JP2002180021A - Adhesive composition, adhesive film given by using the same, semiconductor chip-mounting substrate, and semiconductor device given by using the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition excellent in reliability as a semiconductor-packaging component, to provide an adhesive film given by using the composition, and to provide a semiconductor device given by using the adhesive film. SOLUTION: This adhesive composition contains (1) an epoxy resin having two or more epoxy groups in the molecule, (2) a terpene phenolic novolak resin havingstructural units expressed by general formula (I) as a curing agent, and (3) an acrylic copolymer having carboxy groups, hydroxy groups, acid anhydride groups, amide groups or epoxy groups in an amount of 50-300 pts.wt. based on 100 pts.wt. of the total amount of the resins (1) and (2). The adhesive film is given by using the composition. Further, the semiconductor device is given by using the adhesive film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an adhesive composition having excellent reliability as a member for a semiconductor package, an adhesive film using the same, a substrate for mounting a semiconductor chip, and a semiconductor device using the same.

[0002]

2. Description of the Related Art In recent years, with the miniaturization of electronic devices, semiconductor packages mounted thereon have been required to be mounted at high density on a substrate.
Small packages called P (chip size package) and μBGA (ball grid array) are being developed.

[0003] Reliability is one of the important characteristics of a mounting board on which various electronic components are mounted, and particularly, connection reliability is a very important item because it directly relates to the quality of equipment using the mounting board. ing. As a cause of reducing the connection reliability, a thermal stress caused by a difference in thermal expansion coefficient between a semiconductor chip and a substrate on which electronic components are mounted can be cited. This is because the thermal expansion coefficient of a semiconductor chip is as small as about 4 ppm / ° C., while the thermal expansion coefficient of a wiring board on which electronic components are mounted is 15 ppm.
Since the stress is as high as ppm / ° C. or more, when a strain caused by a thermal shock occurs, the strain generates a thermal stress. For example, in bare chip mounting, thermal stress concentrates on a solder ball portion connecting an electrode of a semiconductor chip and a wiring pad of a wiring board, and connection reliability is reduced.
In order to disperse this thermal stress, it is effective to inject a resin called underfill between the chip and the wiring board.
This causes an increase in mounting processes and cost.

[0004]

As a countermeasure for these problems, many structures have been proposed for the CSP.
In the BGA, a low-elastic insulating adhesive is used between a semiconductor chip and a wiring board called an interposer so as to reduce a thermal stress caused by a difference in thermal expansion coefficient. In recent years, it has been reported that as an insulating adhesive suitable for such a field, a low-elasticity adhesive film has good workability and high connection reliability (publication WO 98/15975).
No.) has been. Physical properties required of the low elasticity adhesive film include adhesion, temperature cycling, moisture resistance and the like, in addition to reduction of thermal stress of the chip and the wiring board. Further, in recent years, there has been an increasing demand for improving the storage stability of the adhesive and the productivity at the time of chip bonding.

[0005] Adhesive films are used for flexible printed wiring boards and the like, and many adhesive-based systems mainly containing various rubbers such as acrylic rubber and acrylonitrile-butadiene rubber are used. These rubbers have been used to improve the strength, flexibility and adhesion of the adhesive.

[0006] Among these, in the system containing acrylic rubber as a main component, the decrease in adhesive strength after long-time treatment at high temperature is relatively small, but the adhesive strength at high temperature is inadequate. There is a disadvantage that the reduction is large. In addition, a system containing acrylonitrile-butadiene rubber as a main component has drawbacks such as a large decrease in adhesive strength after a long-time high-temperature treatment, and poor electrical corrosion resistance. In particular, when a moisture resistance test was performed under severe conditions such as a PCT (pressure cooker test) process used in reliability evaluation of semiconductor-related components, deterioration was large. As an improved solder heat resistance after moisture absorption, an adhesive containing an acrylic resin, an epoxy resin, a polyisocyanate and an inorganic filler disclosed in JP-A-60-243180 is disclosed.
There is an acrylic resin, an epoxy resin, and an adhesive containing a primary amine compound having a urethane bond in each molecule at both ends and a primary amine compound and an inorganic filler described in 1-1138680. However, when a semiconductor chip is mounted on a printed wiring board using these adhesives, the difference in the thermal expansion coefficient between the semiconductor chip and the printed wiring board is large, and cracks occur during reflow, causing a temperature cycle test, PCT processing, or the like. When a moisture resistance test is performed under severe conditions, the deterioration becomes large.

Further, among rubber-epoxy resin adhesives, there are adhesives obtained by mixing reactive acrylic rubber, acrylonitrile butadiene rubber and the like with an epoxy resin, and these adhesives have improved high-temperature adhesion and the like. I have. As shown in JP-A-3-181580, a reactive acrylic adhesive as a reactive rubber adhesive,
There is an adhesive composition comprising a carboxyl group, a hydroxyl group, an epoxy group-containing acrylic elastomer, an alkylphenol, an epoxy resin, and imidazolium trimellitate, and is used in the field of bonding a base film of a flexible printed wiring board to a copper foil. Further, Japanese Patent Application Laid-Open No. 7-766 discloses that the adhesiveness to a glossy surface and the heat resistance are improved.
No. 79, an acrylic elastomer 6 having an epoxy group
0 to 80 parts by weight, 8 to 20 parts by weight of an alkylphenol, 8 to 20 parts by weight of an epoxy resin, and 0.2 to 1.0 part by weight of an imidazole-based curing agent are required. In addition, JP-A-7-1
As shown in JP 73449, there is an epoxy group-containing acrylic elastomer-based adhesive composition.

However, even with these adhesive films having improved high-temperature adhesiveness, lead-free soldering is assumed.
Adhesiveness at 60 ° C. is insufficient, and a problem arises in that a part of the curing agent volatilizes when the adhesive film is adhered to the substrate or the semiconductor chip, and contaminates the base material or the semiconductor chip. Was.

The present invention provides reliability such as heat resistance, moisture resistance, and high-temperature adhesiveness required for mounting a semiconductor chip having a large difference in thermal expansion coefficient on a wiring board called an interposer such as a glass epoxy board and a flexible board. And an adhesive composition having excellent storage stability, an adhesive film using the same, a semiconductor chip mounting substrate using the adhesive film, and a semiconductor device using the same.

[0010]

The present invention provides (1) an epoxy resin having two or more epoxy groups in a molecule; and (2)
As a curing agent, a terpene phenol novolak resin having a structural unit represented by the following general formula (I) may be combined to form 10
0 parts by weight and

Embedded image (3) carboxyl group, hydroxyl group, acid anhydride group,
Acrylic copolymer having an amide group or an epoxy group 5
The present invention relates to an adhesive composition containing 0 to 300 parts by weight. The present invention also relates to an adhesive film using the adhesive composition, a semiconductor chip mounting substrate in which the adhesive film is bonded to an organic support substrate, and a semiconductor device using the substrate.

In the present invention, (1) the epoxy resin having two or more epoxy groups in the molecule may be any as long as it cures and exhibits an adhesive action, and a bifunctional and / or polyfunctional epoxy resin is used. Can be. The bifunctional epoxy resin includes a liquid one and a solid one at room temperature, and these resins can be easily obtained from the market. For example, Epicoat 827, 828, 834, 10
01, 1004, 1007, 1009, 1010 (all manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite GY25
2,250,260,280,6099 (all manufactured by Ciba-Geigy Corporation); E. FIG. R330,331,33
6,337,668,669 (both manufactured by Dow Chemical Co., Ltd.), YD8125, and YDF170 (both manufactured by Toto Kasei Co., Ltd.). Examples of the polyfunctional epoxy resin include a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A novolak epoxy resin, an α-naphthol novolak epoxy resin, and a brominated novolak epoxy resin, and these resins are also easily available from the market. can do. For example, DEN-431, 438, 439 (both manufactured by Dow Chemical Co., Ltd.), Epicoat 152, 154 (both manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN-201, 202
(Nippon Kayaku Co., Ltd.) and other phenol novolak epoxy resins, EOCN-102S, 103S, 104
S, 1020, 1025, 1027 (all manufactured by Nippon Kayaku Co., Ltd.), ESCN-001, 195X, 200S,
220 (all manufactured by Sumitomo Chemical Co., Ltd.), YDCN-70
Cresol novolak epoxy resin such as No. 3 (manufactured by Toto Kasei Co., Ltd.), bisphenol A novolak epoxy resin such as N-865 and N-880 (both manufactured by Dainippon Ink and Chemicals, Inc.), EXB-4300 (Dainippon Ink) Α-naphthol novolak epoxy resin such as Chemical Industry Co., Ltd., and brominated phenol novolak epoxy resin such as BREN-S (Nippon Kayaku Co., Ltd.).

In the present invention, the epoxy resin may be used alone or in combination of two or more.

A terpene phenol novolak resin having a structural unit represented by the following general formula (I) as a curing agent in the present invention can be easily obtained from the market. For example, there is EpiCure MP402 (manufactured by Yuka Shell Epoxy Co., Ltd.).

Embedded image

When the total amount of the epoxy resin and the curing agent in the present invention is 100 parts by weight, the epoxy resin is 40 to 9 parts by weight.
0 parts by weight, preferably 50 to 80 parts by weight.
If the amount of the epoxy resin is too small, the adhesiveness tends to be insufficient, and if it is too large, the heat resistance tends to be insufficient.

In the present invention, in addition to the above-mentioned terpene phenol novolak resin as the curing agent, a polyfunctional phenol resin can be used as a curing agent for other epoxy resins to the extent that the effects of the present invention are not impaired. Examples of the polyfunctional phenol resin include bisphenol A, which is a compound having two or more phenolic hydroxyl groups in one molecule,
There are bisphenol F, bisphenol S, brominated bisphenol A, brominated bisphenol F, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, and the like, which can be easily obtained from the market. For example, Fire Guard FG2000
(Manufactured by Teijin Chemicals Ltd.), brominated bisphenol A, phenolite LF2882, LF2822, TD-209
0, TD-2149, VH4150, VH4170 (all manufactured by Dainippon Ink and Chemicals, Inc.), PSM-4300
(Gunei Chemical Co., Ltd.) H-100 (Meiwa Kasei Co., Ltd.)
And the like. These curing agents are preferably used in a range of 20 parts by weight or less when the total amount of the curing agents is 100 parts by weight. If these amounts are too large, storage stability and low-temperature curability tend to be insufficient.

As the (3) acrylic copolymer having a carboxyl group, a hydroxyl group, an acid anhydride group, an amide group or an epoxy group in the present invention, a nonfunctional monomer and a functional monomer as shown below are used. Obtained by polymerization.

Non-functional monomers include, for example, methyl acrylate, ethyl acrylate, butyl acrylate,
Alkyl acrylates such as 2-ethylhexyl acrylate, norbornyl acrylate, norbornyl methyl acrylate, adamantyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, acrylic acid Tricyclo [5.2.1.0 ^2,6 ] decane-3
(Or 4) -ylmethyl, bornyl acrylate, isobornyl acrylate, cycloalkyl acrylate such as methylcyclohexyl acrylate, aromatic acrylate such as phenyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, Alkyl methacrylates such as butyl methacrylate and 2-ethylhexyl methacrylate, norbornyl methacrylate, norbornylmethyl methacrylate, adamantyl methacrylate, tricyclomethacrylate [5.2.1.0]
^{2, 6]} decan-8-yl methacrylate tricyclo [5.2.1.0 ^{2, 6]} decane-3 (or 4) - ylmethyl, methacrylic acid bornyl, isobornyl methacrylate, methyl methacrylate cyclohexyl methacrylate Cycloalkyl methacrylates such as cyclohexyl, phenyl methacrylate, aromatic methacrylates such as benzyl methacrylate, styrene or α-methylstyrene, α-substituted styrenes such as α-ethylstyrene,
N-alkyl group-substituted maleimides such as chlorostyrene, vinyltoluene, nucleated styrenes such as t-butylstyrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, etc. At least one compound selected from the group consisting of N-aryl group-substituted maleimides such as N-cycloalkyl group-substituted maleimide and N-phenylmaleimide, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile can be used. The non-functional monomer is preferably selected such that the Tg of the copolymer is -20C to 30C, and more preferably -10C to 20C. If the Tg is too low, the tackiness of the adhesive film in the B-stage state tends to be large, and the handleability tends to be deteriorated. If the Tg is too high, the adhesion tends to be insufficient.

Examples of the functional monomer include, for example,
Carboxylic acid-containing monomers such as acrylic acid, methacrylic acid and itaconic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N- Hydroxyl group-containing monomers such as methylol acrylamide, N-methylol methacrylamide, (o-, m-, p-) hydroxystyrene, acid anhydride group-containing monomers such as maleic anhydride, and amide group-containing monomers such as acrylamide and methacrylamide Glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl acrylate α-n-butyl, 3,4-epoxybutyl acrylate, methacrylic acid
3,4-epoxybutyl, acrylate-4,5-epoxypentyl, methacrylate-4,5-epoxypentyl, acrylate-6,7-epoxyheptyl, methacrylate-6,7-epoxyheptyl, α-ethyl 6,7-Epoxyheptyl acrylate, 3-methyl-3,4-epoxybutyl acrylate, 3-methyl-3,4-epoxybutyl methacrylate, 4-methyl-4,5-epoxy acrylate Pentyl, 4-methyl-4,5-epoxypentyl methacrylate, 5-methyl-5,6-epoxyhexyl acrylate, 5-methyl-5,6-epoxyhexyl methacrylate, β-methyl acrylate Glycidyl, β-methyl glycidyl methacrylate, β-methyl glycidyl α-ethylacrylate, 3-methyl-3 acrylate , 4-Epoxybutyl, 3-methyl-3,4-epoxybutyl methacrylate, 4-methyl-4,5-epoxypentyl acrylate, 4-methyl-4,5-epoxypentyl methacrylate, acrylic acid At least one compound selected from the group consisting of epoxy group-containing monomers such as -5-methyl-5,6-epoxyhexyl and -5-methyl-5,6-epoxyhexyl methacrylate can be used. For example,
HTR-860P-3 (manufactured by Teikoku Chemical Industry Co., Ltd., epoxy group-containing acrylic rubber, weight average molecular weight 800,00
0) is used. Among these, an epoxy group-containing monomer is preferable in terms of storage stability, and glycidyl methacrylate is more preferable.

The copolymerization ratio of the non-functional monomer to the functional monomer (non-functional monomer / functional monomer) is preferably 90/10 to 9 with the total amount of these being 100 parts by weight.
9.9 / 0.1 parts by weight, more preferably 9 / 0.1 parts by weight.
It is in the range of 3/7 to 99.5 / 0.5, more preferably in the range of 95/5 to 99/1. If the amount of the functional monomer is too large, gelation tends to occur during copolymerization, and if the amount is too small, adhesiveness tends to be insufficient. Examples of the polymerization method for obtaining these acrylic copolymers include bulk polymerization, pearl polymerization, emulsion polymerization, and solution polymerization. The molecular weight of these acrylic copolymers is preferably a weight average molecular weight (Mw) of 1
It is 20,000 to 2,000,000, more preferably 30,000 to 1,500,000, and still more preferably 50,000 to 1,000,000. If the molecular weight is too large, gelation tends to occur during copolymerization, and if it is too small, adhesiveness tends to be insufficient. Tg of -20 ° C to 30 ° C, weight average molecular weight of 1
Acrylic copolymers having 2,000 to 2,000,000 and an epoxy group are preferred.

In the present invention, (3) the amount of the acrylic copolymer having a carboxyl group, a hydroxyl group, an acid anhydride group, an amide group or an epoxy group is based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. It is 50 to 300 parts by weight, preferably 80 to 300 parts by weight. If the amount of the acrylic copolymer is too small, the adhesiveness tends to decrease, and if it is too large, the tackiness tends to be too high to make it difficult to handle.

Further, in the present invention, it is preferable to use (4) a curing accelerator to such an extent that storage stability is not impaired. As the curing accelerator, those usually used for curing an epoxy resin can be used. Specifically, inorganic acids such as hydrochloric acid, organic acids such as acetic acid and oxalic acid, tertiary amines such as triethylamine and benzyldimethylamine, 1-
Benzyl-2-methylimidazole, 2-ethyl-4-
Methylimidazole, 1-cyanoethyl-2-ethyl-
Imidazoles such as 4-methylimidazole, phosphines such as triphenylphosphine, mention may be made of Lewis acid or Lewis acid salts such as BF _3, preferably imidazoles used from the viewpoint of storage stability, etc. and heat resistance Can be
Imidazoles can be easily obtained from the market, for example, 2E4MZ, 1B2MZ, 2E4MZ-C
N, 2PZ-CN and 2PZ-CNS (all manufactured by Shikoku Chemical Industry Co., Ltd.).

The amount of the curing accelerator is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin and the curing agent.
5 parts by weight. If the amount of the curing accelerator is too large, storage stability and adhesion tend to decrease.

Further, in the present invention, (5) a coupling agent may be blended in order to improve the interfacial bonding between different materials. As the coupling agent, a silane coupling agent is preferable. As the silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ
-Mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane and the like.

The above-mentioned silane coupling agent can be easily obtained from the market, for example, NUC A18
7, A-189, A-1160, A-1120 (all manufactured by Nippon Unicar Co., Ltd.), SH6040, SH6062,
SH6020 (all manufactured by Dow Corning Toray Silicone Co., Ltd.).

The amount of the coupling agent is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. If the amount is too small, the adhesion tends not to be sufficiently improved, and if it is too large, the heat resistance tends to decrease.

Further, in the present invention, in order to adsorb ionic impurities and improve insulation reliability during moisture absorption,
(6) An ion scavenger can be blended. As the ion scavenger, a compound known as a copper harm inhibitor, for example, a triazine thiol compound or a bisphenol-based reducing agent for preventing copper from being ionized and melted out can also be blended. As bisphenol-based reducing agents,
2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 4,4'-thio-bis- (3-methyl-6-tert-butylphenol) and the like. A copper damage inhibitor containing a triazine thiol compound as a component is commercially available from Sankyo Pharmaceutical Co., Ltd. under the trade name Disnet DB. In addition, a copper damage inhibitor containing a bisphenol-based reducing agent as a component is available from Yoshitomi Pharmaceutical Co., Ltd. from Yoshinox B
It is marketed under the trade name B.

As the inorganic ion adsorbent, one having a zirconium compound as a component from Toa Gosei Chemical Industry Co., Ltd. is called IX-100, and one having an antimony bismuth compound as a component is IXE-600. Under the trade name of IXE-700 under the trade name of IXE-700. Further, there is a hydrotalcite that is commercially available from Kyowa Chemical Industry under the trade name of DHT-4A.

The compounding amount of these ion scavengers is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. If the amount is too small, the ion-capturing ability tends to be insufficient, and if too large, the heat resistance tends to decrease.

The adhesive composition of the present invention comprises the components (7)
In addition to using the varnish dissolved and dispersed in the solvent,
It is possible to apply a varnish on a substrate, heat it to remove the solvent, and use it as a film. Solvents for varnishing are relatively low-boiling methyl ethyl ketone, acetone,
Methyl isobutyl ketone, 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol,
It is preferable to use 2-methoxyethanol or the like. In addition, a high boiling point solvent may be added for the purpose of improving the coating properties. As the high boiling point solvent, dimethylacetamide,
Dimethylformamide, methylpyrrolidone, cyclohexanone and the like. The production of the varnish is not particularly limited as long as it can dissolve the constituents of the present invention in the above-mentioned solvent, and is carried out using a dissolving tank equipped with a stirrer or the like. Dissolution is usually at room temperature to 150 ° C, preferably at room temperature to 1 ° C.
The reaction is usually performed at a temperature of 20 ° C. for about 1 hour to 50 hours. If the dissolution temperature is too high, epoxy groups etc. will react during dissolution,
It tends to reduce the adhesiveness.

After forming the varnish, it is preferable to remove bubbles in the varnish by vacuum degassing. As the substrate, a polyester film, a polyethylene film, a polypropylene film, a polyimide film, or the like, a film obtained by subjecting them to a release treatment, or the like can be used. The coating method is not particularly limited, and examples thereof include a roll coat, a reverse roll coat, a gravure coat, and a bar coat. An adhesive film having an adhesive layer on both surfaces of a substrate is obtained by applying an adhesive to each surface of the substrate and heating to remove the solvent. Further, it can be obtained by laminating an adhesive layer applied on a heat-resistant film to both surfaces of a substrate by lamination. At this time, it is preferable to perform the lamination at a pressure that does not cause deformation of the adhesive film. When the adhesive layers are formed on both surfaces, the thickness of the adhesive on one surface may be different from the thickness of the adhesive on the other surface.

When the adhesive layer of the adhesive film according to the present invention is formed, the solvent is removed by heating.
The curing reaction of the adhesive composition proceeds and gels. The cured state at that time affects the fluidity of the adhesive, and optimizes adhesiveness and handleability. DSC (differential scanning calorimetry)
The measurement principle is based on the zero-position method of supplying or removing the amount of heat so as to constantly cancel the temperature difference between the standard sample that has no heat generation and heat absorption within the measurement temperature range, and measurement devices are commercially available. Can be measured using it. The reaction of the adhesive composition of the present invention is an exothermic reaction, and when the sample is heated at a constant heating rate, the sample reacts to generate heat.
The calorific value is output to a chart, and a heating curve and an area surrounded by the base line are obtained based on the base line, and this is defined as a calorific value. The heating value is measured from room temperature to 250 ° C. at a heating rate of 10 ° C./min, and the calorific value is determined. Next, the calorific value of the adhesive obtained by applying the composition to the base material and drying the composition is determined as follows. First, the total calorific value of the uncured sample obtained by drying the solvent using a vacuum dryer at 25 ° C. was measured.
(J / g). Next, the calorific value B of the coated and dried sample
Is measured, and the degree of cure C (%) of the sample (state in which heat generation is completed by heating and drying) is given by the following equation (1).

## EQU1 ## C (%) = (A−B) × 100 / A

Regarding the degree of curing of the adhesive film, DSC
It is preferable that the heat generation of 10 to 40% of the calorific value of the pre-curing when measured by using is completed.

When the degree of curing is less than 10%, the network structure is not sufficiently generated, and the adhesiveness to the surface to be adhered in a state where the fluidity is too large tends to lower the adhesiveness. When the degree of curing exceeds 40%, the network structure becomes dense,
Conversely, there is a tendency for the fluidity to be too low and the adhesiveness to decrease.

Further, other components can be mixed and used in the adhesive composition of the present invention to the extent that the effects of the present invention are not impaired. Such components include phenoxy resin, functional group-containing acrylonitrile-butadiene rubber, inorganic filler and the like.

The phenoxy resin can be mixed for the purpose of reducing tackiness in the B stage, imparting flexibility to the cured adhesive, and the like. Phenoxy resins can be easily obtained from the market. For example, phenototes YP-40, YP-50, YP-60 (all manufactured by Toto Kasei Co., Ltd.) and the like are available. The mixing amount of the phenoxy resin is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. If the mixing amount is too large, the heat resistance tends to decrease.

Examples of the acrylonitrile-butadiene rubber containing a functional group include acrylonitrile-butadiene rubber to which a functional group such as a carboxyl group has been added. The purpose is to reduce tackiness and to impart flexibility to the adhesive after curing. Can be mixed. Such a functional group-containing acrylonitrile-butadiene rubber can be easily obtained from the market. For example, PNR-1 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Nipol 1072 (manufactured by Nippon Zeon Co., Ltd.)
Etc. The amount of such functional group-containing acrylonitrile-butadiene rubber is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. If the mixing amount is too large, the heat resistance and the adhesiveness after the PCT treatment tend to decrease.

The inorganic filler can be mixed for the purpose of imparting thermal conductivity, flame retardancy, thixotropy and the like. As inorganic fillers, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate,
Calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, aluminum nitride,
Examples thereof include aluminum borate whiskers, boron nitride, crystalline silica, and silicon carbide.

In order to improve thermal conductivity, alumina,
Aluminum nitride, boron nitride, crystalline silica, amorphous silica, silicon carbide and the like are particularly preferred. Among them, alumina is suitable because it has good heat dissipation and good heat resistance and insulation properties. In addition, crystalline silica or amorphous silica is inferior to alumina in terms of heat resistance, but has less ionic impurities, and therefore has high insulation properties after PCT treatment, and has high copper foil, aluminum wire,
It is suitable because corrosion of an aluminum plate or the like is small. In order to impart flame retardancy, aluminum hydroxide, magnesium hydroxide, antimony oxide and the like are preferable. Furthermore, for the purpose of imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, crystalline silica, amorphous silica, etc. Is preferred. These inorganic fillers are preferably 100 parts by weight or less, more preferably 60 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin and the curing agent.
It is preferable to mix in a range of not more than part by weight. When the mixing amount is too large, the storage elastic modulus of the adhesive tends to increase and the adhesiveness tends to decrease. The adhesive film according to the present invention is bonded to an organic support substrate on which predetermined wiring and external connection terminals are formed to form a semiconductor chip mounting substrate, and a semiconductor device is manufactured using the substrate.

In summary, the adhesive composition of the present invention has the following features. 1) The unreacted epoxy resin component remains in an appropriate amount, and when pressure is applied, the unreacted component oozes out of the gel, so even if a large amount of high molecular weight components and fillers are contained, adhesion occurs. The properties are good. 2) Since the terpene phenol novolak resin has low volatility, it does not contaminate the base material or the semiconductor chip when attaching the adhesive film to the substrate or the semiconductor chip.
Moreover, the adhesiveness at 260 ° C. assuming lead-free solder is good. 3) By using an acrylic copolymer having a functional group specified in the present invention, it is possible to reduce the elastic modulus of the adhesive, and to impart adhesiveness after PCT treatment and electrolytic corrosion resistance. it can. 4) Because high molecular weight components such as acrylic copolymers are gelled, even if pressure is applied when a large number of unreacted components of the epoxy resin remain, even if pressure is applied, the unreacted components flow extremely and a large amount No bleeding occurs and defects such as covering the connection terminals do not occur. 5) In addition to the above effects, the adhesive composition can be imparted with thermal conductivity and flame retardancy. Hereinafter, the adhesive composition according to the present invention, an adhesive film using the same, a semiconductor chip mounting substrate using the adhesive film, and a semiconductor device using the same will be specifically described with reference to Examples.

[0040]

EXAMPLES Example 1 An adhesive film was prepared from the composition shown below. Bisphenol A as epoxy resin
45 parts by weight of a type epoxy resin (epoxy equivalent: 200, trade name of Yuka Shell Epoxy Co., Ltd., using Epicoat 828) and a cresol novolac type epoxy resin (epoxy equivalent: 220, trade name of Sumitomo Chemical Co., Ltd., ESCN0)
No. 01) 15 parts by weight, terpene phenol novolak resin (trade name, manufactured by Yuka Shell Epoxy Co., Ltd., Epicure MP402) as a curing agent for epoxy resin 54
Parts by weight, epoxy group-containing acrylic rubber (weight average molecular weight 800,00
0, trade name, HTR-860P-, manufactured by Teikoku Chemical Industry Co., Ltd.
3) 200 parts by weight, 1-cyanoethyl-2-phenylimidazole as curing accelerator (Shikoku Kasei Kogyo Co., Ltd. trade name, Curesol 2PZ-CN used)
0.5 parts by weight, 2.5 parts by weight of γ-mercaptopropyltrimethoxysilane (trade name, manufactured by Nippon Unicar Co., Ltd., NUC A-189) as a coupling agent, γ-ureidopropyltriethoxysilane (Nippon Unicar 2.5 (trade name, manufactured by NUC A-1160)
To a composition consisting of parts by weight, methyl ethyl ketone 1,25
0 parts by weight were added, mixed with stirring, and degassed under vacuum. The obtained varnish was applied as a substrate onto a release-treated polyethylene terephthalate film having a thickness of 50 μm,
After drying for 0 minutes, an adhesive film in a B-stage state having a film thickness of 75 μm was prepared. The degree of curing of the adhesive in this state was measured using a DSC (trade name: 912 type DSC manufactured by DuPont) (heating rate, 10 ° C./min). As a result, 16% of the total curing calorific value was generated. Was completed.

<Example 2> A terpene phenol novolak resin (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.)
Epicure MP402) 36 parts by weight and bisphenol novolak resin (LF288 manufactured by Dainippon Ink and Chemicals, Inc.)
An adhesive film was produced in the same manner as in Example 1 except that the amount was changed to 13 parts by weight. The degree of cure of the adhesive in this state was measured using a DSC, and as a result, heat generation of 18% of the total curing calorific value was completed.

Example 3 0.5 to 0.1 parts by weight of a curing accelerator, 1-cyanoethyl-2-phenylimidazole (trade name, Curesol 2PZ-CN, manufactured by Shikoku Chemicals Co., Ltd.) An adhesive film was produced in the same manner as in Example 1 except that the adhesive film was changed. The degree of cure of the adhesive in this state was measured using a DSC, and as a result, the state of heat generation of 12% of the total curing calorific value was completed.

Comparative Example 1 An adhesive film was prepared in the same manner as in Example 1 except that the curing agent was changed to 25 parts by weight of bisphenol novolak resin (LF2882 manufactured by Dainippon Ink and Chemicals, Inc.). The degree of cure of the adhesive in this state was measured using a DSC, and as a result, heat generation of 20% of the total curing calorific value was completed.

<Comparative Example 2> The curing agent was changed to 25 parts by weight of bisphenol novolak resin (using LF2882 manufactured by Dainippon Ink and Chemicals, Incorporated), and 0.1% of a curing accelerator was used.
An adhesive film was produced in the same manner as in Example 1 except that the amount was changed to parts by weight. The degree of cure of the adhesive in this state was measured using a DSC, and as a result, 14% of the total curing calorific value was obtained.
% Exotherm. Table 1 shows the above composition and the degree of curing after coating.

[0045]

[Table 1]

Using the obtained adhesive film, the amount of volatile components and the adhesive strength were evaluated. The amount of the volatile component was measured by a weight change after leaving the adhesive cut out in a fixed size in a dryer at 170 ° C. for 1 hour. That is, the weight of the adhesive before the treatment is A (g). Next, assuming that the weight of the adhesive after drying at 170 ° C. for 1 hour is B (g), the volatile component amount C (%) is given by the following equation (2).

C (%) = (A−B) × 100 / A The adhesive strength was measured using a thermocompression bonding machine manufactured by Tester Sangyo Co., Ltd.
Glass plate and polyimide film (Ube Industries, Ltd.)
After the adhesive is sandwiched between IUPLEX 50S) and thermocompression-bonded at a mold temperature of 160 ° C. (both sides), a pressure of 2 MPa and a compression time of 18 seconds, the curing reaction is completed by leaving it at 170 ° C. for 1 hour. Then, the peel strength of the polyimide film at 260 ° C. was measured using a 90 ° peel strength measuring device manufactured by Tester Sangyo Co., Ltd., and the average value of three different samples at the time of preparing the adhesive was less than 20 g / cm. X: within the range of 20 to 50 g / cm, Δ, 50 g / cm
cm or more was rated as ○. Table 2 shows the results.

[0047]

[Table 2]

The adhesives of Examples 1 to 3 were applied on both surfaces of a 25 μm-thick polyimide film (using Ube Industries Upilex SGA-25) as a substrate at a temperature of 85 ° C., a pressure of 2.5 MPa, and a laminating speed of 1.0 m. The adhesive film was bonded using a hot roll laminator under the conditions of / min to prepare an adhesive film having an adhesive layer on both sides of a polyimide film. Using the obtained adhesive film, a semiconductor chip 5 (having a thickness of 150 μm) as shown in FIG. 2 and a semiconductor wiring board (having a thickness of 75 μm) 4 using a 75 μm polyimide film as a base material were bonded together with an adhesive. Semiconductor device samples (with solder balls 8 formed on one side) were prepared, and the contamination, heat resistance, and moisture resistance of the chip and the substrate were evaluated. In FIG. 2, 3 is a wiring, 6 is a semiconductor chip connecting member, and 7 is a sealing material. As a method for evaluating the contamination of the chip and the substrate, 1
Analysis is performed on a 1,000-piece sample in which a semiconductor chip and a wiring board are bonded together with an adhesive at a mold temperature of 80 ° C., and contamination of 10 pieces or more is evaluated as x; The thing of 0 pieces was evaluated as ○. As a method for evaluating heat resistance, a reflow crack resistance and a temperature cycle test were applied. The reflow crack resistance was evaluated by passing the sample through an IR reflow furnace set at a temperature of 260 ° C. at a temperature of 20 ° C. for 20 seconds and cooling it by leaving it at room temperature twice. This was performed by observing peeling and cracking.剥離 indicates that no peeling or cracking occurred, and x indicates that occurred. The temperature cycle test was performed on the sample
The process of leaving in a 5 ° C. atmosphere for 30 minutes and then leaving in a 125 ° C. atmosphere for 30 minutes was measured as one cycle,
The samples that did not break down by 0 cycles were indicated by ○. The moisture resistance was evaluated in a pressure cooker tester for 500 hours (121 ° C., 2 atm, PCT).
This was performed by observing the peeling of the post-adhesion member. When the peeling of the adhesive member was not recognized, it was evaluated as ○, and when peeled, it was evaluated as ×.

Using the adhesives of Comparative Examples 1 and 2, an adhesive film having an adhesive layer on both surfaces of a polyimide film was prepared in the same manner as in Example 4, and the chip and the base material were formed in the same manner as in Example 4. Contamination, heat resistance and moisture resistance were evaluated. Table 3 shows the above results.

[0050]

[Table 3]

[0051]

The adhesive composition of the present invention, the adhesive film using the same, and the semiconductor device using the adhesive film have a low elastic modulus near room temperature. The thermal stress generated at the time of heating and cooling can be relaxed from the difference in thermal expansion coefficient between the two. Further, the adhesive composition of the present invention and the adhesive film using the same, since the high adhesiveness particularly at a high temperature of 260 ℃,
No exfoliation or cracking during reflow is observed, and excellent heat resistance. Further, when the epoxy-containing acrylic copolymer is contained as a low elastic modulus component, the adhesive, the adhesive film and the adhesive film have excellent characteristics with little deterioration when subjected to a moisture resistance test under severe conditions such as PCT treatment, especially when subjected to a moisture resistance test. A semiconductor device using this can be provided. Furthermore, the adhesive composition and the adhesive film using the same according to the present invention have low volatility of the curing agent, so that the chip and the base material are less contaminated, and the reliability of the package can be improved.

[Brief description of the drawings]

FIG. 1 is a sectional view of an adhesive film according to the present invention.

FIG. 2 is a cross-sectional view of a semiconductor device using the adhesive film according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Adhesive 2 Base material 3 Wiring 4 Semiconductor wiring board 5 Semiconductor chip 6 Semiconductor chip connecting member 7 Sealing material 8 Solder ball

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/60 311 H01L 21/60 311S F term (Reference) 4J004 AA10 AA12 AA13 AB01 AB05 CA04 CA06 CB03 EA05 FA05 FA08 4J036 AA01 AA05 AK08 DA02 DA05 FA03 FA10 FA12 FA13 FB03 FB06 JA06 KA01 4J040 DB042 DF042 DF052 EB071 EC071 GA05 GA07 GA11 GA22 HB09 HB19 HC03 HC11 HC22 HC25 HD04 HD25 HD32 HD36 JA02 J1602KA03 PA03 LA16 KK02 KK03

Claims (9)

[Claims] 1. A total of 100 parts by weight of (1) an epoxy resin having two or more epoxy groups in a molecule and (2) a terpene phenol novolak resin having a structural unit represented by the following general formula (I) as a curing agent. Part and (3) carboxyl group, hydroxyl group, acid anhydride group,
Acrylic copolymer having an amide group or an epoxy group 5
An adhesive composition containing 0 to 300 parts by weight. 2. The acrylic copolymer (3) has a glass transition point (Tg) of −20 ° C. to 30 ° C., a weight average molecular weight of 10,000 to 2,000,000, and has an epoxy group. The adhesive composition according to claim 1. (4) a curing accelerator: 0.01 to 10
The adhesive composition according to claim 1, wherein the adhesive composition comprises parts by weight. 4. Coupling agent 0.1 to 1 (5)
The adhesive composition according to any one of claims 1 to 3, wherein 0 part by weight is blended. 5. The (6) ion scavenger 0.01 to 1
The adhesive composition according to any one of claims 1 to 4, wherein 0 part by weight is blended. 6. The method according to claim 1, further comprising (7) a solvent.
5. The adhesive composition according to any one of the above items 5. 7. An adhesive film obtained by forming the adhesive composition according to claim 1 into a film. 8. A semiconductor chip mounting substrate in which the adhesive film according to claim 7 is adhered to an organic support substrate. 9. A semiconductor device using the adhesive film according to claim 8.