JP2001240838A - Adhesive composition for semiconductor device, and adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive composition usable for semiconductor devices such as BGA(Ball Grid Allay) and CSP(Chip Size Package), having preferable elasticity and high insulating properties and excellent in electrical reliability at a high temperature and humidity, and to obtain an adhesive sheet. SOLUTION: This adhesive composition for semiconductor devices is obtained by including (A) an epoxy resin, (B) an epoxy-curing agent and (C) a vinyl copolymer containing ethylene and an unsaturated carboxylic acid derivative having a functional group capable of reacting with the epoxy resin or the epoxy curing agent as monomer components, and the adhesive sheet is obtained by forming a layer composed of the adhesive composition on a support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device using various semiconductors, and more particularly, to a surface-mount type semiconductor device suitable for a semiconductor device in which an IC chip is laminated on an IC substrate composed of an insulator layer and a conductor circuit. The present invention relates to an adhesive composition and an adhesive sheet suitable for a semiconductor device, particularly suitable for bonding an IC chip or a heat sink.
More specifically, the present invention relates to an adhesive composition and an adhesive sheet suitable for adhering 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 spread of portable personal computers and mobile phones, 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, are QFP
(Quad Flat Package) and SOP (Small Outline P)
ackage) has been the mainstream, but recently
GA (Ball Grid Allay), CSP (Chip Size Packag)
e) ICs that can be mounted at high density using surface mount type
It is in the spotlight as a package.

[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. Depending on the type of the IC substrate, a plastic BGA (hereinafter abbreviated as P-BGA), a ceramic BGA (hereinafter abbreviated as C-BGA), a tape BGA.
(Hereinafter abbreviated as T-BGA), high performance (Enhanc)
ed) BGA (hereinafter abbreviated as E-BGA) and the like.
They are being developed. Until recently, P-BGAs that could use wire bonding technology in QFP were the mainstream, but T-BGAs using TAB (Tape Automated Bonding) technology have been further densified (multiple pins).
Is becoming mainstream because of its excellent heat dissipation. The CSP is a package obtained by further reducing the size and density of the BGA, and is called a micro BGA or a fine pitch BGA. In particular, the CSP is a package having excellent electrical characteristics such as low impedance and high-speed frequency response based on 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 a semiconductor (IC) chip 6 via an adhesive layer 7. The IC chip 6 is connected to the wiring 3 formed on one surface of the insulating film 4 via the electrode 5 via the gold wire 2, and further electrically connected to the outside via the solder ball 1. FIG. 2 shows a cross-sectional view of an example of the micro-BGA.
The insulating film 4 provided with the wiring 3 is laminated on the IC chip 6 via the adhesive layer 7, and the IC chip 6 is provided on the one side of the insulating film 4 via the electrode 5. And further electrically connected to the outside via the solder ball 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]

Generally, a polyimide film is used as the insulating film 4 and an epoxy resin adhesive is used as the adhesive for the adhesive layer 7. The IC package is an IC when driven
The temperature rises from 100 ° C. or more due to the heat generated by the adhesive, and therefore, a temperature change from room temperature to high temperature and humidity resistance at high temperature are required. Was not enough. As the epoxy resin-based adhesive, a method of adding an elastic body to an epoxy resin to impart a film property is generally used. However, in terms of cost and workability, an NBR (acrylonitrile-butadiene copolymer) is used for the elastic body. ) Or acrylic rubber is exclusively used. However, since NBR has a higher polarity due to the effect of the nitrile group, it easily propagates impurities contained in the resin, and acrylic rubber is mainly composed of butyl acrylate. Decomposes into polyhydric alcohols, and the generated acids cause corrosion of the electrodes and increase in ionic substances, which lowers the electrical reliability (for example,
A short circuit occurred between the wirings, the resistance dropped, and the current leaked).

There is also a hot-melt type adhesive in which a polyethylene resin having a glycidyl group and epoxy resin curing agent are partially blended, but the resin is hot-melted and kneaded without using a solvent, so that the curing component is low. When the amount is too large, the viscosity increases due to the thermosetting reaction of the epoxy, and the resin is often not discharged, and the film thickness is often uneven. Also,
When the amount of the curing component is reduced, the film can be formed uniformly, but the elastic modulus at a high temperature becomes low, and the adhesive causes a decrease in viscosity in a reflow process, and the adhesive and the adherend adhere to the moisture absorbing portion. Evaporation often resulted in voids called popcorn.

[0007] In recent years, as the fine pitch of the wiring substrate has advanced, it has been required that the adhesive has a reliable insulating property even under high temperature and high humidity. Further, as Pb becomes free in the solder reflow process, it is necessary to increase the reflow temperature and to reduce the size of a package such as a CSP, so as to have a stress relaxation property.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive composition and an adhesive sheet satisfying the above requirements. The adhesive composition for a semiconductor device of the present invention can react with at least ethylene as the (A) epoxy resin, (B) the epoxy curing agent, and (C) the monomer component with the epoxy resin or the epoxy curing agent. It is characterized by containing a vinyl copolymer containing an unsaturated carboxylic acid derivative having a functional group. Also,
The adhesive sheet of the present invention is characterized in that a layer made of the adhesive composition is laminated on at least one surface of a support.

[0009]

Embodiments of the present invention will be described below in detail. First, the essential components (A) to (C) in the adhesive composition of the present invention will be described. (A) Epoxy resin: An epoxy resin is a resin having two or more epoxy groups in a molecule, for example, glycidyl ether, glycidyl ester, glycidylamine,
Resins of any structure, such as linear aliphatic epoxides and alicyclic epoxides, may be used alone or in combination of two or more. Specifically, bisphenol A
Diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, resol phenol diglycidyl ether, brominated bisphenol A diglycidyl ether, fluorinated bisphenol A diglycidyl ether, phenol novolak glycidyl ether, cresol novolac glycidyl ether, bromination Glycidyl ethers such as novolak glycidyl ether, diglycidyl hexahydrophthalate, diglycidyl phthalate, diglycidyl dimer, and the like, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl metaxylene diamine, etc. Glycidylamines, epoxidized polybutadienes, epoxidized Linear aliphatic epoxides such as soybean oil, 3,4-epoxy-6-methylcyclohexyl methyl carboxylate, alicyclic epoxides such as 3,4-epoxycyclohexylmethyl carboxylate.

The epoxy resin preferably used in the present invention is, specifically, a bifunctional epoxy resin such as Epicoat 806, 828, 834, 1001, etc., manufactured by Yuka Shell Epoxy, and Epicoat 152, 154, 180S6.
5, 1032H60, 157S70 and other polyfunctional epoxy resins, manufactured by Nippon Kayaku Co., Ltd., trade names: EOCN102S, 10
3S, 104S, 1020, EPPN501H, 502
H and other trifunctional or higher polyfunctional epoxy resins. To impart flame retardancy, it is effective to use a halogenated epoxy resin, particularly a brominated epoxy resin. Specific examples of the brominated epoxy resin include trade names of Epicoat 5045 and 50 manufactured by Yuka Shell Epoxy.
46, 5050, product name: Nippon Kayaku Co., Ltd .: BREN-
S, BREN-105, BREN-301 and the like.

Among them, polyfunctional epoxy resins, more preferably triphenolmethane type, novolak phenol type, cresol novolak type, tetraglycidyldiphenylalkane type, tetraglycidyl metaxylenediamine type and diglycidyldiphenolpropane type A functional epoxy resin is preferably used because of its excellent insulating properties and heat resistance. Further, bisphenol A type epoxy resin is preferably used because of its good compatibility with the component (C).

The epoxy equivalent of these epoxy resins is:
Those having 100 to 4000 are preferable, and more preferably 1 to 4000.
It is in the range of 00-2000, optimally 170-1000. When the epoxy equivalent exceeds 4000 and is large, the elastic modulus of the cured product is reduced, and the insulation and heat resistance are reduced. On the other hand, when the epoxy equivalent is less than 100, the adhesive strength decreases. The weight average molecular weight of these epoxy resins is preferably from 100 to 2,000, more preferably from 150 to 1500, and most preferably from 200 to 1200. If the weight average molecular weight is larger than 2,000, the compatibility with the component (C) decreases. On the other hand, when the weight average molecular weight is less than 100, the adhesive strength decreases. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using styrene as a standard. The content of the epoxy resin is 3 to 40% by weight, preferably 5% by weight, based on the total amount of the resin solid.
２５25% by weight.

(B) Epoxy curing agent: Epoxy curing agent refers to a chemical substance that 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'-aminodiphenylmethane,
4,4'-diaminodiphenyl ether, diaminodiphenylsulfone, diaminodiphenylsulfide, m
-Phenylenediamine, 2,4-toluylenediamine,
m- or o-toluylenediamine, metaxylylenediamine, metaaminobenzylamine, benzidine, 4-chloro-o-phenylenediamine, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine,
Aromatic polyamines such as isophthalic dihydrazide, diethylenetriamine, dipropylenetriamine, diethylenetetramine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, hexamethylenediamine,
N-aminoethylpiperazine, bis-aminopropylpiperazine, trimethylhexamethylenediamine, adipic dihydrazide, aliphatic polyamines such as dicyandiamide, dimer acid polyamide, maleic anhydride, dodecenyl succinic anhydride, sebacic anhydride, phthalic anhydride,
Pyromellitic anhydride, trimellitic anhydride, cyclopentane / tetracarboxylic dianhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Acid anhydrides such as methylnadic anhydride, phenol derivatives such as resole phenolic resins, phenol novolak resins, cresol novolak resins, and xylene resins;

2,2-dimercaptodiethyl ether,
Polymercaptans such as 1,2-dimercaptopropane, 1,3-dimercaptopropanol, bis (2-mercaptoethylsulfide), dimethylaminomethylphenol, 2,4,6-tri (dimethylaminomethyl)
Phenol, 2-methylimidazole, 2-ethyl-4
-Methylimidazole, 2-undecylimidazole,
2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole, 1-cyanoethyl-2-methylimidazole, 1
-Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6- [2'- Methylimidazolyl- (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,
Tertiary amines such as -phenyl-4,5-dihydroxymethylimidazole, 2-methylimidazole / triazine complex, boron trifluoride / monoethylamine complex compound, boron trifluoride / triethanolamine complex compound;
Lewis acid complexes such as boron trifluoride / piperidine complex compound and boron trifluoride / n-butyl ether complex compound are exemplified. Among them, phenol derivatives are excellent in reactivity and excellent in heat and humidity resistance even in applications of semiconductor devices,
It can be used preferably.

In the present invention, a polymer epoxy curing agent such as a phenol derivative, a polyamine, or a polyamide is used in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the epoxy resin.
0 parts by weight, preferably 80 to 500 parts by weight, and the other epoxy curing agent is added in the range of 0.1 to 20 parts by weight, preferably 0.5 to 5 parts by weight. When the amount is more than the upper limit, the adhesiveness deteriorates. On the other hand, when the amount is less than the lower limit, the wet heat resistance deteriorates.

(C) Vinyl copolymer: The vinyl copolymer contains at least ethylene and an unsaturated carboxylic acid derivative having a functional group capable of reacting with the epoxy resin or epoxy curing agent as a main monomer component. In addition, a small amount of, for example, vinyl acetate, alkyl (meth) acrylate and the like may be contained as a monomer component. Functional groups that can react with the epoxy resin or epoxy curing agent include an amino group, an isocyanate group,
Glycidyl group, carboxyl group (including anhydride group), silanol group, hydroxyl group, vinyl group, methylol group, mercapto group, ester group, etc., among which amino group, carboxyl group, glycidyl group and hydroxyl group are reactive It is preferable because it is rich. Particularly preferred functional groups are a glycidyl group and a carboxyl group. Specific examples of the unsaturated carboxylic acid derivative having these groups include the following. Examples of those having a carboxyl group include olefins such as acrylic acid, methacrylic acid, (anhydride) maleic acid, and propylene having a carboxyl group.
Examples of those having a glycidyl group include glycidyl acrylate and glycidyl methacrylate, and those having a hydroxyl group include hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate.

The third monomer copolymerizable with the ethylene and the unsaturated carboxylic acid derivative having a functional group includes (meth) acryl such as methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate. Acid alkyl or aryl esters, vinyl acetate and the like.

The content of the unsaturated carboxylic acid derivative having a functional group constituting the copolymer is preferably 0.1 to 40% by weight, more preferably 0.8 to 20% by weight. When the content of the unsaturated carboxylic acid derivative component in the copolymer molecule is less than 0.1% by weight,
When the reactivity with the component (A) or (B) is low, the solubility in an organic solvent is low, and when the content exceeds 40% by weight, the stability in a paint state is deteriorated. When the third monomer component is present, its content is 40% by weight.
Or less, more preferably 30% by weight or less.

In the present invention, preferable examples of the vinyl copolymer include ethylene- (meth) acrylate-maleic anhydride copolymer and ethylene- (meth) acrylate.
Alkyl acrylate-glycidyl (meth) acrylate copolymer, ethylene-glycidyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-glycidyl (meth) acrylate-vinyl acetate copolymer No. Among them, ethylene-
(Meth) acrylic acid alkyl ester-maleic anhydride copolymer, ethylene- (meth) acrylic acid alkyl ester-glycidyl (meth) acrylate copolymer, ethylene-glycidyl (meth) acrylate copolymer are preferred.

[0020] The vinyl copolymer is added for the purpose of imparting flexibility to the adhesive composition.
Those containing (meth) acrylic acid esters are desirable. Since the copolymer containing ethylene- (meth) acrylate does not contain a diene bond in the main chain, it hardly undergoes thermal degradation (loss of elasticity) when left at high temperatures, and can maintain stress relaxation for a long period of time. . In addition, since the side chain has an ester bond, it has a relatively high solubility in an organic solvent, and is hardly hydrolyzed. It is suppressed and has high electrical reliability. In this case, the monomer ratio of the acrylate is preferably 5 to 40 mol%. If the amount is less than 5 mol%, the solubility in an organic solvent is extremely reduced, and the solution is unsuitable for a coating solution (paint). If the amount exceeds 40 mol%, the electrical properties are reduced due to hydrolysis. I will. The weight average molecular weight of the vinyl copolymer is 1000 to
2,000,000, preferably 100,000 to 10,000
00.

In the present invention, the vinyl copolymer is
It is preferable that the tensile elongation at break has 500% or more.
More preferably, it is at least 700%. In the present invention, the tensile elongation at break refers to JI
It means the value measured according to SK6760. When the tensile elongation at break is less than 500%, the film formability is poor, and the flexibility of the adhesive composition layer after curing of the resin is also low. The solubility of the vinyl copolymer in an organic solvent is preferably 5% or more, more preferably 10% or more. When the solubility is less than 5%, the thickness at the time of film formation becomes extremely thin, which is not practical. In addition,
Solubility: toluene / xylene (= 1/1) mixed solution 1
100 g of a sample was added to 00 g, dissolved by stirring at 80 ° C. for 12 hours, cooled to room temperature, and then the solution was filtered through a nylon 600 mesh filter to determine the amount (x) g of the insoluble residue. It can be obtained by the following equation. Solubility (%) = [(100 g− (x) g) / 100 g]
× 100 It is also preferable to use two or more of the above vinyl copolymers in the adhesive composition of the present invention.

In the present invention, the vinyl copolymer is
20 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin and the epoxy curing agent.
It is blended in the range of parts by weight. If the amount is more than 200 parts by weight, the film-forming properties deteriorate. If the amount is less than 20 parts by weight, the film becomes brittle.

In order to accelerate the curing reaction of the adhesive composition of the present invention, in addition to the above essential components (A), (B) and (C), imidazoles, 1,8-diazabicyclo (5, It is preferable to add a reaction accelerator (curing accelerator) such as an amine catalyst such as (4,0) undecene or a phosphorus catalyst such as triphenylphosphine.

In the adhesive composition of the present invention, the preferred mixing ratio of the components (A), (B) and (C) and the reaction accelerator optionally added is such that the component (A) is 3 to 40.
% By weight, component (B) 0.5 to 50% by weight, component (C)
Is in the range of 30 to 80% by weight, and the reaction accelerator is in the range of 0 to 10% by weight.

The adhesive composition for a semiconductor device 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, Zirconium carbide, molybdenum carbide,
Mica, zinc oxide, carbon black, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, antimony trioxide or those obtained by treating the surface of these with a trimethylsiloxyl group or the like, and the like, as an organic filler, polyimide, Examples thereof include polyamide imide, polyether ether ketone, polyether imide, polyester imide, nylon, and silicone. The compounding amount of the filler is in the range of 3 to 95 parts by weight, preferably 10 to 50 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C) and the reaction accelerator.

Further, it is preferable to add a coupling agent to the adhesive composition of the present invention in order to improve adhesion to an adherend. As the coupling agent, a silane coupling agent, a titanium coupling agent and an aluminum coupling agent are preferably used.

The above essential components (A) to (C) and additives are dissolved in an organic solvent and used in the form of an adhesive solution. Preferred organic solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
N, N-dimethylformamide, pyridine, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, 1,4-dioxane, tetrahydrofuran, ethanol, methanol, methyl cellosolve and the like.

The adhesive sheet for a semiconductor device of the present invention has a structure in which a layer made of the adhesive composition is laminated on at least one surface of a support, and the adhesive solution is applied to at least one surface of the support. It is produced by coating. As the support, a peelable film, an insulating film, a release paper or the like can be used, and in particular, a peelable film and an insulating film are preferably used.

Film materials used for the peelable film and the insulating film include polyesters such as polyethylene terephthalate (hereinafter abbreviated as PET), polyolefins such as polyethylene, polyimide, polyamide, polyether sulfone, and polyphenylene sulfide. , Polyether ketone, triacetyl cellulose and the like are mentioned as preferred, more preferably,
Examples include polyesters, polyolefins and polyimides. As the releasable film, a film obtained by subjecting a film made of these film materials to a release treatment with a release agent such as silicone is preferably used.

An adhesive sheet is prepared by forming a layer of the above-mentioned adhesive composition on one or both sides of these supports. In the present invention, the layer made of the adhesive composition is a semi-cured adhesive. It is preferably a layer, and a protective film is adhered as needed during storage and peeled off during use. The thickness of the formed layer of the adhesive composition after drying is in the range of 3 to 200 μm, preferably 5 to 50 μm.

As shown in FIGS. 1 to 4, the adhesive sheet of the present invention is temporarily bonded to an object to be bonded and then cured by heating, and the adhesive composition in the adhesive sheet is as follows.
The dynamic elastic modulus at 200 to 280 ° C. after curing is 1
It is preferably in the range of MPa to 100 MPa. That is, the adhesive composition is heated to 200 to 280 ° C. in a reflow step (soldering step) when BGA or the like is mounted on the main board via solder balls.
Therefore, the adhesive composition has a viscosity of 200 to 280 after curing.
It is preferable that the dynamic elastic modulus in the range of 1 MPa to 100 MPa be excellent in void resistance and stress relaxation during the reflow step. In addition, the dynamic elastic modulus is a value measured at a frequency of 11 Hz and a temperature rising rate of 3 ° C./min using a Leo Vibron DDV-II manufactured by Orientec Co., Ltd. for a film made of a cured adhesive composition having a thickness of 100 μm. It is.

The adhesive composition and the adhesive sheet of the present invention comprise:
Particularly, it is preferably used for a semiconductor device in which an IC chip is laminated on an IC substrate composed of an insulator layer and a conductor circuit, and is further suitably used for a surface mount type semiconductor device.
Among them, it is most suitable for bonding an IC chip or bonding a heat sink. Specifically, FIG. 1 and FIG.
Is suitably used as an adhesive for bonding the IC chip 6 and the insulating film 4 of the IC substrate. Further, it can be suitably used for the semiconductor devices illustrated in FIGS.

Referring to FIGS. 3 and 4, in the semiconductor device shown in FIG.
The IC chip 6 and the reinforcing plate 9 are bonded through the
The insulating film 4 is adhered thereon via an adhesive layer 7,
Further, the wiring 3 wired on the insulating film 4 via the adhesive 10 is connected to the electrode 5 formed on the IC chip 6. Further, the solder ball 1 is formed on the wiring 3,
A resin 11 is potted around the IC chip 6. The adhesive composition of the present invention is suitable as an adhesive for bonding the IC chip 6 and the heat sink 8 in this semiconductor device.

In the semiconductor device shown in FIG.
The IC chip 6 and the insulating film 4 are bonded on the heat radiating plate 12 via the adhesive layer 7, and the wiring 3 wired on the insulating film 4 via the adhesive 10 is attached to the IC chip 6. It is connected to the formed electrode 5. Further, solder balls 1 are formed on the wirings 3, and around the IC chip 6,
The resin 11 is potted. The adhesive composition of the present invention is suitable as an adhesive for bonding the IC chip 6 and the insulating film 4 to the heat sink 12 in this semiconductor device.

[0035]

Examples [Preparation of adhesive composition paint] Epoxy resin (A), epoxy curing agent (B), vinyl copolymer (C) or copolymer for comparative example shown in the following Examples and Comparative Examples In each of the coalescing and the curing accelerator, a solution dissolved in an organic solvent or a solution not dissolved in an organic solvent is blended and mixed so as to have a weight% (weight ratio of the blend) shown in Table 1 and mixed with the present invention. A paint for a semiconductor device adhesive composition for comparison was obtained.

Example 1 Epoxy resin: Triphenylmethane-type polyfunctional epoxy resin (trade name: EPPN501H, manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight: 600) was added to the ME so that the concentration became 70% by weight.
A solution in K. Epoxy curing agent: A solution in which novolak phenolic resin (trade name: Shonor CKM2400, manufactured by Showa Polymer Co., Ltd.) is dissolved in MEK to a concentration of 50% by weight. Copolymer: ethylene- Solution prepared by dissolving ethyl acrylate-maleic anhydride copolymer (trade name: Bondyne AX8390, manufactured by Sumitomo Atchem Co., Ltd., tensile elongation at break 900%, solubility 15% or more) in toluene to a concentration of 5% by weight. Accelerator: 2-undecylimidazole (trade name:
(C11Z, manufactured by Shikoku Chemical Industry Co., Ltd.) dissolved in MEK to a concentration of 1% by weight.

Examples 2 to 4 Epoxy resin: Triphenylmethane type polyfunctional epoxy resin (trade name: EPPN501H, manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight: 600) was added to the ME so that the concentration became 70% by weight.
Solution in K. Epoxy curing agent: A solution in which novolak phenolic resin (trade name: Retopo PSM4261, manufactured by Gunei Chemical Co., Ltd.) is dissolved in MEK to a concentration of 50% by weight. Copolymer: ethylene-glycidyl A solution in which a methacrylate copolymer (trade name: Bondfast 7M, manufactured by Sumitomo Chemical Co., Ltd., tensile elongation at break: 1000%, solubility: 20% or more) is dissolved in toluene to a concentration of 20% by weight. -Undecyl imidazole (trade name:
(C11Z, manufactured by Shikoku Chemical Industry Co., Ltd.) dissolved in MEK to a concentration of 1% by weight.

Example 5 Epoxy resin: A triphenylmethane-type polyfunctional epoxy resin (trade name: EPPN502H, manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight: 650) was adjusted to a concentration of 70% by weight in ME.
Solution in K. Epoxy curing agent: A solution in which novolak phenolic resin (trade name: Retopo PSM4261, manufactured by Gunei Chemical Co., Ltd.) is dissolved in MEK to a concentration of 50% by weight. Copolymer: ethylene-glycidyl A solution in which a methacrylate copolymer (trade name: Bondfast 7B, manufactured by Sumitomo Chemical Co., Ltd., tensile elongation at break: 750%, solubility: 10% or more) is dissolved in MEK to a concentration of 20% by weight. -Undecyl imidazole (trade name:
(C11Z, manufactured by Shikoku Chemical Industry Co., Ltd.) dissolved in MEK to a concentration of 1% by weight.

Example 6-Epoxy resin: bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy, weight average molecular weight 400)-Epoxy curing agent: novolak phenol resin (trade name: Shonor CKM2400, Solution prepared by dissolving Showa Polymer Co., Ltd. in toluene to a concentration of 50% by weight. Copolymer: ethylene-ethyl acrylate-maleic anhydride copolymer (trade name: Bondyne AX8390, manufactured by Sumitomo Atochem Co., Ltd.) Solution prepared by dissolving a tensile elongation at break of 900% and a solubility of 15% or more in toluene to a concentration of 10% by weight. -Curing accelerator: 2-undecyl imidazole (trade name:
(C11Z, manufactured by Shikoku Chemical Industry Co., Ltd.) dissolved in toluene to a concentration of 1% by weight.

Examples 7 to 9 Epoxy resin: Triphenylmethane type polyfunctional epoxy resin (trade name: EPPN501H, manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight: 600) is dissolved in toluene to a concentration of 50% by weight. Solution: Epoxy curing agent: A solution in which novolak phenol resin (trade name: Shonor CKM2400, manufactured by Showa Polymer Co., Ltd.) is dissolved in toluene to a concentration of 50% by weight. Copolymer: ethylene-glycidyl methacrylate copolymer A solution obtained by dissolving the coalesced product (trade name: Bondfast 7M, manufactured by Sumitomo Chemical Co., Ltd., tensile elongation at break 1000%, solubility 20% or more) in toluene to a concentration of 20% by weight. -Curing accelerator: 2-undecyl Imidazole (trade name:
(C11Z, manufactured by Shikoku Chemical Industry Co., Ltd.) dissolved in toluene to a concentration of 1% by weight.

Example 10 Epoxy resin: A solution obtained by dissolving a triphenylmethane type polyfunctional epoxy resin (trade name: EPPN502H, manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight: 650) in toluene to a concentration of 50% by weight. -Epoxy curing agent: A solution in which novolak phenol resin (trade name: Shonor CKM2400, manufactured by Showa Polymer Co., Ltd.) is dissolved in toluene to a concentration of 50% by weight.-Copolymer: Ethylene-glycidyl methacrylate copolymer ( (Product name: Bond First 7B, manufactured by Sumitomo Chemical Co., Ltd., tensile elongation at break: 750%, solubility: 10% or more) dissolved in toluene to a concentration of 20% by weight ・ Curing accelerator: 2-undecyl imidazole ( Product name:
(C11Z, Shikoku Chemical Industry Co., Ltd.) dissolved in toluene to a concentration of 1% by weight.

Example 11 Epoxy resin: bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co., weight average molecular weight 400) Epoxy curing agent: novolac phenol resin (trade name: Shonor CKM2400, Solution prepared by dissolving Showa Polymer Co., Ltd. in toluene to a concentration of 50% by weight. Copolymer: ethylene-ethyl acrylate-maleic anhydride copolymer (trade name: Bondyne AX8390, manufactured by Sumitomo Atochem Co., Ltd.) A solution in which a tensile elongation at break of 900% and a solubility of 15% or more) is dissolved in toluene so as to have a concentration of 20% by weight. -Curing accelerator: 2-undecylimidazole (trade name:
(C11Z, manufactured by Shikoku Chemical Industry Co., Ltd.) dissolved in toluene to a concentration of 1% by weight.

Example 12 Epoxy resin: bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd., weight average molecular weight: 400) Epoxy curing agent: novolac phenol resin (trade name: Shonor CKM2400, Solution prepared by dissolving Showa Polymer Co., Ltd. in toluene to a concentration of 50% by weight. Copolymer: Ethylene-glycidyl methacrylate copolymer (trade name: Bondfast 7M, manufactured by Sumitomo Chemical Co., Ltd., tensile elongation at break) A solution in which 1000% and a solubility of 20% or more are dissolved in toluene so as to have a concentration of 20% by weight. -Curing accelerator: 2-undecylimidazole (trade name:
(C11Z, manufactured by Shikoku Chemical Industry Co., Ltd.) dissolved in toluene to a concentration of 1% by weight.

Example 13 Epoxy resin: bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy, weight average molecular weight: 400) Epoxy curing agent: novolac phenol resin (trade name: Shonor CKM2400, Solution prepared by dissolving 50% by weight of Showa Polymer Co., Ltd. in toluene. Copolymer: Ethylene-glycidyl methacrylate copolymer (trade name: Bondfast 7B, manufactured by Sumitomo Chemical Co., Ltd., tensile elongation at break) A solution in which 750% and a solubility of 10% or more are dissolved in toluene so as to have a concentration of 10% by weight. -Curing accelerator: 2-undecylimidazole (trade name:
(C11Z, manufactured by Shikoku Chemical Industry Co., Ltd.) dissolved in toluene to a concentration of 1% by weight.

Comparative Example 1 Epoxy resin: Bisphenol A type epoxy resin (trade name: Epikote 834, manufactured by Yuka Shell Epoxy Co., Ltd., weight average molecular weight: 500) was adjusted to a concentration of 80% by weight.
Solution dissolved in EK ・ Epoxy hardener: Novolac phenol resin (trade name: Retop PSM4261, manufactured by Gunei Chemical Co., Ltd.) dissolved in MEK to a concentration of 70% by weight ・ Copolymer: Carboxyl group-containing NBR (trade name: Nippol 1072J, manufactured by Zeon Corporation) at a concentration of 15% by weight
A solution dissolved in MEK so as to obtain a curing accelerator: 2-undecylimidazole (trade name:
(C11Z, manufactured by Shikoku Chemical Industry Co., Ltd.) dissolved in MEK to a concentration of 1% by weight.

Comparative Example 2 Epoxy resin: Bisphenol A type epoxy resin (trade name: Epikote 834, manufactured by Yuka Shell Epoxy Co., Ltd., weight average molecular weight: 500) was adjusted to a concentration of 80% by weight.
Solution dissolved in EK ・ Epoxy curing agent: Solution prepared by dissolving novolak type phenol resin (trade name: Shonor BRG-557, manufactured by Showa Polymer Co., Ltd.) in MEK to a concentration of 70% by weight ・ Copolymer : A solution in which a carboxyl group-containing polyester (trade name: BX218, manufactured by Toyobo Co., Ltd.) is dissolved in cyclohexanone / petroleum-based solvent to a concentration of 35% by weight. -Curing accelerator: 2-undecylimidazole (trade name:
(C11Z, manufactured by Shikoku Chemical Industry Co., Ltd.) dissolved in MEK to a concentration of 1% by weight.

Comparative Example 3 Epoxy resin: Bisphenol A type epoxy resin (trade name: Epikote 834, manufactured by Yuka Shell Epoxy Co., Ltd., weight average molecular weight: 500) was prepared so that the concentration was 80% by weight.
Solution dissolved in EK ・ Epoxy hardener: Novolac phenol resin (trade name: Retop PSM4261, manufactured by Gunei Chemical Co., Ltd.) dissolved in MEK to a concentration of 70% by weight ・ Copolymer: Carboxyl group-containing A solution in which acrylic rubber (trade name: WS023DR, manufactured by Teikoku Chemical Industry Co., Ltd.) is dissolved in MEK to a concentration of 20% by weight. -Curing accelerator: 2-undecyl imidazole (trade name:
(C11Z, manufactured by Shikoku Chemical Industry Co., Ltd.) dissolved in MEK to a concentration of 1% by weight.

[Evaluation of Electrical Characteristics] Thickness 3 after peeling treatment
An 8 μm polyester film support was coated with a coating of an adhesive composition having the composition shown in Examples 1 to 13 and Comparative Examples 1 to 3 in Table 1 and dried by heating at 130 ° C. for 5 minutes to bond to a thickness of 50 μm. After forming an agent layer and forming an adhesive sheet, a 50 μm-thick polyethylene protective film subjected to a release treatment was bonded. Separately, 3/4 oz copper foil is thermocompression bonded to the adhesive surface of a polyimide film with adhesive for TAB (manufactured by Hamakawa Seisakusho), and bonded by heating at 90 ° C for 1 hour and further at 150 ° C for 2 hours. The agent layer was cured. Next, a photoresist film is thermocompressed and etched on the copper foil surface,
The resist film is peeled off, and the distance between conductors / conductors is 50 μm / 5
A 0 μm comb-shaped circuit was formed. On this circuit surface, while peeling off the polyethylene protective film of the adhesive sheet,
The adhesive sheet is pressure-bonded so that the adhesive layers are opposed to each other, the polyester film is peeled off, and at 90 ° C. for 1 hour, further 15 hours
The adhesive layer was cured by heating at 0 ° C. for 4 hours to obtain an electrical property evaluation sample. A 5 VDC voltage was applied to this evaluation sample in a thermostatic chamber at 130 ° C. and 85% RH for 3 hours.
It was applied continuously for 00 hours, the insulation resistance before and after the constant temperature and humidity test was measured, and the presence or absence of electrolytic corrosion of the conductor (copper foil portion) of the comb-shaped circuit was observed. The results are shown in Tables 2 and 3.

[Evaluation of Warpage Characteristics] Thickness 3 after peeling treatment
An 8 μm polyester film support was coated with a coating of an adhesive composition having the composition shown in Examples 1 to 13 and Comparative Examples 1 to 3 in Table 1 and dried by heating at 130 ° C. for 5 minutes to bond to a thickness of 50 μm. After forming an adhesive layer and forming an adhesive layer, a 50 μm-thick polyethylene protective film subjected to a release treatment was bonded. Then, while peeling off the polyethylene protective film and polyester film, the thickness 75
μm polyimide film (trade name: Upilex 7)
5S, manufactured by Ube Industries, Ltd.) was thermocompression-bonded to both surfaces of the adhesive layer.
After cutting it to a width of 70 mm, it was heated at 90 ° C. for 1 hour and further at 150 ° C. for 2 hours to cure the adhesive layer, thereby producing a polyimide film laminate. The cured polyimide film laminate was cut into 70 mm x 5 mm to obtain a warpage characteristic evaluation sample. The evaluation sample was placed on a horizontal table so as to be in a convex state, and the height of the convex portion was measured with a digital measuring microscope (Olympus: STM-UM). The results are shown in Tables 2 and 3.

[Evaluation of Reflow Property] Using the coatings of the adhesive compositions of Examples 6 to 13 and Comparative Examples 1 to 3, simulated T-BGA packages having the structure shown in FIG. 3 were produced. After leaving this package at a temperature of 85 ° C. and a humidity of 85% RH for 72 hours, an IR reflow device (temperature conditions: maximum 240 ° C., 22
(0 ° C. or more for 10 seconds), and after standing to cool, the presence of popcorn phenomenon in the adhesive layer was confirmed by ultrasonic flaw detection. Table 3 shows the results. The numbers in the table are the number of good packages without occurrence of the popcorn phenomenon when n = 20.

[Dynamic Modulus After Curing] A coating of the adhesive composition of Examples 6 to 13 and Comparative Examples 1 to 3 was applied to a release-treated polyester film support having a thickness of 38 μm and dried. To form an adhesive layer having a thickness of 100 μm.
After curing at 50 ° C. for 2 hours, the dynamic elastic modulus was measured. Dynamic modulus of elasticity: Orientec Co., Ltd .: Leo Vibron DD
The measurement was performed using V-II under the conditions of a frequency of 11 Hz and a heating rate of 3 ° C./min. Table 3 shows the results.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

The adhesive composition of the present invention has suitable elasticity and high insulation properties, and does not generate electrolytic corrosion even in a high-temperature and high-humidity environment, that is, has high electrical reliability.
Further, the adhesive sheet of the present invention has less warpage of the film and is excellent in reflow resistance. Therefore, the adhesive composition and the adhesive sheet of the present invention can be used for T-BGA, CSP
It is suitable for use in semiconductor packages with high density,
Particularly, it is suitable for bonding an IC chip or a heat sink.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a fine pitch BGA.

FIG. 2 is a cross-sectional view of an 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 another example of the semiconductor device.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Solder ball, 2 ... Gold wire, 3 ... Wiring, 4 ... Insulating film, 5 ... Electrode, 6 ... Semiconductor (IC) chip, 7
... adhesive layer, 8 ... heat sink, 12 ... heat sink.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshihiro Nakajima 3-1 Yomoba-cho, Shizuoka-shi, Shizuoka Prefecture F-term in the Electronic Materials Division of Hamakawa Paper Mill Co., Ltd. 4J004 AA07 AA09 AA10 AA13 AB04 FA05 4J040 DA002 DA052 DA062 DA072 DA082 DE022 DF032 DG022 EC001 EC232 GA07 GA11 KA16 LA01 NA20 5F047 AA02 AA17 BA21 BB03

Claims (11)

[Claims] 1. At least (A) an epoxy resin,
(B) an epoxy curing agent, and (C) a vinyl copolymer containing at least ethylene and an unsaturated carboxylic acid derivative having a functional group capable of reacting with the epoxy resin or the epoxy curing agent as a monomer component. An adhesive composition for a semiconductor device, comprising: 2. The adhesive composition for a semiconductor device according to claim 1, wherein the functional group capable of reacting with the epoxy resin or epoxy curing agent of the unsaturated carboxylic acid derivative is a glycidyl group or a carboxyl group. 3. The method according to claim 1, wherein the vinyl copolymer has a tensile elongation at break of 5.
2. The adhesive composition for a semiconductor device according to claim 1, wherein the composition has a content of at least 00%. 4. The vinyl copolymer is an ethylene-alkyl (meth) acrylate-maleic anhydride copolymer, an ethylene-alkyl (meth) acrylate-glycidyl (meth) acrylate copolymer, an ethylene-alkyl ester. The semiconductor device according to claim 1, wherein the glycidyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid copolymer and ethylene-glycidyl (meth) acrylate-vinyl acetate copolymer are at least one selected from the group consisting of: Adhesive composition. 5. The adhesive composition for a semiconductor device according to claim 1, wherein the solubility of the vinyl copolymer in an organic solvent is 5% or more. 6. The content of the vinyl copolymer is 20 per 100 parts by weight of the total amount of the epoxy resin and the epoxy curing agent.
The adhesive composition for a semiconductor device according to claim 1, wherein the amount is from 200 to 200 parts by weight. 7. The adhesive composition for a semiconductor device according to claim 1, wherein the epoxy resin is a polyfunctional epoxy resin. 8. An epoxy resin having a weight average molecular weight of 10
The adhesive composition for a semiconductor device according to claim 1, wherein the composition has 0 to 2,000. 9. The adhesive composition for a semiconductor device according to claim 1, wherein a dynamic elastic modulus at 200 to 280 ° C. after curing is in a range of 1 MPa to 100 MPa. 10. The adhesive composition for a semiconductor device according to claim 1, which is used for bonding an IC chip or a heat sink. 11. The method according to claim 1, wherein at least one surface of the support is provided.
An adhesive sheet for a semiconductor device, wherein a layer made of the adhesive composition described above is laminated.