polyamines such as 4-diaminophenyl) sulfone, 2,6-diaminopyridine, isophthalic dihydrazide, diethylene triamine, dipropylene triamine, diethylene tetramine, triethylene tetramine;
Tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, hexamethylenediamine, N-aminoethylpiperazine, bis-aminopropylpiperazine,
Aliphatic polyamines such as trimethylhexamethylenediamine, bis- (hexamethylene) triamine, adipic dihydrazide, sebacic dihydrazide, dicyandiamide, dimer acid polyamide, maleic anhydride, dodecenylsuccinic anhydride, chlorendexic anhydride, sebacic anhydride, Phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, cyclopentane / tetracarboxylic dianhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydro Phthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, 5- (2,
5-dioxotetrahydroxyfuryl) -3-methyl-
Acid anhydrides such as 3-cyclohexene-1,2-dicarboxylic anhydride and methylnadic anhydride; phenol derivatives such as resole phenolic resin, phenol novolak resin, cresol novolak resin, resorcinol resin and xylene resin; Polymercaptans such as dimercaptodiethyl ether, 1,2-dimercaptopropane, 1,3-dimercaptopropanol, bis (2-mercaptoethylsulfide), dimethylaminomethylphenol, 2,4,6-tri (dimethylamino) Methyl) phenol, tri (dimethylaminomethyl) phenol
Tri-2-ethylhexane salt, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2
-Phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole,
2-ethylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-methylimidazole, 1-
Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-
Methylimidazole trimellitate, 1-cyanoethyl-2-ethyl 4-methylimidazole trimellitate,
1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1) ′]-ethyl-s-triazine, 2 , 4-Diamino-6- [2'undecylimidazolyl- (1) ']-ethyl-s-triazine, 2,4-diamino-6- [2'-
Ethyl-4′-methylimidazolyl- (1) ′]-ethyl-s-triazine, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1,3-dibenzyl-
2-methylimidazolium chloride, 2-phenyl-4
-Methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1
Tertiary amines such as cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, 2-methylimidazole-triazine complex, 2-phenylimidazole-triazine complex, etc. Examples include Lewis acid complexes such as ethylamine complex compounds, boron trifluoride / triethanolamine complex compounds, boron trifluoride / piperidine complex compounds, and boron trifluoride / n-butyl ether complex compounds. Among them, phenol derivatives are preferable because of their excellent reactivity and excellent wet heat resistance even in semiconductor device applications.

[(C) Elastic body] The elastic body can be used as long as it imparts flexibility to the adhesive. Preferably, a polymer having no diene bond, for example, a polymer having an ester bond can be preferably used. Above all, a (co) polymer of acrylic acid ester (so-called acrylic rubber) and a polyester resin are particularly preferable elastic materials because they hardly deteriorate at high temperature and change in dynamic elastic modulus after standing at 150 ° C. for 250 hours. The weight average molecular weight of these polymers is 1.0
00 to 2,000,000, preferably 100,000 to
It is 1,000,000.

[0013] The acrylic rubber generally comprises a main component obtained by polymerizing an acrylate ester by an emulsion polymerization method, and the monomers include ethyl acrylate, methyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and the like. And acrylonitrile are preferably used. Acrylic ester has 20 carbon atoms
The following are preferred. Further, by changing the copolymerization ratio of acrylonitrile, the elastic component characteristics (elongation, tensile strength, etc.) can be controlled, so that the acrylonitrile copolymerization ratio preferably used in the present invention is 1 to 50% by weight. It is also an example of an acrylic rubber that it is preferable to use two or more acrylate monomers in combination and copolymerize with acrylonitrile. By using acrylic acid, a hydroxyl group or an amino group-containing acrylate, an acrylic rubber having a functional group such as a carboxyl group, a hydroxyl group, or an amino group can be obtained. As described later, (a) an epoxy resin or (b) ) React with epoxy curing agent.

Examples of the polyester resin include polyester urethane rubber, fluorine-containing polyester rubber, polyester elastomer, and the like. Particularly, polyester urethane rubber and polyester elastomer are suitable.
Polyester urethane rubber is a rubber-like elastic body derived from a polyester of an acid component and a glycol by diisocyanate or the like. As the glycol component, ethylene glycol, propylene glycol, butylene glycol, hexanediol, hexahydroresolecin, diethylene glycol, di and triethylene ether glycol, diethylene thioether glycol, and the like are preferable. As the acid component, succinic acid, adipic acid, pimelic acid, sebacic acid, phthalic acid, methyladipic acid and the like are preferable. The desired properties can be obtained by replacing a part of the glycol component with triol or the like. From the single polyester or co-condensed polyester obtained as described above, polyester urethane is synthesized using diisocyanate and the like, and further cross-linked if necessary, to obtain a polyester urethane rubber. Fluorinated polyester rubber is
For example, it is synthesized from adipyl chloride and hexafluoropentanediol and has excellent chemical stability. The polyester elastomer is a single polyester or a polyester elastomer using polyester for the segment. Polyester may be used for at least one of the hard segment and the soft segment, and the polyester used for the segment may be either an aromatic polyester or an aliphatic polyester. As the polyester elastomer, for example, those having a structure such as an aromatic polyester such as polybutylene terephthalate in a hard segment, a structure such as a polyether such as polytetramethylene ether glycol, or an aliphatic polyester in a soft segment are known. This polyester elastomer is excellent in load resistance, oil / chemical resistance, and moldability.

Further, these elastic bodies desirably have a functional group capable of reacting with (a) an epoxy resin or (b) an epoxy curing agent in order to improve heat resistance after curing. Specific functional groups include amino groups, isocyanate groups,
Examples include an epoxy group, a carboxyl group (including an anhydride), a silanol group, a hydroxyl group, a vinyl group, a methylol group, and a mercapto group. Among them, amino group, carboxyl group,
An epoxy group, a hydroxyl group, and a vinyl group are preferable because of their high reactivity. Most preferably, the elastic body has an epoxy group, a carboxyl group, and an amino group. The content of the functional group is 0.2 to 20
Mol% is preferable, 0.5 to 15 mol% is more preferable, and 2 to 8 mol% is more preferable. When the amount of the functional group is less than 0.2 mol%, the reactivity is low, and when the amount exceeds 20 mol%, the stability of the paint is deteriorated.

In addition to the above components (a), (b) and (c), imidazoles, 1,8
It is also effective to add a reaction accelerator such as an amine catalyst such as diazabicyclo (5,4,0) undecene or a phosphorus catalyst such as triphenylphosphine. The adhesive composition for electronic parts of the present invention preferably contains an inorganic or organic filler for the purpose of adjusting the coefficient of thermal expansion and thermal conductivity or controlling workability. As the inorganic filler, pulverized silica, fused silica, alumina, titanium oxide, beryllium oxide, magnesium oxide, calcium carbonate, titanium nitride, silicon nitride, boron nitride, titanium boride, tungsten boride, silicon carbide, titanium carbide, carbonized Examples include zirconium, molybdenum carbide, mica, zinc oxide, carbon black, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, antimony trioxide, and those obtained by treating the surface thereof with a trimethylsiloxyl group or the like. Examples of the organic filler include polyimide, polyamide imide, polyether ether ketone, polyether imide, polyester imide, nylon, and silicone.
The compounding amount of these fillers is in the range of 5 to 95 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the total of each component (a), (b) and (c).

Further, a silane coupling agent may be added to improve the adhesion to the adherend and the compatibility of each component. As shown in the following formula (1), the silane coupling agent has a structure in which silicon has an organic functional group (X) capable of binding or binding to an organic matrix and a hydrolyzing group (Y) capable of binding to an inorganic material. ing. X _n -Si-Y _(4-n) (1) Examples of the organic functional group include an alkyl group, a phenyl group, an amino group, an epoxy group, a vinyl group, a methacryloxy group, and a mercaptoxy group. Has a bond with a silicon atom via an alkylene group having 1 to 6 carbon atoms. Further, the organic functional group having an epoxy group or an amino group is preferable because of good reactivity with an epoxy curing agent. Examples of the hydrolyzable group include a methoxy group, an ethoxy group, a chloro group, and an acetoxy group. Specific silane coupling agents include, when X is a functional group having a vinyl group, vinyltrimethoxysilane, vinyltriethoxysilane, N-β
(N-vinylbenzyl) aminopropyltrimethoxysilane.hydrochloride. When X is a functional group having a methacryloxy group, γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane are exemplified. Can be When X is a functional group having an epoxy group, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane are exemplified. Can be Further, when X is a functional group having a mercapto group, γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane, when X is a functional group having an amino group,
γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, triaminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltri Methoxysilane is mentioned.

The adhesive composition for electronic parts of the present invention has a temperature of -15 ° C., 50 ° C., and 15 ° C., which is subjected to a heat treatment of being left at 150 ° C. for 250 hours after curing and a heat-treated one.
It is necessary that the dynamic elastic modulus ratio (after heat treatment / before heat treatment) at each temperature of 0 ° C. is in the range of 0.1 to 10. The dynamic modulus ratio is preferably between 0.3 and 8, optimally between 0.5 and 5.
It is. When the dynamic elastic modulus ratio is less than 0.1 or more than 10, the temperature cycle resistance is poor. Specifically, the ratio of the dynamic elastic modulus is obtained as follows. Dynamic modulus is thickness 1
The single-layer adhesive film after curing of 00 μm was manufactured using Orientec Co., Ltd. “Reo Vibron DDV-01FP”.
Frequency 11Hz, heating rate 3 ° C / min, temperature -65
The temperature is raised from 200C to 200C. The heat treatment at 150 ° C. for 250 hours can be performed by a hot air circulation type dryer. The dynamic elastic modulus after standing is measured by the method for measuring the dynamic elastic modulus after the adhesive film is allowed to cool to room temperature.

The preferred mixing ratio of the above components (a) to (c) is such that [(a) + (b)] / (c) is 0.2 to 5, and more preferably 0.3 to 3.3. It is. in this case,
If it is less than 0.2, the modulus of elasticity is low, and the solder heat resistance is low. On the other hand, if it is larger than 5, the film adhesive loses flexibility, which is not preferable. The components (a) to (c) are dissolved and mixed in an organic solvent to prepare an adhesive solution. Preferred organic solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, MEK, methyl isobutyl ketone, toluene, xylene, 1,4-dioxane, tetrahydrofuran, Ethanol, methanol, isopropanol, methyl cellosolve, ethyl cellosolve and the like may be used in combination.

The adhesive sheet of the present invention is characterized in that the adhesive composition is laminated on at least one surface of a support. The adhesive sheet is obtained by applying the above-mentioned adhesive composition solution to a support, followed by drying. Examples of the support used include heat-resistant films such as polyimide, polyamide, polyetheramide, polyphenylene sulfide, polyetherketone, polyparabanic acid, polyethylene terephthalate, and fluororesin; heat-resistant films such as glass cloth, aramid, nylon, amideimide, and polyimide. A non-woven fabric is used, and a releasable film obtained by subjecting the heat-resistant film surface to a release treatment is also suitably used. The heat resistance,
The thickness of the peelable film is 7.5 to 500 μm, preferably 10 to 130 μm. On the surface of the adhesive composition layer of the adhesive sheet, a protective film is provided on the surface of the adhesive layer as necessary. As the protective film, a film having releasability is preferable. For example, a film obtained by subjecting a surface of a heat-resistant film to a release treatment is also a preferable film, and has the same thickness as described above. The thickness of the adhesive layer formed on the film after drying varies depending on the package shape, but is generally 10 to 200 μm, preferably 30 to 100 μm.

The adhesive composition and the adhesive sheet of the present invention comprise:
Although it can be applied to various electronic components, it is particularly suitable for a semiconductor device in which an IC chip is laminated on a circuit surface of an IC substrate including an insulator layer and a conductor circuit or on a back surface thereof. Specifically, there is a T-BGA or a surface-mount type CSP semiconductor device using the TAB technology. In particular,
In the semiconductor device shown in FIGS.
It is suitable for the adhesive 7 for bonding the chip 6 and the insulating film 4 of the IC substrate. It is also suitable for the semiconductor device illustrated in FIGS. In the semiconductor device shown in FIG. 3, the IC chip 6 and the reinforcing plate 9 are bonded on the heat sink 8, the insulating film 4 is bonded on the reinforcing plate 9, and connected to the electrode 5 formed on the IC chip 6. The wiring 3 is formed on the insulating film 4 with an adhesive 10. The solder balls 1 are formed on the wirings 3, and the resin 11 is potted around the IC chip 6. In this semiconductor device, the adhesive according to the present invention is suitable as an adhesive for bonding the IC chip 6 and the heat sink 8. In the semiconductor device shown in FIG. 4, the IC chip 6 and the insulating film 4 are bonded on the heat sink 12, and the wiring 3 connected to the electrode 5 formed on the IC chip 6 is formed on the insulating film 4. It is formed with the adhesive 10. A solder ball 1 is formed on the wiring 3, and a resin 1 is provided around the IC chip 6.
1 is potted. In this semiconductor device, the IC chip 6, the insulating film 4, and the heat sink 1
The adhesive according to the present invention is suitable as the adhesive for bonding the two.

[0022]

EXAMPLES [Preparation of Paint of Adhesive Composition] A solution was prepared by dissolving an epoxy resin, an epoxy curing agent, an elastic material, and a curing accelerator in methyl ethyl ketone (MEK) so as to have the following weight percentages. The weight percent of the solution is shown in Table 1.
(Solid content) to obtain a coating of the adhesive composition for a semiconductor device of the present invention.

Example 1 Epoxy resin: ortho-cresol novolak type epoxy resin (trade name: EOCN1020, manufactured by Nippon Kayaku Co., Ltd.)
... 80% solution-Epoxy curing agent: Novolac type phenolic resin (trade name: resin top PSM4261, manufactured by Gunei Chemical Co., Ltd.) ...
70% solution-Elastic body: carboxyl group-containing polyester urethane resin (prototype, Mw: 60,000) ... 40% solution-Curing accelerator: 2-undecyl imidazole (trade name;
(C11Z, manufactured by Shikoku Chemicals) 1% solution

Next, an adhesive sheet and a semiconductor device for evaluation of the present invention were produced by the following procedure. : A coating of the adhesive composition of the present invention shown in Table 1 was applied to a support made of a 38 μm-thick polyester film subjected to a release treatment, and heated and dried at 130 ° C. for 5 minutes to obtain a thickness after drying. An adhesive layer having a thickness of 50 μm was formed. Then
A 50 μm-thick polyethylene protective film subjected to a release treatment was bonded to the adhesive layer to prepare an adhesive sheet of the present invention. : 18 μm electrolytic copper foil on a polyimide film with adhesive for TAB (manufactured by Tomagawa Paper) at 130 ° C./linear pressure 2 kg /
after laminating at 70 ° C./2 hours and 150 ° C.
/ 4 hour heat treatment was performed. This was used to etch the copper foil using a photoresist method to produce an IC wiring pattern substrate (hereinafter abbreviated as evaluation wiring pattern substrate) having an insulator layer and a conductor circuit used for evaluation. : The adhesive layer was made to face while peeling off the polyethylene protective film of the adhesive sheet made on the polyimide (insulator layer) surface of the wiring pattern board for evaluation created in
Crimping was performed at 100 ° C./linear pressure of 2 kg / cm to produce a wiring pattern substrate for evaluation with an adhesive. : Peel off the polyester film of the wiring pattern substrate for evaluation with an adhesive prepared in and mount an IC chip with a photosensitive passivation film at 150 ° C./1 MPa / 1.
After temporary compression bonding in 90 seconds, 90 ° C / 1 hour and 150 ° C /
After curing for 4 hours, the semiconductor device was sealed to produce the semiconductor device for evaluation shown in FIG. (However, bonding such as gold wire is not performed.)

Example 2 A semiconductor device for evaluation was produced in the same manner as in Example 1 except that the following paints were used and the compositions shown in Table 1 were used.・ Epoxy resin: bisphenol A type epoxy resin (trade name; Epicoat 1001, manufactured by Yuka Shell Epoxy)
... 80% solution-Epoxy curing agent: Novolac type phenol resin (trade name; Shonor BRG-557, manufactured by Showa Kogyo KK)
... 70% solution Elastic body: carboxyl group-containing polyester elastomer (trade name: BX218, manufactured by Toyobo, Mw: 3000)
0) ... 35% solution-Cure accelerator: 2-undecyl imidazole (trade name;
(C11Z, manufactured by Shikoku Chemicals) 1% solution

Example 3 A semiconductor device for evaluation was produced in the same manner as in Example 1 except that the following paint was used and the compositions shown in Table 1 were used.・ Epoxy resin: bisphenol A type epoxy resin (trade name; Epicoat 1001, manufactured by Yuka Shell Epoxy)
... 80% solution-Epoxy curing agent: Novolac type phenolic resin (trade name: resin top PSM4261, manufactured by Gunei Chemical Co., Ltd.) ...
70% solution-Elastic body: carboxyl group-containing acrylic rubber (trade name;
(SG-70 LDR, manufactured by Teikoku Chemical Industry Co., Ltd., Mw: 800,000)
... 20% solution -Curing accelerator: 2-undecylimidazole (trade name;
(C11Z, manufactured by Shikoku Chemicals) 1% solution

Example 4 A semiconductor device for evaluation was produced in the same manner as in Example 1 except that the following paint was used and the composition shown in Table 1 was used.・ Epoxy resin: bisphenol A type epoxy resin (trade name; Epicoat 1001, manufactured by Yuka Shell Epoxy)
... 80% solution-Epoxy curing agent: novolak phenol resin (trade name; resin top PSM4261, manufactured by Gunei Chemical Co., Ltd.) ...
70% solution-Elastic body: carboxyl group-containing acrylic rubber (trade name;
WS023DR, manufactured by Teikoku Chemical Industry Co., Ltd., composition: butyl acrylate / ethyl acrylate / acrylonitrile / others (carboxyl group Ac, etc., Mw: 450,000) ... 22
% Solution ・ Curing accelerator: 2-undecylimidazole (trade name;
(C11Z, manufactured by Shikoku Chemicals) 1% solution

Comparative Example 1 A semiconductor device for evaluation was produced in the same manner as in Example 1 except that the following paint was used and the composition shown in Table 1 was used.・ Epoxy resin: bisphenol A type epoxy resin (trade name; Epicoat 1001, manufactured by Yuka Shell Epoxy)
... 80% solution-Epoxy curing agent: novolak phenol resin (trade name; resin top PSM4261, manufactured by Gunei Chemical Co., Ltd.) ...
70% solution ・ Elastic body: NBR containing carboxyl group (trade name: PNR)
-1H, manufactured by Nippon Synthetic Rubber Co., Ltd., Mw: 400,000) ... 20
% Solution ・ Curing accelerator: 2-undecylimidazole (trade name;
(C11Z, manufactured by Shikoku Chemicals) 1% solution

Comparative Example 2 A semiconductor device for evaluation was produced in the same manner as in Example 1 except that the following paint was used and the composition shown in Table 1 was used.・ Epoxy resin: bisphenol A type epoxy resin (trade name; Epicoat 1001, manufactured by Yuka Shell Epoxy)
... 80% solution-Epoxy curing agent: novolak phenol resin (trade name; resin top PSM4261, manufactured by Gunei Chemical Co., Ltd.) ...
70% solution-Elastic body: NBR (trade name; Nippol 1072J, manufactured by Zeon Corporation, Mw: 160,000) ... 20% solution-Curing accelerator: 2-undecylimidazole (trade name;
(C11Z, manufactured by Shikoku Chemicals) 1% solution

[0030]

[Table 1]

[Measurement of Dynamic Elastic Modulus] A support made of a polyester film having a thickness of 38 μm and subjected to a release treatment,
A coating of the adhesive composition of the present invention (Examples 1 to 4) and comparative examples (Comparative Examples 1 and 2) shown in Table 1 was applied, and 130
The resultant was dried by heating at 5 ° C. for 5 minutes to form an adhesive layer having a thickness of 100 μm after drying to obtain an adhesive sheet. <Dynamic Modulus after Curing> The adhesive sheet having a thickness of 100 μm obtained as described above was cured at 90 ° C. for 1 hour and 150 ° C. for 4 hours.
The dynamic elastic modulus at 150 ° C. and 150 ° C. was measured, and the results are shown in Table 2.
It was shown to. <Dynamic elastic modulus after standing at 150 ° C. for 250 hours> The adhesive sheet cured in the same manner as above was placed in a hot air circulation type dryer for 1 hour.
After standing at 50 ° C. for 250 hours, it was allowed to cool to room temperature. The dynamic elastic moduli at −50 ° C., 50 ° C., and 150 ° C. were measured by the above-described measuring method.

[0032]

[Table 2]

<Dynamic Elastic Modulus Ratio> A dynamic elastic modulus ratio was determined from the dynamic elastic modulus obtained above, and the results are shown in Table 3.

[0034]

[Table 3]

[Evaluation of temperature cycle resistance]
20 and each of the evaluation semiconductor devices manufactured in Comparative Example 1 and Comparative Example 1 and Comparative Example 2 were prepared, and a thermal cycle test at −65 ° C. to 150 ° C. was performed. However, in this case, 150 ° C. and -6
At 5 ° C., a one-hour temperature history was essential, and the cycle was performed at [normal temperature-high temperature-low temperature-normal temperature] for 500 cycles. As a result, the packages of Examples 1 to 4 were not abnormal, but some of the packages of Comparative Examples 1 and 2 had cracks at the interface between the adhesive layer 7 and the IC chip 6.

[0036]

The adhesive composition of the present invention has permanent elasticity and is less likely to cause delamination even when the stress of the adherend increases due to exposure to a temperature cycle. Therefore, a semiconductor package using this adhesive composition has high reliability in which the adhesive layer does not peel off at the interface even when room temperature to high temperature is repeated, that is, it has excellent temperature cycle resistance and does not cause cracks at the adhesive interface. It has.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a CSP package.

FIG. 2 is a cross-sectional view of another example of a micro-BGA package.

FIG. 3 is a cross-sectional view illustrating an example of a semiconductor device.

FIG. 4 is a cross-sectional view illustrating an example of a semiconductor device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Solder ball 3 Wiring 4 Insulating film 5 Electrode 6 Semiconductor (IC) chip 7 Adhesive 8 Heat sink 9 Gold wire 12 Heat sink

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Ichiro Kotani 3-1, Yomomoe-cho, Shizuoka-shi, Shizuoka Pref. CB01 CC02 DB02 DB03 FA05 4J040 DF042 DF062 DF082 EB052 EB062 EB082 EC061 EC071 EC081 EC091 EC121 EC131 EC151 EC171 EC241 EC261 ED072 EF112 EF282 EG022 GA02 GA03 GA05 GA07 GA11 GA12 GA13 HC20 HC16 HC22 HC16 HC22 HC16 HC22 HC24 JB02 KA16 LA01 LA07 MA02 MA10 NA19 NA20

Claims (6)

[Claims] An adhesive composition comprising (a) an epoxy resin, (b) an epoxy curing agent, and (c) an elastic body as essential components, wherein the cured adhesive composition is left at 150 ° C. for 250 hours. After the heat treatment, the ratio of the dynamic elastic modulus at each temperature of −50 ° C., 50 ° C., and 150 ° C. to the elastic modulus at each corresponding temperature before the heat treatment is in the range of 0.1 to 10. An adhesive composition for an electronic component, comprising: 2. The adhesive composition for electronic parts according to claim 1, wherein the elastic body is a polymer having an ester bond. 3. The adhesive composition for electronic parts according to claim 1, wherein the elastic body has a functional group having reactivity with an epoxy resin or an epoxy curing agent. 4. The semiconductor device according to claim 1, wherein the semiconductor device has a structure in which an IC substrate having an insulator layer and a conductor circuit and an IC chip are stacked. 3. The adhesive composition for electronic components according to 1.). 5. The adhesive composition for an electronic component according to claim 4, which is used for bonding an IC chip or a heat sink. 6. An adhesive sheet for electronic parts, wherein the adhesive composition for electronic parts according to claim 1, 2 or 3 is formed on at least one surface of a support.