JPH11246829A - Double-side adhesive film and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive film having heat, electrolytic corrosion and moisture resistances necessary when a semiconductor chip having large difference of coefficient of thermal expansion is mounted on a printed circuit board, scarcely causing deterioration in carrying out moisture resistant test under severe conditions and excellent in handleability and workability and provide a semiconductor device prepared by using the film. SOLUTION: This both-side adhesive film comprises a core material comprising a heat-resistant film, an adhesive layer comprising an adhesive (A) formed on one side of the core material and an adhesive layer comprising an adhesive (B) formed on the other side of the core material, and the adhesive (A) comprises a thermosetting resin composition in which storage elastic modulus obtained when measured by using a dynamic viscoelasticity-measuring device after curing the composition until curing degree becomes 100% is 10-2000 MPa at 25 deg.C and 3-50 MPa at 260 deg.C and the adhesive (B) comprises a heat-resistant thermoplastic resin in which storage elastic modulus at 25 deg.C obtained when measured by a dynamic viscoelasticity-measuring device is 100-5,000 MPa and glass transition temperature is >=140 deg.C. This semiconductor device is prepared by using the both-side adhesive film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating adhesive film suitably used for bonding a semiconductor chip and a printed wiring board, and a semiconductor device manufactured using the adhesive film.

[0002]

2. Description of the Related Art In recent years, with the development of electronic equipment, the mounting density of electronic components has increased, and bare chip mounting of semiconductors on printed wiring boards and semiconductor packages using organic substrates, which can be expected to be low cost, have been put to practical use. I have.

[0003] Ceramic substrates such as alumina have been widely used as substrates for mounting semiconductor chips. this is,
Since the thermal expansion coefficient of the semiconductor chip is as small as about 4 ppm / ° C., it has been required to use a mounting substrate having a relatively small thermal expansion coefficient in order to secure connection reliability. The main reason was that it was required to use a mounting substrate having a relatively high thermal conductivity in order to easily radiate heat to the outside. Liquid adhesives typified by silver paste are used to mount semiconductor chips on such ceramic substrates, but the silver filler is not dispersed uniformly due to the sedimentation of silver filler. There are problems such as the need to pay attention to stability and the inferior workability of semiconductor chip mounting as compared to LOC and the like.

As means for facilitating the heat generated by the semiconductor chip to be radiated to the outside, a plastic BGA is used.
In such a case, by providing a heat radiating plate such as a copper plate, it is possible to take a better heat countermeasure than a ceramic substrate.

Accordingly, an adhesive film has been developed which can maintain high connection reliability by relaxing thermal stress caused by a difference in thermal expansion coefficient between the semiconductor chip and the mounting substrate, and has excellent workability. Such an adhesive film has a low modulus of elasticity at room temperature, does not transmit thermal stress due to expansion and contraction of the mounting substrate to the semiconductor chip, and has a low temperature from room temperature to the mounting temperature of the semiconductor chip and electronic components. It is required that the thermal expansion coefficient in a wide temperature range is small and no thermal stress is generated.

In the examination as a material related to a printed wiring board, as a material having improved solder heat resistance after absorbing moisture,
JP-A-60-243180 discloses an adhesive containing an acrylic resin, an epoxy resin, a polyisocyanate and an inorganic filler.
There is an acrylic resin, an epoxy resin, and an adhesive containing a primary amine compound having a urethane bond in its molecule and having both ends terminated with a primary amine compound and an inorganic filler, which are disclosed in Japanese Patent Application Laid-Open No. 0-0. However, even when the semiconductor chip is mounted on the printed wiring board using the adhesive as a material related to the printed wiring board, cracks occur during reflow due to a large difference in thermal expansion coefficient between the semiconductor chip and the printed wiring board, Not practical. In addition, there is also a disadvantage that when a humidity resistance test is performed under severe conditions such as a temperature cycle test or a PCT process, the deterioration is large.

[0007] Film adhesives have been conventionally used in flexible printed wiring boards and the like, and systems containing acrylonitrile-butadiene rubber as a main component are often used. However, this type of film adhesive is
There are drawbacks such as a large decrease in adhesive strength after long-time treatment at a high temperature and inferior electric 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.

An adhesive film having a low elastic modulus, which can avoid these problems and can maintain high connection reliability of a semiconductor chip or the like by relaxing thermal stress, has low rigidity even at room temperature. There was a problem in handling and workability that it was not possible.

[0009]

SUMMARY OF THE INVENTION The present invention provides heat resistance, electrolytic corrosion resistance, and moisture resistance necessary for mounting a semiconductor chip having a large difference in thermal expansion coefficient on a printed wiring board such as a glass epoxy board or a flexible board. Adhesive film with low degradation, especially when subjected to a moisture resistance test under severe conditions such as PCT treatment, and excellent in handleability and workability, and a semiconductor device manufactured using this film The purpose is to provide.

[0010]

Means for Solving the Problems The present inventors provide an adhesive layer comprising a thermosetting resin composition having a specific storage elastic modulus on one side of a heat-resistant film and a specific storage elasticity on the other side. Heat-resistant adhesive film formed with an adhesive layer made of a heat-resistant thermoplastic resin having a specific glass transition temperature and a specific rate solves the above problems, and is excellent in heat resistance, corrosion resistance, and moisture resistance,
In addition, they have found that they are excellent in handleability and work, and have reached the present invention.

That is, the present invention relates to a core material comprising a heat-resistant film, an adhesive layer comprising an adhesive (A) formed on one surface of the core material, and an adhesive layer (B) formed on the other surface of the core material. A double-sided adhesive film comprising an adhesive layer consisting of an adhesive (A), wherein the adhesive (A) is cured to a state in which heat generation of 100% of the total curing calorific value as measured by using a DSC has been completed, and the dynamic adhesiveness is obtained. The storage elastic modulus when measured using an elasticity measuring device is 10 to 2,000 MPa at 25 ° C., 2
It is a thermosetting resin composition having a pressure of 3 to 50 MPa at 60 ° C., and the adhesive (B) has a storage elastic modulus at 25 ° C. of 100 to 5 when measured using a dynamic viscoelasticity measuring device.
000 MPa and glass transition temperature of 140 ° C.
An object of the present invention is to provide a double-sided adhesive film which is the above-mentioned heat-resistant thermoplastic resin.

The present invention also provides a semiconductor device manufactured using the double-sided adhesive film of the present invention.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive (A) used in the present invention is cured to a state where heat generation of 100% of the total curing calorific value measured by using a DSC has been completed, and dynamic viscoelasticity measurement is performed. Any thermosetting resin composition having a storage elastic modulus of 10 to 2,000 MPa at 25 ° C. and 3 to 50 MPa at 260 ° C. when measured using an apparatus can be used without particular limitation. Such a thermosetting resin composition is, for example, compatible with (2) epoxy resin (1a) with respect to 100 parts by weight in total of (1) epoxy resin (1a) and curing agent (1b). And a high molecular weight resin having a weight average molecular weight of 30,000 or more
40 parts by weight, containing 2 to 6% by weight of copolymer units derived from (3) glycidyl (meth) acrylate, having a glass transition temperature of -10 ° C or higher and a weight average molecular weight of 800,000.
The above epoxy group-containing acrylic copolymer 100 ~
300 parts by weight, and (4) a thermosetting resin composition containing 0.1 to 5 parts by weight of a curing accelerator optionally blended; and (1) an epoxy resin (1a) and a curing agent (1)
The glass transition temperature including (3) 2 to 6% by weight of copolymerized units derived from glycidyl (meth) acrylate is -10 ° C or more and the weight average molecular weight is 800,000 or more based on 100 parts by weight of the total amount of b). A thermosetting resin composition containing 100 to 300 parts by weight of an epoxy group-containing acrylic copolymer, and (4) 0.1 to 5 parts by weight of a curing accelerator, if necessary. Can be

The epoxy resin (1a) may be any resin as long as it cures and exhibits an adhesive action. Bifunctional or more, preferably having a molecular weight or a weight average molecular weight (polystyrene conversion value, the same applies hereinafter) of less than 5,000, preferably 3,000
Less than zero epoxy resin is used. In particular, it is preferable to use a bisphenol A type or bisphenol F type liquid resin having a weight average molecular weight of 500 or less, since the fluidity during lamination can be improved. Bisphenol A type or bisphenol F type liquid resin having a weight average molecular weight of 500 or less was obtained from Yuka Shell Epoxy Co., Ltd.
7, Epicoat 827, Epicoat 828. In addition, Dow Chemical Japan Co., Ltd. E. FIG. R. 330, D.I. E. FIG. R. 331;
E. FIG. R. 361. Furthermore, YD128, YDF170 from Toto Kasei Co., Ltd.
It is marketed under the trade name.

As the epoxy resin (1a), a trifunctional or higher polyfunctional epoxy resin may be used for the purpose of increasing Tg. Examples of the polyfunctional epoxy resin include a phenol novolak type epoxy resin and a cresol novolak type epoxy resin. Is exemplified. When using a trifunctional or higher polyfunctional epoxy resin, the amount is preferably 10 to 50% by weight of the total amount of the bifunctional epoxy resin and the polyfunctional epoxy resin.

Examples of the phenol novolak type epoxy resin include those commercially available from Nippon Kayaku Co., Ltd. under the trade name EPPN-201. Also,
Examples of the cresol novolak type epoxy resin include ESCN-001, ESCN from Sumitomo Chemical Co., Ltd.
-195 and EOCN1012, EOCN1025, EOCN
A product marketed under the trade name of 1027 is exemplified.

As the curing agent (1b) for the epoxy resin (1a), those usually used as curing agents for the epoxy resin can be used, and amine, polyamide, acid anhydride, polysulfide, boron trifluoride and phenolic Examples thereof include bisphenol A, bisphenol F, bisphenol S, and phenol resins, which are compounds having two or more hydroxyl groups in one molecule. In particular, it is preferable to use a phenol novolak resin, a bisphenol novolak resin, or a cresol novolak resin because of its excellent electric corrosion resistance during moisture absorption. As these resins, for example, those having a weight average molecular weight of 500 to 2,000, particularly 700 to 1,400 are suitably used.

Examples of such particularly preferred curing agents include phenolite LF2882 and phenolite LF2 available from Dainippon Ink and Chemicals, Inc.
822, phenolite TD-2090, phenolite T
D-2149, phenolite VH4150, phenolite VH4170, Plyofen LF2882 (trade name) and the like.

The curing agent (1b) contains a group having a reactivity with an epoxy group, for example, a phenolic hydroxyl group of 0.8 to 1 per mol of epoxy group in the adhesive (A).
It is preferably used in an amount of 2 mol,
More preferably, it is used in an amount of 1.05 mol.

A curing accelerator (4) together with the curing agent (1b)
It is preferable to use As the curing accelerator (4),
It is preferable to use various imidazoles. As imidazole, 2-methylimidazole, 2-ethyl-
4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like.

Examples of commercially available imidazoles include 2E4MZ, 2PZ-CN and 2E4MZ from Shikoku Chemicals.
Examples include those commercially available under the trade name of PZ-CNS.

The amount of the curing accelerator is determined by the amount of the epoxy resin (1a)
And 0.1 part of the total amount of the curing agent (1b) and 100 parts by weight.
It is preferable that the amount be 1 to 5 parts by weight.

Examples of the high molecular weight resin (2) which is compatible with the epoxy resin (1a) and has a weight average molecular weight of 30,000 or more include phenoxy resin, high molecular weight epoxy resin, ultrahigh molecular weight epoxy resin, and highly polar functional group. Group-containing rubbers and functional group-containing reactive rubbers having a large polarity are exemplified. By blending a high molecular weight resin having a weight average molecular weight of 30,000 or more, the tackiness of the adhesive (A) at the B stage can be reduced and the flexibility at the time of curing can be improved. Therefore, the weight average molecular weight of the high molecular weight resin (2) is set to 30,000 or more, preferably 30,000 to 300,000, and more preferably 45,000 to 200,000. Here, “compatible with the epoxy resin (1a)” means a property of forming a homogeneous mixture without being separated from the epoxy resin (1a) after curing and being separated into two or more phases.

Examples of commercially available phenoxy resins include those commercially available from Toto Kasei Co., Ltd. under the trade names such as Phenotote YP-40, Phenotote YP-50, and Phenotote YP-60.

As the high molecular weight epoxy resin, a high molecular weight epoxy resin having a weight average molecular weight of 30,000 to 80,000 is used, and as the ultrahigh molecular weight epoxy resin, one having a weight average molecular weight exceeding 80,000, preferably 80 ,
000 and 200,000 or less (Japanese Patent Publication No. 7-59617, Japanese Patent Publication No. 7-59618).
JP, JP-B7-59619, JP-B7-59
No. 620, Japanese Patent Publication No. 7-64911, Japanese Patent Publication No. 7-64911
All are manufactured by Hitachi Chemical Co., Ltd. and are commercially available.

Examples of the highly polar functional group-containing reactive rubber include acrylonitrile butadiene rubber and acrylic rubber to which a highly polar functional group such as a carboxyl group is added. Commercially available carboxyl group-containing acrylonitrile butadiene rubber includes PNR-1 (trade name) commercially available from Nippon Synthetic Rubber Co., Ltd. and Nipol 1072M commercially available from Zeon Corporation.
(Product name). Commercially available carboxyl group-containing acrylic rubbers include HTR-860P (trade name) commercially available from Teikoku Chemical Industry Co., Ltd.

The amount of the high molecular weight resin (2) compatible with the epoxy resin and having a weight average molecular weight of 30,000 or more is 100 parts by weight of the total amount of the epoxy resin (1a) and the curing agent (1b). The amount is 10 to 40 parts by weight.
If the amount of the high-molecular-weight resin (2) is less than 10 parts by weight, a phase containing an epoxy resin as a main component (hereinafter referred to as an epoxy resin phase) is insufficient in flexibility, tackiness is reduced, and insulation is reduced due to cracks or the like. Tends to be insufficient, and if it exceeds 40 parts by weight, the Tg of the epoxy resin phase may decrease.

The epoxy group-containing acrylic copolymer (3) contains 2 to 6% by weight of copolymerized units derived from glycidyl (meth) acrylate, has a Tg (glass transition temperature) of -10 ° C. or higher, and Weight average molecular weight of 800,0
00 or more. As such an epoxy group-containing acrylic copolymer, HTR-860P-38 (trade name) commercially available from Teikoku Chemical Industry Co., Ltd. can be used. Here, (meth) acrylate means acrylate and / or methacrylate, for example,
Glycidyl (meth) acrylate means glycidyl acrylate and / or glycidyl methacrylate. When the amount of the copolymer unit derived from glycidyl (meth) acrylate in the epoxy group-containing acrylic copolymer is less than 2% by weight, the adhesive strength of the adhesive (A) tends to be insufficient. If the amount is more than 10% by weight, gelling of the epoxy group-containing acrylic copolymer may easily occur. The Tg of the epoxy group-containing acrylic copolymer is -10
When the temperature is lower than 0 ° C., the tackiness of the adhesive film in the B-stage state is increased, and the handling property may be deteriorated. When the weight-average molecular weight of the epoxy group-containing acrylic copolymer is less than 800,000, the strength and flexibility of the adhesive (A) layer are reduced and the tackiness is increased. Strength and handleability may deteriorate.

Epoxy group-containing acrylic copolymer (3)
Preferred examples of the copolymerizable monomer other than glycidyl (meth) acrylate used in the synthesis of acrylonitrile, alkyl (meth) acrylate, and the like. Examples of the alkyl (meth) acrylate include ethyl (meth) acrylate, butyl (meth) acrylate, and the like. When a monomer having a functional group such as a carboxyl group or a hydroxyl group, for example, a carboxylic acid type acrylic acid or a hydroxyl group type hydroxymethyl (meth) acrylate is used, the cross-linking reaction easily proceeds, and the adhesive (A) is in a varnish state. This is not preferable because of problems such as gelation of the polymer and a decrease in adhesive strength due to an increase in the degree of curing in the B-stage state.

The Tg (glass transition temperature) containing 2 to 6% by weight of copolymerized units derived from glycidyl (meth) acrylate is -10 ° C. or more and the weight average molecular weight is 800,0
Specific examples of the epoxy group-containing acrylic copolymer having a molecular weight of 00 or more include (a) acrylonitrile 18 to
40% by weight, (b) 2 to 6% by weight of glycidyl (meth) acrylate as a functional group monomer, and (c) at least one monomer 54 to 80 selected from the group consisting of ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate. Copolymers obtained by copolymerizing by weight% are exemplified. Ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate can be used alone or in combination of two or more, and the mixing ratio is determined in consideration of the Tg of the copolymer. Examples of the polymerization method include pearl polymerization, solution polymerization, and the like, which can be obtained.

Epoxy group-containing acrylic copolymer (3)
Of the epoxy resin (1a) and the curing agent (1b)
Is 100 to 300 parts by weight, preferably 100 to 200 parts by weight, based on 100 parts by weight of the total amount. If the amount of the epoxy group-containing acrylic copolymer is less than 100 parts by weight, the strength of the layer made of the adhesive (A) may decrease or the tackiness may increase.
Since the number of phases of the epoxy group-containing acrylic copolymer (3) as a rubber component in the adhesive (A) increases and the number of epoxy resin phases decreases, the handleability at high temperatures may deteriorate.

The adhesive (A) may contain a coupling agent in order to improve the interfacial bonding between different materials. As the coupling agent, a silane coupling agent is preferable.

Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β-aminoethyl -Γ-aminopropyltrimethoxysilane and the like.

The above-mentioned silane coupling agent is such that γ-glycidoxypropyltrimethoxysilane is NCU A-
187, γ-mercaptopropyltrimethoxysilane is NCU A-189, γ-aminopropyltriethoxysilane is NCU A-1100, γ-ureidopropyltriethoxysilane is NCU A-1160, N-β-
Aminoethyl-γ-aminopropyltrimethoxysilane is commercially available from Nippon Unicar Co., Ltd. under the trade name of NCU A-1120, and can be suitably used.

The amount of the coupling agent is preferably 0.1 to 10% by weight in the adhesive (A) in view of the effect of the addition and the cost.

Further, in order to adsorb ionic impurities and improve insulation reliability at the time of moisture absorption, an ion scavenger may be blended. The amount of the ion scavenger is 5 to 10 in the adhesive (A) depending on the effect of the addition, heat resistance and cost.
% By weight is preferred. 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 ionization and dissolution of copper can also be blended. As the bisphenol-based reducing agent, 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 triazinethiol compound as a component is commercially available from Sankyo Pharmaceutical Co., Ltd. under the trade name Disnet DB. Further, a copper damage inhibitor containing a bisphenol-based reducing agent as a component is commercially available from Yoshitomi Pharmaceutical Co., Ltd. under the trade name Yoshinox BB.

Further, it is necessary to improve the handleability and thermal conductivity of the adhesive (A), impart flame retardancy, adjust the melt viscosity, impart thixotropic properties, and improve the surface hardness. For the purpose, an inorganic filler may be blended in the adhesive (A). The amount of the inorganic filler in the adhesive (A) is preferably 2 to 20% by volume. If the amount of the inorganic filler is less than 2% by volume, the effect of the compounding may be insufficient, and if it exceeds 20% by volume, the adhesive (A)
May cause problems such as an increase in storage modulus, a decrease in adhesiveness, and a decrease in electrical properties due to residual voids.

Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina powder, aluminum nitride powder, aluminum borate whisker, and boron nitride powder. And silica such as crystalline silica and amorphous silica.

In order to improve the thermal conductivity, alumina,
Aluminum nitride, boron nitride, crystalline silica, amorphous silica and the like are preferred.

Of these, alumina is preferred 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 radiation, but has less ionic impurities, so it has high insulation properties during PCT processing, and corrodes copper foil, aluminum wire, aluminum plate, etc. It is suitable in that it has few points.

In order to impart flame retardancy, aluminum hydroxide, magnesium hydroxide and the like are preferable.

For the purpose of adjusting the melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, Silica and amorphous silica are preferred.

For improving the surface hardness, short fiber alumina, aluminum borate whisker and the like are preferable.

The formation of the adhesive layer comprising the adhesive (A) on the heat-resistant film serving as the core material is usually carried out by using the adhesive (A)
Is carried out by applying a varnish in which is dissolved in a solvent and drying by heating.

Solvents for varnishing include relatively low boiling point methyl ethyl ketone, acetone, methyl isobutyl ketone,
It is preferable to use 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol, 2-methoxyethanol and the like. Further, a high boiling point solvent may be added for the purpose of improving the coating properties. Examples of the high boiling point solvent include dimethylacetamide, dimethylformamide, methylpyrrolidone, cyclohexanone and the like.

In consideration of the dispersion of the inorganic filler, the varnish can be produced by a mill, a three-roll mill, a bead mill, or a combination thereof. By mixing the inorganic filler and the low molecular weight substance in advance and then blending the high molecular weight substance, the time required for mixing can be shortened. After the varnish is formed, it is preferable to remove bubbles in the varnish by vacuum degassing.

The adhesive layer made of the adhesive (A) can be obtained by applying a varnish of the adhesive (A) on a heat-resistant film as a core material and drying by heating to remove the solvent. The adhesive layer thus obtained is preferably in a state in which heat generation of 10 to 40% of the total curing calorific value measured using DSC has been completed. Heat is applied to remove the solvent. At this time, the curing reaction of the adhesive (A) proceeds and gels. The curing state at that time affects the fluidity of the adhesive,
Optimize the adhesiveness and handleability. The DSC (differential scanning calorimetry) is based on a zero-position method of supplying or removing a calorific value so as to constantly cancel a temperature difference between a standard sample having no heat generation and heat absorption within a measurement temperature range. The device is commercially available and can be measured using it. The reaction of the resin composition is an exothermic reaction, and when the sample is heated at a constant heating rate, the sample reacts and generates 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 temperature is measured from room temperature to 250 ° C. at a rate of temperature increase of 5 to 10 ° C./min, and the above-mentioned calorific value is obtained. Some of these are performed automatically, and can be easily performed by using them. Next, the calorific value of the adhesive (A) obtained by applying the composition to the heat-resistant film serving as the core material and drying it is determined as follows.

First, the total calorific value of the uncured sample obtained by drying and removing the solvent from the varnish using a vacuum dryer at 25 ° C. was measured.
This is defined as A (J / g) (total curing calorific value). Next,
A varnish is applied to the core material, and the calorific value of a sample of the adhesive layer formed by heating and drying is measured, and this is defined as B (J / g). The degree of cure C (%) of the sample (state in which heat generation has been completed by heating and drying) is given by the following equation 1.

C (%) = (Α−B) × 100 / Α
Formula 1 The adhesive (A) (thermosetting resin composition) was measured by a dynamic viscoelasticity measuring device when it was cured to a state where the heat generation of the total curing calorific value was completed (hereinafter referred to as a curing degree of 100%). Storage elastic modulus is 10 to 2,000 MPa at 25 ° C., preferably 50 to 1,000 MPa, and 3 to 50 MPa at 260 ° C.
Low elastic modulus. The storage elastic modulus was measured by applying a tensile load to the cured adhesive and applying a frequency of 10H.
z, in a temperature-dependent measurement mode in which the temperature is measured from -50 ° C to 300 ° C at a heating rate of 5 to 10 ° C / min. If the storage elastic modulus at 25 ° C. is less than 10 MPa, the adhesive strength at high temperature cannot be maintained, and the storage elastic modulus at 25 ° C. becomes 2,000.
If the pressure exceeds 0 MPa, cracks are generated because the effect of relieving the stress generated during reflow is reduced due to the difference in the thermal expansion coefficient between the semiconductor chip and the printed wiring board. The storage elastic modulus at 260 ° C. is 3 MPa.
If it is less than the above, sufficient adhesive strength cannot be maintained.

The adhesive (A) is compatible with (2) the epoxy resin (1a) and the weight average with respect to 100 parts by weight of the total of (1) the epoxy resin (1a) and the curing agent (1b). High molecular weight resin having a molecular weight of 30,000 or more 1
0-40 parts by weight and (3) 2-6% by weight of copolymer units derived from glycidyl (meth) acrylate having a glass transition temperature of -10 ° C or more and a weight average molecular weight of 800,
Epoxy group-containing acrylic copolymer having a molecular weight of 000 or more
When a thermosetting resin composition containing 100 to 300 parts by weight is used, the epoxy resin (1a) and the high molecular weight resin (2)
Are compatible and uniform, and the epoxy group contained in the epoxy group-containing acrylic copolymer (3) partially reacts with them, and the whole includes unreacted epoxy resin (1a). Since it is crosslinked and gelled, it suppresses the fluidity and does not impair the handleability even when it contains many components having a relatively small molecular weight such as the epoxy resin (1a). In addition, since a large number of unreacted epoxy resins (1a) remain in the gel, if pressure is applied, unreacted components exude from the gel, and even if the whole is gelled, the adhesiveness is reduced. Is reduced.

When the varnish coating of the adhesive (A) is dried, the epoxy group and the epoxy resin (1a) contained in the epoxy group-containing acrylic copolymer (3) react together. The copolymer (3) has a large molecular weight and contains a large number of epoxy groups in one molecular chain, and therefore gels even when the reaction proceeds slightly. Usually DS
10 to 40 of the total curing calorific value as measured using C
%, Ie, gelation occurs in the first half of the A or B stage. Therefore, epoxy resin (1
It is gelled in a state containing a large amount of unreacted components such as a), and the melt viscosity is greatly increased as compared with the case where it is not gelled, and the handling property is not impaired. In addition, when pressure is applied, unreacted components exude from the gel, and therefore, even when gelled, the adhesiveness is hardly reduced. Furthermore, since the adhesive can be formed into a film with a large amount of unreacted components such as epoxy resin, there is an advantage that the life (effective use period) of the adhesive film is extended.

In the conventional epoxy resin-based adhesive, gelation occurs for the first time in the C-stage state from the latter half of the B-stage, and the unreacted components such as the epoxy resin at the stage of the gelation are small, so that the fluidity is low. Even when pressure is applied, the amount of unreacted components oozing out of the gel is small, so that the adhesiveness is reduced.

Although it is not clear how easily the epoxy group contained in the epoxy group-containing acrylic copolymer (3) reacts with the epoxy group of the low molecular weight epoxy resin (1a), at least the same degree of reaction is obtained. It is only necessary that the epoxy group contained in the epoxy group-containing acrylic copolymer (3) react selectively during drying.

In this case, the A, B, and C stages are
Indicates the degree of curing of the adhesive. The A stage is in a state of being almost uncured and not gelling, and is a state in which heat generation of 0 to less than 20% of a total curing calorific value measured by using a DSC has been completed. The B stage is in a state in which curing and gelation have progressed slightly, and in a state in which heat generation of less than 20 to 60% of the total curing calorific value has been completed. The C stage is in a state where the curing has progressed considerably and is in a gelled state, and a state where heating of 60 to 100% of the total curing calorific value has been completed.

Regarding the determination of gelation, the adhesive was immersed in a highly permeable solvent such as THF (tetrahydrofuran) and allowed to stand at 25 ° C. for 20 hours, after which the adhesive was swollen without being completely dissolved. The product was determined to have gelled. In addition, it experimentally determined as follows.

An adhesive (weight W1) is immersed in THF,
After standing at 5 ° C. for 20 hours, undissolved components were filtered through a 200-mesh nylon cloth, and the weight after drying was measured (weight W2). The THF extraction rate (%) was calculated as in the following equation 2. Those with a THF extraction rate of more than 80% by weight were not gelled, and those with 80% by weight or less were judged to be gelled.

[0058]

(Equation 1) In the present invention, by adding an inorganic filler to the adhesive (A), the melt viscosity can be increased and the thixotropic property can be further exhibited, so that the above-mentioned effect can be further enhanced.

Further, in addition to the above-mentioned effects, it is possible to impart properties such as improvement in heat dissipation of the adhesive, imparting flame retardancy to the adhesive, imparting an appropriate viscosity at the temperature at the time of bonding, and improving surface hardness. .

The heat-resistant thermoplastic resin used in the adhesive (B) of the present invention has a storage elastic modulus at 25 ° C. of 100 to 5,000 M when measured using a dynamic viscoelasticity measuring device.
Pa, preferably 400 to 3,500 MPa, and a glass transition temperature (Tg) of 140 ° C. or higher, preferably 14 ° C.
Those having a temperature of 0 to 300 ° C, more preferably 160 to 250 ° C are used. When the storage elastic modulus at 25 ° C. of the heat-resistant thermoplastic resin is out of the range of 100 to 5,000 MPa,
The handling of the adhesive film is extremely poor. When the Tg of the heat-resistant thermoplastic resin is lower than 140 ° C., the film is pressed with a mold from the surface of the adhesive layer made of the adhesive (B), and the adhesive layer made of the adhesive (A) is bonded to the substrate. When doing so, problems such as operability such as adhesion of the adhesive (B) to the mold occur.

Preferred examples of the heat-resistant thermoplastic resin used for the adhesive (B) include aromatic polyamide, aromatic polyimide, aromatic polyamideimide, aromatic polyetheramide, and aromatic polyether having a Tg of 140 ° C. or higher. Resins selected from at least one kind among resins such as imide, aromatic polyether amide imide, aromatic polyester, and aromatic polyether are exemplified.

The adhesive (B) may contain a silicone rubber filler in order to lower the storage modulus.

As the silicone rubber filler, a spherical or amorphous ultrafine silicone rubber elastic material is used. In particular, a silicone having an epoxy group or an amino group on the surface due to its compatibility and bonding with a heat-resistant thermoplastic resin. Rubber fillers are preferred. When a silicone rubber filler having an epoxy group on the surface is used, a heat-resistant thermoplastic resin, and a sealing resin and an epoxy group are used during a heat drying step of forming an adhesive layer on a copper foil or a molding step using a sealing resin. React to form a crosslinked structure having good heat resistance. The average particle size of the silicone rubber filler is 0.1 to 20 μm.
Is preferably, and more preferably 1 to 5 μm.

The amount of the silicone rubber filler is preferably from 10 to 80% by weight based on the weight of the heat-resistant thermoplastic resin.
20-40% by weight is more preferred. When the amount of the silicone rubber filler exceeds 80% by weight, the adhesive strength of the adhesive layer is reduced. If the content is less than 10% by weight, the insulating property and the reflow resistance may decrease.

The adhesive layer composed of the adhesive (B) is obtained by applying a varnish obtained by dissolving the adhesive (B) in a solvent on a heat-resistant film serving as a core material, and drying by heating to remove the solvent. Can be

The organic solvent is not particularly limited, but may be one which dissolves the above-mentioned heat-resistant resin, for example,
Examples include polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, m-cresol, pyridine, cyclohexanone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, and dioxane.

When the silicone rubber filler is mixed with the adhesive (B), the method of dispersing the silicone rubber filler is as follows.
Although not particularly limited, it can be carried out by using a mill, a three-roll mill, a planetary mixer, or a combination thereof.

The adhesive layer composed of the adhesive (B) obtained by coating and drying the varnish on the heat-resistant film preferably contains 0.5 to 10% by weight of an organic solvent.
More preferably, the content is 5% by weight. By containing the organic solvent in an amount of 0.5 to 10% by weight, bonding at a low temperature becomes possible even when a heat-resistant thermoplastic resin having a high Tg is used. However, if the organic solvent content is less than 0.5% by weight,
Since the bonding temperature of the heat-resistant thermoplastic resin does not decrease and the bonding is performed at a high temperature when bonding the adhesive layer made of the adhesive (B), it is considered that thermal stress applied to the adherend becomes a problem. On the other hand, if the content of the organic solvent exceeds 10% by weight, a large amount of the solvent is vaporized at the reflow temperature during mounting, the internal pressure becomes high, and problems such as cracks in the sealing resin occur.

The method for forming an adhesive layer containing an organic solvent on the surface of the core material is as follows. A varnish obtained by dissolving a heat-resistant thermoplastic resin in the above-mentioned organic solvent is applied to the surface of the core material, and the amount of the solvent is 0.5%. It can be easily obtained by a method of drying so as to be 10 to 10% by weight.

Further, a crosslinking agent can be added to the adhesive (B). The crosslinking agent is not particularly limited as long as it is a compound capable of crosslinking the heat-resistant thermoplastic resin by heat. Examples thereof include an amino resin, a phenol resin, a urethane resin, an acid anhydride, and a silane compound. . Examples of the silane compound include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane,
Aminosilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, Silane coupling agents such as vinyltrimethoxysilane, and titanate-based coupling agents such as isopropyltriisostearoyl titanate, isopropyltrioctanoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, and isopropyl tris (dioctyl pyrophosphate) titanate; and Aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate are exemplified. In the adhesive (B),
When additives such as a cross-linking agent and a filler are added, the adhesion to the substrate and the adherend is improved, and the reflow resistance is improved. The amount of the crosslinking agent is preferably 0.5 to 20% by weight, more preferably 2 to 10% by weight, based on the total weight of both the heat-resistant thermoplastic resin and the crosslinking agent.

When the amount of the crosslinking agent exceeds 20% by weight, heat resistance and adhesiveness decrease, and contamination of the adherend by outgassing becomes a problem.

The heat-resistant film used as the core material in the three-layered double-sided adhesive film of the present invention is preferably a film using a polymer having a glass transition temperature Tg of 200 ° C. or higher or a liquid crystal polymer, and is preferably made of polyamide or polyimide. Polyamide imide, polyether amide, polyether imide, polyether amide imide, polyether sulfone or wholly aromatic polyester is used. If a heat-resistant film having a Tg of less than 200 ° C. is used as the core material, plastic deformation may occur at a high temperature such as during solder reflow, which is not preferable.

The thickness of the core material is preferably 5 to 200 μm, but is not particularly limited.

In the present invention, the adhesive layer composed of the adhesive (A) and the adhesive layer composed of the adhesive (B) formed on the surface of the core material are obtained by dissolving or dispersing the components of each adhesive in a solvent. Varnish, and can be prepared by coating on a heat-resistant film serving as a core material, heating and removing the solvent, and forming three layers by forming an adhesive layer on one surface of the heat-resistant film serving as a core material, respectively. A double-sided adhesive film having a structure can be obtained. At this time, an adhesive layer made of the adhesive (B) is first formed on one side of the core material to form a one-sided adhesive film, and then the other side of the uncoated surface is coated with the adhesive (A). Is preferred.

The thickness of the adhesive layer made of the adhesive (A) is 2
To 150 μm is preferred. When the thickness is less than 2 μm, the adhesiveness and the thermal stress buffering effect tend to be inferior. The thickness of the adhesive layer made of the adhesive (B) is 2 to 1
50 μm is preferable, and if it is thinner than 2 μm, adhesion and productivity are poor, and if it exceeds 150 μm, it is not economical.
It is not particularly limited to the above range.

Although the coating method is not particularly limited,
For example, a roll coat, a reverse roll coat, a gravure coat, a bar coat and the like can be mentioned.

The double-sided adhesive film of the present invention is cured by curing as a material of one adhesive layer of the double-sided adhesive film to a state where heat generation of 100% of the total curing calorific value measured by using a DSC is completed. Storage elastic modulus when measured using a viscoelasticity measuring device is 10 to 2,000 M at 25 ° C.
The use of a thermosetting resin composition as low as 3 to 50 MPa at Pa and 260 ° C. has an effect of reducing the stress generated due to the difference in the thermal expansion coefficient of the adherend with the adhesive layer.

Further, by using a heat-resistant film as a core material, the modulus of elasticity at around room temperature becomes higher than that of a single-layer film composed of one adhesive layer, whereby
The problem of film elongation during film processing and transport is eliminated, and workability is improved.

Further, by using a heat-resistant thermoplastic resin having no tackiness for the adhesive (B), when the surface of the adhesive (A) having tackiness is adhered to the substrate at a predetermined temperature,
The adhesive (B) is pressed with a mold from the surface. At this time, the adhesive (B) does not stick to the mold and can be adhered with good workability.

In the present invention, the problems in handling and workability due to a decrease in rigidity of the conventional low elastic modulus adhesive film have been solved by the following method.

1) By adopting a three-layer structure in which a heat-resistant film is disposed on a core material, a low-modulus adhesive can be easily handled in a film form.

2) By using the heat-resistant film as the core material specified in the present invention, plastic deformation of the adhesive film during reflow can be suppressed.

3) By using a heat-resistant thermoplastic resin on one side of the adhesive film having a three-layer structure, it is possible to perform a work of attaching to a substrate with good workability.

According to the present invention, a semiconductor device having good reliability can be supplied by using the above-mentioned adhesive film.

The structure of the semiconductor device of the present invention is not particularly limited as long as the double-sided adhesive film of the present invention is used for bonding components in the semiconductor device. In the semiconductor device of the present invention, the double-sided adhesive film of the present invention is generally suitably used for bonding a semiconductor chip to a printed wiring board using a glass epoxy board or a flexible board, or bonding printed wiring boards. .

Hereinafter, the present invention will be described in more detail with reference to examples.

[0087]

Example 1 In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a condenser tube, under nitrogen, 205 g (0.5 g) of 2,2-bis [4 (4-aminophenoxy) phenyl] propane was added. Mol), 69.6 g (1.2 mol) of propylene oxide
And dissolved in 1,200 g of N-methyl-2-pyrrolidone. The solution was cooled to −5 ° C. and at this temperature 100.5 g (0.495 mol) of isophthalic chloride were added so that the temperature did not exceed 20 ° C. Thereafter, stirring was continued at room temperature for 3 hours. The obtained reaction solution was put into methanol to isolate the polymer. After drying, it is dissolved in dimethylformamide, and this is poured into methanol,
After drying under reduced pressure, a purified aromatic polyamide powder was obtained.
40 g of the obtained polyamide powder was dissolved in 140 g of N-methyl-2-pyrrolidone and 60 g of butyl cellosolve, and a silicone rubber filler (Trefle E-601 manufactured by Dow Corning Toray) having an average particle size of 5 having an epoxy group on the surface was used.
20 g of a silicone rubber filler (μm) was added and mixed with a three-roll mill to obtain a varnish (B). The storage elastic modulus of the aromatic polyamide at 25 ° C. was 2,800 MPa.
a. This varnish is used as an adhesive (B) to a thickness of 5
It is coated on a UPILEX S (product name, polyimi resin film, manufactured by Ube Industries, Ltd.) which has been subjected to a surface treatment by a chemical treatment of 0 μm, and is coated at 100 ° C. for 6 minutes, and then 160
The film was dried at 6 ° C. for 6 minutes to prepare a film having an adhesive (B) on one side. The glass transition temperature of the adhesive was 230 ° C. when measured.

Next, a bisphenol A type epoxy resin (epoxy equivalent: 200, epoxy coat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) was used as an epoxy resin on the surface of the single-sided adhesive film on which the adhesive of the polyimide film was not applied. 30 parts by weight, 10 parts by weight of cresol novolak type epoxy resin (epoxy equivalent: 220, ESCN001 manufactured by Sumitomo Chemical Co., Ltd.), phenol novolak resin (Pryofen manufactured by Dainippon Ink and Chemicals, Inc.) as a curing agent for the epoxy resin LF288
2) 25 parts by weight, a phenoxy resin (weight average molecular weight 50,000, phenothoto YP-50 manufactured by Toto Kasei Co., Ltd.) as a high molecular weight resin having a weight average molecular weight of 30,000 or more, which is compatible with the epoxy resin. Use) 1
0 parts by weight of an epoxy group-containing acrylic rubber (molecular weight: 1,000,000) as an epoxy group-containing acrylic copolymer
0, 100 parts by weight of HTR-860P-3 manufactured by Teikoku Chemical Industry Co., Ltd., and a curing accelerator (2
0.5 parts by weight of PZ-CN) and γ-glycidoxypropyltrimethoxysilane as a silane coupling agent (using NUC A-187 manufactured by Nippon Unicar Co., Ltd.)
A varnish (A) obtained by adding methyl ethyl ketone to a resin composition consisting of 5 parts by weight, stirring and mixing, and degassing under vacuum.
And dried by heating at 140 ° C. for 5 minutes.
An adhesive layer made of the adhesive (A) in the B-stage state of μm was formed to prepare a double-sided adhesive film having a three-layer structure.

The degree of curing of the adhesive (A) of this double-sided adhesive film was measured using a DSC (912 type DS manufactured by DuPont).
C) as a result of measurement (heating rate, 10 ° C./min)
Heat generation of 15% of the total curing calorific value was completed. Also, an adhesive (weight W1) is immersed in THF,
After standing for 0 hours, the undissolved matter was filtered through a 200-mesh nylon cloth, and the weight after drying was measured (weight W
2) Then, the THF extraction rate (= (W1−W2) × 100 / W)
When 1) was obtained, the THF extraction ratio was 35% by weight. Further, the storage elastic modulus of the cured adhesive (curing degree: 100%) was measured using a dynamic viscoelasticity measuring device, and as a result,
It was 360 MPa at 5 ° C. and 4 MPa at 260 ° C.

The solvent content of the adhesive layer composed of the adhesive (B) of this double-sided adhesive film was 3% by weight.

Example 2 The phenoxy resin used in Example 1 was replaced with a carboxyl group-containing acrylonitrile-butadiene rubber (weight average molecular weight 4).
A double-sided adhesive film having a three-layer structure was prepared in the same manner as in Example 1, except that the P.R. The degree of curing of the layer of the adhesive film made of the adhesive (A) was measured using a DSC, and as a result, heat generation of 20% of the total curing calorific value was completed. The THF extraction rate was 35% by weight. Further, the storage elastic modulus of the cured adhesive (curing degree: 100%) was measured using a dynamic viscoelasticity measuring device, and as a result,
It was 300 MPa at 5 ° C. and 3 MPa at 260 ° C. The thickness of the layer made of the adhesive (A) of this double-sided adhesive film was 50 μm, and the thickness of the layer made of the adhesive (B) was 30 μm. The solvent content of the adhesive layer composed of the adhesive (B) of the double-sided adhesive film was 3% by weight.

Comparative Example 1 The varnish of the adhesive (A) used in Example 1 was 50 μm thick.
On a polyethylene terephthalate film of
The film was heated and dried at 40 ° C. for 5 minutes to form a coating film in a B-stage state having a thickness of 150 μm, thereby producing an adhesive film using no core material. The degree of cure of the adhesive film was a state where heat generation of 15% of the total curing calorific value was completed, and the THF extraction rate was 35% by weight. The storage elastic modulus of this adhesive film at a curing degree of 100% is 360 at 25 ° C.
Mpa was 4 MPa at 260 ° C.

Comparative Example 2 The same procedure as in Example 1 was repeated except that the polyimide film used as the core heat-resistant film in Example 1 was changed to a polypropylene film having a glass transition temperature of 120 ° C. An adhesive film was produced. The degree of cure of the adhesive (A) of this adhesive film is 15% of the total curing calorific value.
% Heat generation was completed, and the THF extraction rate was 35% by weight. The storage elastic modulus at a curing degree of 100% was 360 MPa at 25 ° C. and 4 MPa at 260 ° C. The thickness of the layer made of the adhesive (A) of this double-sided adhesive film was 50 μm, and the thickness of the layer made of the adhesive (B) was 3 μm.
It was 0 μm. The solvent content of the adhesive layer composed of the adhesive (B) of the double-sided adhesive film was 4% by weight.

Comparative Example 3 A double-sided adhesive film having a three-layer structure was prepared in the same manner as in Example 1 except that the epoxy group-containing acrylic copolymer of Example 1 was changed to a phenoxy resin (trade name: PNR-1). Produced. The curing degree of the adhesive (A) of this double-sided adhesive film is
This is a state in which heat generation of 20% of the total curing calorific value has been completed.
The F extraction rate was 90% by weight. In addition, curing degree 100
% Is 3,400 MPa at 25 ° C.,
It was 3 MPa at 260 ° C. The thickness of the layer made of the adhesive (A) of this double-sided adhesive film was 50 μm, and the thickness of the layer made of the adhesive (B) was 30 μm. The solvent content of the adhesive layer composed of the adhesive (B) of the double-sided adhesive film was 4% by weight.

Comparative Example 4 An adhesive layer composed of the adhesive (A) on both sides in the same manner as in Example 1 except that the adhesive (A) was used instead of the varnish of the adhesive (B) of Example 1. Was formed to obtain a double-sided adhesive film.

The degree of cure of the adhesive (A) of this double-sided adhesive film was in a state where heat generation of 15% of the total curing calorific value was finished on both sides, and the THF extraction rate was 35% by weight. The storage elastic modulus at a curing degree of 100% is 2 on both sides.
It was 360 MPa at 5 ° C. and 3 MPa at 260 ° C.

With respect to the adhesive films obtained in Examples 1 and 2 and Comparative Examples 1 to 4, heat resistance, electrolytic corrosion resistance and moisture resistance were examined. As a heat resistance evaluation method, a reflow crack resistance and a temperature cycle test of a sample in which a semiconductor chip and a printed wiring board were bonded with an adhesive film were applied. At this time,
In the double-sided adhesive film produced using the adhesive (A) and the adhesive (B), the adhesive (A) side is adhered to the printed wiring board side under the conditions of a pressure of 4 kg / cm ² , a temperature of 140 ° C., and a time of 5 seconds. After the application, the adhesive (B) side was attached to the semiconductor chip side under the conditions of a pressure of 4 kg / cm ² , a temperature of 300 ° C., and a time of 1 second.

The reflow crack resistance was evaluated by passing the sample through an IR reflow furnace set at a maximum temperature of the sample surface of 240 ° C. so as to maintain this temperature for 20 seconds, and cooling the sample by leaving it at room temperature. The observation was carried out by observing cracks in the sample which was repeated twice. Those with no cracks were evaluated as good, and those with cracks were evaluated as poor.

In the temperature cycle test, the sample was subjected to -55 ° C.
Leave it in the atmosphere for 30 minutes, and then
The number of cycles up to the occurrence of destruction is shown assuming that the step of leaving for 0 minutes is one cycle.

For the evaluation of the corrosion resistance, a sample was prepared in which a comb pattern of line / space = 75/75 μm was formed on an FR-4 substrate, and the adhesive (A) side of the adhesive film was laminated thereon. And 85 ° C / 85% RH / DC6
The measurement was performed by measuring the insulation resistance value after 1,000 hours under the condition of V application. Those having an insulation resistance value of 109Ω or more were evaluated as good, and those having an insulation resistance of less than 109Ω were evaluated as defective.

The moisture resistance was evaluated by treating the sample for heat resistance in a pressure cooker tester for 96 hours (PCT treatment, conditions: 121 ° C., 2 atm), and observing peeling and discoloration of the adhesive film. . A sample in which no peeling or discoloration of the adhesive film was observed was regarded as good, and a sample in which peeling or discoloration was observed was regarded as bad. Table 1 shows the results.

[0102]

[Table 1] Examples 1 and 2 are both three-layered double-sided adhesive films using a heat-resistant film for the core material, and the adhesive (A)
The adhesive layer consisting of an epoxy resin and a curing agent for the adhesive component, an epoxy-containing acrylic copolymer in addition to the high-molecular-weight resin compatible with the epoxy resin, at 25 ° C. The storage elastic modulus at 260 ° C. is shown. These were excellent in handleability and sticking workability, and good in reflow crack resistance, temperature cycle test, electrolytic corrosion resistance, and PCT resistance.

Comparative Example 1 was inferior in handleability because it was not a three-layer double-sided adhesive film using a heat-resistant film for the core material specified in the present invention but a single-layer double-sided adhesive film. In addition, when sticking to a printed wiring board, a phenomenon of sticking to a mold was observed, and a protective film was required, resulting in poor workability. Comparative Example 2 was inferior in reflow resistance and temperature cycle test results because a polypropylene film which was not a heat-resistant film was used as the core material. In Comparative Example 3, the layer of the cured product of the adhesive was defined as 2
It showed a high value exceeding the storage modulus at 5 ° C., and was inferior to the reflow crack resistance and the results of the temperature cycle test. Comparative Example 4 is a three-layer film in which an adhesive layer composed of the adhesive (A) specified in the present invention is formed on both sides of a core material, and a phenomenon of sticking to a mold when sticking to a printed wiring board. And required a protective film, resulting in poor workability.

[0104]

As described above, the double-sided adhesive film having a three-layer structure of the present invention is excellent in handleability and bonding workability, and is also a rigid printed wiring board represented by a glass epoxy substrate or a polyimide substrate. Further, it is possible to alleviate the thermal stress at the time of heating and cooling caused by the difference in the coefficient of thermal expansion when the semiconductor chip is mounted on the flexible printed wiring board. Therefore, generation of cracks during reflow is not recognized, and the heat resistance is excellent. In addition, it is possible to provide an adhesive material having excellent characteristics with little deterioration when subjected to a moisture resistance test under severe conditions such as electric corrosion resistance and moisture resistance, especially PCT treatment.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hiroshi Kirihara 14 Goi-minamikaigan, Ichihara-shi, Chiba Hitachi Chemical Industry Co., Ltd. Inside the Shimodate Research Laboratory

Claims (16)

[Claims] 1. A core material comprising a heat-resistant film, an adhesive layer comprising an adhesive (A) formed on one surface of the core material, and an adhesive (B) formed on the other surface of the core material. A dynamic viscoelasticity measuring apparatus comprising a double-sided adhesive film comprising an adhesive layer, wherein the adhesive (A) is cured to a state in which heat generation of 100% of the total curing calorific value when measured using DSC has been completed. Storage elastic modulus is 25 ° C when measured using
10 to 2,000 MPa at 260 ° C.
An adhesive (B) having a storage elastic modulus at 25 ° C. of 100 to 5,000 MPa when measured using a dynamic viscoelasticity measuring device, and And a double-sided adhesive film which is a heat-resistant thermoplastic resin having a glass transition temperature of 140 ° C. or higher. 2. The double-sided adhesive film according to claim 1, wherein the adhesive (A) has been heated to 10 to 40% of the total curing calorific value measured by DSC. 3. The double-sided adhesive film according to claim 1, wherein the heat-resistant film used for the core material has a glass transition temperature of 200 ° C. or higher. 4. The glass transition temperature used for the core material is 200.
4. The double-sided film according to claim 3, wherein the heat-resistant film at a temperature of not less than ° C is selected from the group consisting of polyamide, polyimide, polyamideimide, polyetheramide, polyetherimide, polyetheramideimide, polyethersulfone and wholly aromatic polyester. Adhesive film. 5. The double-sided adhesive film according to claim 1, wherein the heat-resistant film used for the core material is a liquid crystal polymer. 6. The adhesive (A) is based on 100 parts by weight of (1) epoxy resin (1a) having a weight average molecular weight of less than 5,000 and curing agent (1b) thereof, and (2) epoxy resin (1a) is compatible and has a weight average molecular weight of 3
High molecular weight resin of 000 to 300,000 10 to 40
The glass transition temperature containing 2 to 6% by weight of a copolymer unit derived from (3) glycidyl (meth) acrylate is −
An epoxy group-containing acrylic copolymer having a weight average molecular weight of at least 10 ° C. and 800,000 or more.
A thermosetting resin composition containing 0 parts by weight and (4) 0.1 to 5 parts by weight of a curing accelerator, wherein the adhesive (B) is made of an aromatic polyamide, an aromatic polyimide, an aromatic polyamideimide, or an aromatic polyamide. The double-sided adhesive film according to claim 1, wherein the double-sided adhesive film is at least one heat-resistant thermoplastic resin selected from the group consisting of aromatic polyetheramide, aromatic polyetherimide, and aromatic polyetheramideimide. 7. The adhesive (A) is based on (1) 100 parts by weight of the total amount of the epoxy resin (1a) and the phenol resin (1b ′) having a weight average molecular weight of less than 5,000.
(2 ′) 10 to 40 parts by weight of a phenoxy resin, (3) copolymerized unit 2 derived from glycidyl (meth) acrylate 2
100 to 300 parts by weight of an epoxy group-containing acrylic copolymer containing 6% by weight and having a glass transition temperature of −10 ° C. or more and a weight average molecular weight of 800,000 or more, and (4) a curing accelerator of 0.1 to 5 A thermosetting resin composition containing parts by weight, wherein the adhesive (B) is an aromatic polyamide, an aromatic polyimide, an aromatic polyamideimide, an aromatic polyetheramide, an aromatic polyetherimide, and an aromatic polyether. 2. A heat-resistant thermoplastic resin selected from the group consisting of amide imides.
The double-sided adhesive film as described. 8. The adhesive (A) may contain (3) glycidyl (1) based on a total of 100 parts by weight of the epoxy resin (1a) having a weight average molecular weight of less than 5,000 and the curing agent (1b) thereof. Copolymerized units 2 to 6 derived from (meth) acrylate
(4) an epoxy group-containing acrylic copolymer having a glass transition temperature of not less than -10 ° C and a weight average molecular weight of not less than 800,000 including 100% by weight, and
A thermosetting resin composition containing 0.1 to 5 parts by weight of a curing accelerator, wherein an adhesive (B) is an aromatic polyamide, an aromatic polyimide, an aromatic polyamideimide, an aromatic polyetheramide, or an aromatic The double-sided adhesive film according to claim 1, which is at least one heat-resistant thermoplastic resin selected from the group consisting of polyetherimide and aromatic polyetheramideimide. 9. The adhesive (A) may contain (1) an epoxy resin (1a) having a weight-average molecular weight of less than 5,000 and a phenol resin (1b ′) in a total amount of 100 parts by weight,
100 to 300 weight% of an epoxy group-containing acrylic copolymer containing 2 to 6 weight% of copolymerized units derived from glycidyl (meth) acrylate, having a glass transition temperature of -10 ° C or more and a weight average molecular weight of 800,000 or more. And (4) a thermosetting resin composition containing 0.1 to 5 parts by weight of a curing accelerator, wherein the adhesive (B) is composed of an aromatic polyamide, an aromatic polyimide, an aromatic polyamideimide, or an aromatic polyamide. 2. A heat-resistant thermoplastic resin selected from the group consisting of ether amides, aromatic polyether imides and aromatic polyether amide imides.
The double-sided adhesive film as described. 10. The double-sided adhesive film according to claim 6, wherein the adhesive (A) contains 2 to 20% by volume of an inorganic filler. 11. The double-sided adhesive film according to claim 10, wherein the inorganic filler is alumina. 12. The method according to claim 1, wherein the inorganic filler is silica.
0 double-sided adhesive film. 13. The adhesive (A) contains 0.1 to 10% by weight.
The double-sided adhesive film according to any one of claims 6 to 12, further comprising a coupling agent. 14. The adhesive (B) may contain a silicone rubber filler having an epoxy group or an amino group on its surface.
The double-sided adhesive film according to any one of claims 1 to 13, comprising 80% by weight and 0.5 to 10% by weight of an organic solvent. 15. The double-sided adhesive film according to any one of claims 6 to 14, wherein the adhesive (A) has been heated to 10 to 40% of the total curing calorific value when measured using DSC. . 16. A semiconductor device manufactured using the double-sided adhesive film according to claim 1.