JP2003060127A - Semiconductor device, substrate for mounting semiconductor chip, manufacturing method for them, adhesive agent and double-sided adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve resistance to heat cycle after mounting in a semiconductor device and resistance to moisture absorption reflow. SOLUTION: An adhesive agent which is used, when a semiconductor chip is mounted on an organic support substrate, and whose storage elastic modulus at 25 deg.C measured with a dynamic viscoelestic measuring instrument is 10-2,000 MPa and further the storage elastic modulus at 260 deg.C is 3-50 MPa, a double- sided adhesive film, the semiconductor device, a semiconductor chip mounted substrate using the adhesive agent, and a method for manufacturing them are provided.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to a semiconductor device, a method for manufacturing the same, a semiconductor chip mounting substrate suitably used for manufacturing the semiconductor device, a method for manufacturing the same, an adhesive and a double-sided adhesive film.

2. Description of the Related Art In recent years, along with the trend toward miniaturization of electronic equipment and high frequency operation, it is required that semiconductor packages mounted on the electronic equipment be mounted on a substrate at a high density.
As the size and weight are getting smaller, the external terminals are arranged in an area array at the bottom of the package in a micro BGA (ball grid array) or CSP (chip size package).
The development of a small package called a.

In these packages, a chip is mounted via an insulating adhesive on an organic substrate such as a glass epoxy substrate having a two-layer wiring structure or a polyimide substrate having a one-layer wiring structure, and terminals and wiring on the chip side. The board-side terminals are connected by wire bonding or TAB (Tape Automated Bonding) inner bonding method, and the connection portion and the chip upper surface portion or end surface portion are sealed with an epoxy-based sealing material or an epoxy-based liquid sealing material. A structure in which metal terminals such as solder balls are arranged in an area array on the back surface of the wiring board is adopted. Then, a method of mounting a plurality of these packages on a substrate of an electronic device by a solder reflow method at a high density and in a batch is being adopted.

However, as an example of an insulating adhesive used for these packages, a liquid epoxy die bond material having a storage elastic modulus at 25 ° C. of 3000 MPa or more measured by a dynamic viscoelastic device is used. Solder ball connection part (secondary side) after mounting the package on the board
The connection reliability was poor and the temperature cycle resistance was poor.

Further, in another case, a liquid silicon elastomer having a storage elastic modulus at 25 ° C. of 10 MPa or less has been proposed as an insulating adhesive, and the above-mentioned wiring board is excellent in temperature cycle resistance. There is a problem that the adhesiveness to the surface at high temperature is poor and the moisture absorption reflow resistance is poor.

In particular, regarding the reflow resistance, in both cases, voids are easily caught in the process of applying the liquid insulating adhesive to the organic substrate, and the voids become the starting points.
During the hygroscopic reflow, a defective mode in which cracks propagate and the organic substrate swells was observed.

Further, with the development of electronic equipment, the mounting density of electronic parts is increasing, and bare chip mounting of semiconductors on a printed wiring board, which is expected to be low in cost, has been promoted.

Ceramic substrates such as alumina have been often used as substrates for mounting semiconductor chips. this is,
Since the thermal expansion coefficient of the semiconductor chip is as low as about 4 ppm / ° C., it was required to use a mounting board with a relatively small thermal expansion coefficient in order to secure the connection reliability. The main reason was that it was required to use a mounting board having a relatively high thermal conductivity in order to facilitate heat dissipation to the outside. A liquid adhesive represented by a silver paste is used for mounting a semiconductor chip on such a ceramic substrate.

Film adhesives are used in flexible printed wiring boards and the like, and systems based on acrylonitrile butadiene rubber are often used.

In the examination as a printed wiring board-related material, it is found that the solder heat resistance after absorbing moisture is improved.
There is an adhesive containing an acrylic resin, an epoxy resin, a polyisocyanate and an inorganic filler disclosed in JP-A-60-243180, and JP-A-61-1386.
No. 80, acrylic resin, epoxy resin,
There is an adhesive containing a primary amine compound having an urethane bond in its molecule at both ends and an inorganic filler.
(Pressure cooker test) When a moisture resistance test was conducted under severe conditions such as treatment, deterioration was large and insufficient.

When a silver paste adhesive is used for mounting a semiconductor chip on a ceramic substrate, the dispersion of the silver filler is not uniform because of the sedimentation of the silver filler, and the storage stability of the paste must be taken into consideration. There is a problem that workability is inferior to that of LOC (lead-on-chip).

As the film adhesive, a system containing acrylonitrile butadiene rubber as a main component is often used, but the adhesive strength after treatment for a long time at a high temperature is largely reduced and the electrolytic corrosion resistance is poor. There were drawbacks such as. In particular, P used for reliability evaluation of semiconductor-related parts
When the humidity resistance test was performed under severe conditions such as CT treatment, the deterioration was large.

In Japanese Patent Application Laid-Open No. 60-243180 and Japanese Patent Application Laid-Open No. 61-138680, PCT
When a moisture resistance test was conducted under severe conditions such as treatment, the deterioration was large and insufficient.

When a semiconductor chip is mounted on a printed wiring board by using an adhesive as a material related to the printed wiring board, a large difference in thermal expansion coefficient between the semiconductor chip and the printed wiring board causes cracks during reflow. Could not be used for. Further, when the humidity resistance test was conducted under severe conditions such as a temperature cycle test and a PCT treatment, the deterioration was large, and it could not be used. DISCLOSURE OF THE INVENTION The present invention has 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 substrate or a flexible substrate, and particularly, Provided are an adhesive agent, an adhesive film, and a semiconductor device in which a semiconductor chip and a wiring board are adhered using the adhesive film, which is less likely to deteriorate when subjected to a moisture resistance test under severe conditions such as a PCT treatment. is there.

Further, according to the present invention, in a semiconductor device in which a semiconductor chip is mounted on an organic support substrate via an adhesive and external terminals are arranged in an area array on the back surface of the substrate, the temperature cycle resistance after mounting is improved. In addition, a semiconductor device having improved moisture absorption reflow resistance, a method for manufacturing the same, a semiconductor chip mounting substrate that is preferably used for manufacturing the semiconductor device, a method for manufacturing the same, an adhesive and a double-sided adhesive film are provided. .

The semiconductor device of the present invention is a semiconductor device in which a semiconductor chip is mounted on an organic support substrate via an adhesive member, and a predetermined wiring is provided on the side of the organic support substrate on which the semiconductor chip is mounted. External connection terminals are formed in an area array shape on the side opposite to the side of the organic support substrate on which the semiconductor chip is mounted, and the predetermined wiring is the semiconductor chip terminal and the external connection. Dynamic viscoelasticity measurement of the adhesive agent, in which at least a connecting portion between the semiconductor chip terminal and a predetermined wiring is resin-sealed, and the adhesive member includes an adhesive layer. Storage elastic modulus at 25 ° C. measured by the device is 10 to 20
Storage elastic modulus at 00 MPa and 260 ° C. is 3 to 50 MP
It is characterized by being a.

The semiconductor chip mounting substrate of the present invention is a semiconductor chip mounting substrate of an organic substrate on which the semiconductor chip is mounted via an adhesive member, and the side of the organic substrate on which the semiconductor chip is mounted. And a predetermined wiring is formed on at least one side opposite to the side on which the semiconductor chip is mounted, and an external connection terminal is provided on the opposite side of the organic substrate on which the semiconductor chip is mounted. The adhesive member is formed in an area array shape, and the adhesive member has an adhesive layer, and has a storage elastic modulus at 25 ° C. of 10 to 2000 MPa and 260 ° C. measured by a dynamic viscoelasticity measuring device of the adhesive cured product. Storage elastic modulus is 3 to 50 MPa, and the adhesive member is formed in a predetermined size at a predetermined location on the organic substrate.

According to the method of manufacturing a semiconductor chip mounting substrate of the present invention, a predetermined wiring is formed on at least one of the side on which the semiconductor chip is mounted and the side opposite to the side on which the semiconductor chip is mounted, On the side opposite to the side on which the chip is mounted, an external connection terminal is formed in an area array shape on an organic substrate, and the cured product of the cured product has a storage elastic modulus of 10 at 25 ° C. measured by a dynamic viscoelasticity measuring device. 2000 MPa and 26
An adhesive member having an adhesive layer having a storage elastic modulus at 0 ° C. of 3 to 50 MPa, wherein the adhesive has a total curing heat value of 10 to 40 when measured using a DSC (differential calorimeter).
% Of the semi-cured adhesive member film, which is cut into a predetermined size, and thermocompression-bonded onto the organic substrate.

According to the method of manufacturing a semiconductor device of the present invention, a predetermined wiring is formed on at least one of the side on which the semiconductor chip is mounted and the side opposite to the side on which the semiconductor chip is mounted, and the semiconductor chip is mounted. On the side opposite to the side where the external connection terminals are formed in an area array shape, an organic substrate for semiconductor mounting has a storage elastic modulus of 25 ° C. at 25 ° C. measured by a dynamic viscoelasticity measuring device. ~ 2000 MPa and a step of adhering an adhesive member having an adhesive layer having a storage elastic modulus at 260 ° C of 3 to 50 MPa, a step of mounting a semiconductor chip via the adhesive member, the predetermined wiring to the semiconductor chip terminal and the The method is characterized by including a step of connecting to an external connection terminal, and a step of resin-sealing at least a connecting portion between the semiconductor chip terminal and a predetermined wiring.

The adhesive of the present invention has the following compositions A to D. A. (1) Tg (glass transition temperature) containing 2 to 6% by weight of glycidyl (meth) acrylate is −10 ° C. or more and weight average molecular weight is 800,000 or more based on 100 parts by weight of epoxy resin and its curing agent. 100 to 300 parts by weight of an epoxy group-containing acrylic copolymer and (3)
An adhesive containing 0.1 to 5 parts by weight of a curing accelerator. B. (1) With respect to 100 parts by weight of the epoxy resin and its curing agent, (2) 10 to 40 parts by weight of a high molecular weight resin compatible with the epoxy resin and having a weight average molecular weight of 30,000 or more,
(3) 100 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a Tg (glass transition temperature) of -10 ° C or more and a weight average molecular weight of 800,000 or more containing 2 to 6% by weight of glycidyl (meth) acrylate And (4) an adhesive containing 0.1 to 5 parts by weight of a curing accelerator. C. (1) 2 parts of glycidyl (meth) acrylate 2 to 100 parts by weight of epoxy resin and phenol resin
100 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a Tg of -6 ° C and a weight average molecular weight of 800,000 or more, and (3) a curing accelerator.
An adhesive containing 1 to 5 parts by weight. D. (1) Epoxy resin and phenol resin 100 parts by weight, (2) Phenoxy resin 10 to 40 parts by weight,
(3) Epoxy group-containing acrylic copolymer 100 having Tg of 2 to 6% by weight of glycidyl (meth) acrylate of −10 ° C. or more and a weight average molecular weight of 800,000 or more
An adhesive containing 300 parts by weight and 0.1 to 5 parts by weight of (4) a curing accelerator.

The double-sided adhesive film of the present invention has the following E to H:
It has a three-layer structure. E. A heat-resistant thermoplastic film is used as a core material, and (2) glycidyl (meth) acrylate 2 to 100 parts by weight of (1) epoxy resin and its curing agent on both sides of the core material.
100 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a Tg (glass transition temperature) of 6% by weight or more and a weight average molecular weight of 800,000 or more, and (3) a curing accelerator 0.1. A three-layer double-sided adhesive film having an adhesive containing ˜5 parts by weight. F. A heat-resistant thermoplastic film is used for the core material, and (1) 100 parts by weight of the epoxy resin and its curing agent are (2) compatible with the epoxy resin and have a weight average molecular weight of 30,000 or more on both sides of the core material. Containing 10 to 40 parts by weight of the high molecular weight resin and (3) 2 to 6% by weight of glycidyl (meth) acrylate and having a Tg (glass transition temperature) of -10 ° C or higher and a weight average molecular weight of 800,000 or higher. A three-layer double-sided adhesive film having an adhesive containing 100 to 300 parts by weight of an acrylic copolymer and (4) 0.1 to 5 parts by weight of a curing accelerator. G. A heat-resistant thermoplastic film is used as the core material, and (1) epoxy resin and phenol resin 100 are provided on both sides of the core material.
100 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a Tg of (2) 2 to 6% by weight of glycidyl (meth) acrylate of −10 ° C. or more and a weight average molecular weight of 800,000 or more based on parts by weight. And (3) a three-sided double-sided adhesive film having an adhesive containing 0.1 to 5 parts by weight of a curing accelerator. H. A heat-resistant thermoplastic film is used as the core material, and (1) epoxy resin and phenol resin 100 are provided on both sides of the core material.
Based on parts by weight, (2) 10 to 40 parts by weight of phenoxy resin and (3) 2 to 6% by weight of glycidyl (meth) acrylate, Tg is -10 ° C or higher and the weight average molecular weight is 8
Epoxy group-containing acrylic copolymer having a number of at least 100,000
0 to 300 parts by weight and (4) curing accelerator 0.1 to 5
A three-layer double-sided adhesive film having an adhesive containing parts by weight.

In the semiconductor device of the present invention, the predetermined wiring can be directly connected to the semiconductor chip terminal by an inner bonding method such as wire bonding or TAB (tape automated bonding).

In the semiconductor device of the present invention, the adhesive member is preferably in the form of a film, and the adhesive member has an adhesive layer. The resin component of the adhesive is epoxy resin, epoxy group-containing acrylic copolymer, Those containing an epoxy resin curing agent and an epoxy resin curing accelerator are used.

As the adhesive member, a heat-resistant thermoplastic film having a glass transition temperature of 200 ° C. or higher, such as polyimide, polyether sulfone, polyamideimide or polyetherimide film, is used as the core material, and the adhesive is applied to both sides of the core material. A layered structure is preferred. Liquid crystal polymer films are also used as heat resistant thermoplastic films. The residual solvent amount in the adhesive layer is preferably 5% by weight or less.

In the substrate for mounting a semiconductor chip of the present invention, the adhesive member is preferably in the form of a film, and the adhesive member has an adhesive layer, and the resin component of the adhesive is epoxy resin or epoxy group. Those containing an acryl copolymer, an epoxy resin curing agent, and an epoxy resin curing accelerator are used.

As the adhesive member, a heat-resistant thermoplastic film having a glass transition temperature of 200 ° C. or higher such as polyimide, polyether sulfone, polyamideimide or polyetherimide film is used as the core material, and the adhesive is applied to both sides of the core material. A layered structure is preferred. Liquid crystal polymer films are also used as heat resistant thermoplastic films. The residual solvent amount in the adhesive layer is preferably 5% by weight or less.

The adhesive member formed at a predetermined position on the organic substrate is a film punched by a punching die to a predetermined size, and the adhesive member formed at a predetermined position on the organic substrate. Is a film in a semi-cured state in which the adhesive of the adhesive member has finished heat generation of 10 to 40% of the total heat generation of curing when measured using DSC, and is cut into a predetermined size, and then the organic film is formed. It is thermocompression bonded onto the system substrate.

In the method of manufacturing a substrate for mounting a semiconductor chip of the present invention, the cut adhesive member films are individually precisely positioned and then temporarily adhered by a hot press to form a plurality of organic adhesive member substrates. After being placed on the substrate, it can be adhered together by pressing with a heated release surface treatment die. Mold release surface treatment The surface mold release material of the mold is preferably at least one of Teflon and silicone. At least one step of removing the static electricity generated when the adhesive member film is conveyed can be added before the adhesive member film cutting step.

In the method of manufacturing a semiconductor device of the present invention, the temperature of at least the chip side can be raised by heating from both the lower surface side and the semiconductor chip side of the semiconductor mounting substrate.

In the adhesive of the present invention, it is preferable to use it after the heat generation of 10 to 40% of the total curing calorific value measured by DSC is finished, and the dynamic viscoelasticity measuring device is used. The storage elastic modulus of the cured adhesive when measured using is 10 to 2000 MPa at 25 ° C. and 3 at 260 ° C.
It is preferably ˜50 MPa.

The inorganic filler is used in an amount of 2 to 20 parts by volume with respect to 100 parts by volume of the adhesive resin component, and the inorganic filler is preferably alumina or silica.

A semiconductor device can be obtained by forming an adhesive film on a base film to form an adhesive film, and using this adhesive film to bond a semiconductor chip and a wiring board.

In the double-sided adhesive film of the present invention, the adhesive has a total curing heat value of 10 when measured by DSC.
It is preferable to use it after the heat generation of -40% is finished, and the storage elastic modulus of the cured adhesive is 10-2000 MPa at 25 ° C and 260 ° C when measured using a dynamic viscoelasticity measuring device. Is preferably 3 to 50 MPa. The inorganic filler is used in an amount of 2 to 20 parts by volume with respect to 100 parts by volume of the adhesive resin component, and the inorganic filler is preferably alumina or silica.

The heat-resistant thermoplastic film used as the core material preferably has a glass transition temperature of 200 ° C. or higher. Examples of such a heat-resistant thermoplastic film having a glass transition temperature of 200 ° C. or higher include polyimide, polyether sulfone and polyamide. Imide or polyetherimide films are preferred. A liquid crystal polymer film is also used as the heat-resistant thermoplastic film used for the core material.

In order to solve the problems described in the prior art, first, a semiconductor chip is mounted on an organic wiring substrate via an insulating adhesive, and the chip side terminal and the wiring board side terminal are connected by gold wire bonding. For the semiconductor package in which the solder ball external terminals are arranged in an area array on the back surface of the substrate, the relationship between the physical properties of the insulating adhesive used for the semiconductor package and the temperature cycle resistance after mounting on the motherboard is analyzed by the FEM elastic-plastic analysis method. I looked it up.

As a result, the CTE of the chip (coefficient of linear thermal expansion: 3.5 ppm) and the CTE of the mother board (14 to 1)
The stress applied to the external terminals of the solder balls of the substrate caused by the difference of 8 ppm) decreases as the elastic modulus E of the insulating adhesive decreases, and the elastic modulus E measured by a dynamic viscoelasticity measuring device is 2000 MPa or less, Desirably 1000MP
It was found that if it was a or less, the equivalent strain of the solder terminal in the re-outer peripheral portion was sufficiently small, and even if it was applied to the Coffin-Manson rule, there was a fatigue life of 1000 cycles or more at a temperature cycle of -55 ° C to 125 ° C. .

On the contrary, the elastic modulus E of the usual epoxy type die bonding material is 3000 MPa or more, and it has been found that there is a problem in the temperature cycle reliability of the solder ball.

On the other hand, when the elastic modulus E of the insulating adhesive is reduced to 10 MPa or less, which is about the level of a silicone elastomer, the elastic modulus E becomes so small as to exceed the measurement limit at the reflow temperature upper limit temperature of 260 ° C., and the function as a strength member. It becomes a region that disappears, and it is not possible to expect adhesion and holding with the substrate surface and the silicon chip. The temperature dependence of the shear adhesive strength has the same tendency as the temperature dependence of the elastic modulus, and becomes smaller as the temperature rises. That is, unless the elastic modulus E at the reflow temperature of 260 ° C. is at least 3 MPa or more, the shear adhesive strength cannot be expected. If peeling occurs at the interface with the chip or the substrate at the reflow temperature of 260 ° C., the gold wire disconnection failure will occur in the temperature resistance cycle test and the corrosion disconnection failure will occur in the moisture resistance test.

Therefore, the elastic modulus of the insulating adhesive (adhesive cured product) for mounting the chip on the organic wiring substrate is in the range of 10 to 2000 MPa, preferably 50 to 1500 MPa, and most preferably 100 to 100 MPa. 100
It has been found that the use of one having a range of 0 MPa and an elastic modulus of 3 to 50 MPa at a reflow temperature of 260 ° C. is a condition for satisfying the temperature cycle resistance and the moisture absorption reflow resistance.

As a result of searching various thermosetting resins having the above-mentioned temperature dependence of elastic modulus, it was found that the epoxy group-containing acrylic copolymer is a suitable adhesive capable of realizing the physical properties in the range.

Further, as a factor that deteriorates the moisture absorption reflow resistance, there is a void generated at the interface between the organic wiring board and the insulating adhesive. In a usual method in which a small amount of a liquid thermosetting adhesive is dropped and applied, voids are easily caught, which causes cracks and swelling of the substrate during moisture reflow.

Therefore, the above epoxy-containing acrylic copolymer is processed into a film, and the residual solvent amount is 5% or less,
Desirably, it is dried to 2% or less, and 10 to 10% of the total curing heat value when measured using a DSC (differential calorimeter).
40% B-stage cured adhesive film,
The substrate is cut into a predetermined size and attached to an organic wiring substrate by hot pressing to obtain a semiconductor mounting substrate.

After that, a chip is mounted and thermocompression bonded, and a wire bonding process and a sealing process are performed to obtain a package finished product.

The package thus obtained is less likely to have gaps or voids at the interface between the chip and the substrate, but is heated not only on the semiconductor mounting substrate side but also on both sides of the chip side during thermocompression bonding of the chip. It was found that a gap is less likely to occur at the interface between the chip and the adhesive, the resin is sufficiently embedded between the wiring portions of the substrate, and the moisture absorption reflow resistance is improved. Further, it was found that when the residual solvent amount of the adhesive film is controlled to 5% or less, preferably 2% or less, bubbles are not generated during the curing process of the adhesive film and the moisture absorption reflow resistance is not deteriorated. It was

The application of the adhesive film having the above-mentioned physical properties is not limited to the semiconductor package in which the chip side terminals and the wiring board side terminals are connected by gold wire bonding and the external terminals are arranged on the back surface of the substrate in an area array form. , The same effect also applies to a package in which the chip side terminal and the wiring board side terminal are connected by a TAB (tape automated bonding) inner bonding method (a package in which the chip side terminal and the wiring board side terminal are directly connected). And the semiconductor chip is bonded to the organic wiring board via an adhesive, and the temperature cycle resistance and the moisture absorption reflow resistance of all area array packages are simultaneously satisfied. The external connection terminals are arranged in an area array, that is, in a grid pattern on the entire back surface of the substrate or in a row or several rows in the peripheral portion.

The organic wiring substrate is not limited to a substrate material such as a polyimide film substrate even if it is a FR-4 substrate such as a BT (bismaleimide) substrate or a glass epoxy substrate. The above-mentioned adhesive film may be formed of a thermosetting adhesive having the above-mentioned physical properties, but it is applied to both sides of the polyimide film in order to secure rigidity when wound or fed as a tape. You may make it a layered structure. It has been found that it has the same action and effect as described above.

As a method for adhering the adhesive film to the organic wiring board, the adhesive film is cut into a predetermined shape, then the cut film is accurately aligned and thermocompression bonded to the organic wiring board.

The method for cutting the adhesive film may be any method as long as it accurately cuts the film into a predetermined shape, but in consideration of workability and adhesiveness, the adhesive film is cut using a punching die. After that, it is preferable to perform temporary pressure bonding or final pressure bonding to the organic wiring board.

The thermo-compression bonding of the cut adhesive film to the organic wiring board is performed by cutting the adhesive film, adhering to the press material by suction and accurately aligning it, and then temporarily press-bonding it on the organic wiring board, and then performing thermocompression bonding. There are a method of main press-bonding with a press and a method of punching an adhesive film with a punching die and then performing temporary pressure-bonding, and then performing main press-bonding with a hot press. Further, when a punching die is used, there is a method in which the tape punched by the punching die is directly pressure-bonded as it is.

Temporary pressure bonding may be performed by adhering the punched adhesive tape to the organic wiring substrate, and the conditions are not particularly limited.

At the time of main pressure bonding, the pressure bonding temperature of the adhesive film is 30.
-250 degreeC is preferable and 70-150 degreeC is more preferable. When the pressure-bonding temperature is 30 ° C. or lower, the elastic modulus of the adhesive film is high and the adhesive strength is low, and when the adhesive film is adhered to the wiring of the organic wiring substrate, the embedding property of the adhesive around the wiring is poor, which is not preferable. When the bonding temperature is 250 ° C. or higher, the wiring is oxidized and the organic wiring board becomes soft, which is not preferable in terms of workability.

[0052] The pressure of the crimping is preferably 1~20kg / cm ^2, more preferably 3~10kg / cm ^2. When the pressure bonding pressure is 1 kg / cm ² or less, the adhesive force of the adhesive film and the embedding property around the wiring are poor, and when the pressure is 20 kg / cm ² or more, the adhesive sticks out at a position other than a predetermined position, and the dimensional accuracy of the adhesive becomes poor.

The main pressure bonding time may be any time that can be bonded at the above pressure bonding temperature and pressure bonding time, but in consideration of workability, it is 0.3 to 6
0 second is preferable, and 0.5 to 10 seconds is more preferable.

It is preferable that the hot pressing for main pressure bonding has a release agent on the surface so that the adhesive does not adhere to the surface of the press, and that using Teflon or silicone is particularly preferable from the viewpoint of mold release property and workability.

The epoxy resin used in the present invention may be any resin that cures and exhibits an adhesive action. An epoxy resin having a functionality of two or more and having a molecular weight of less than 5000, preferably less than 3000, is used. Particularly, it is preferable to use a bisphenol A type or bisphenol F type liquid resin having a molecular weight of 500 or less because the fluidity at the time of lamination can be improved. Bisphenol A type or bisphenol F type liquid resin having a molecular weight of 500 or less is available from Yuka Shell Epoxy Co., Ltd.
7, Epikote 827, and Epikote 828 are commercially available. Also, from Dow Chemical Japan Co., Ltd., E. R. 330, D.I. E. R. 331, D.I.
E. R. It is marketed under the trade name of 361. In addition, YD128, YDF170 from Tohto Kasei Co., Ltd.
It is marketed under the product name.

As the epoxy resin, a polyfunctional epoxy resin may be added for the purpose of increasing the Tg (glass transition temperature). Examples of the polyfunctional epoxy resin include phenol novolac type epoxy resin and cresol novolac type epoxy resin. To be done.

The phenol novolac type epoxy resin is
It is marketed by Nippon Kayaku Co., Ltd. under the trade name of EPPN-201. In addition, cresol novolac type epoxy resin is ESCN-0 from Sumitomo Chemical Co., Ltd.
01, ESCN-195, and from the above-mentioned Nippon Kayaku Co., Ltd., EOCN1012, EOCN10
25, and is marketed under the trade name of EOCN1027. Further, as the epoxy resin, a brominated epoxy resin, a brominated bisphenol A type epoxy resin (for example, Sumitomo Chemical Co., Ltd., trade name ESB-400), a brominated phenol novolac type epoxy resin (for example, Nippon Kayaku Co., Ltd. trade name BREN-105, BREN-
S) etc. can be used.

As the curing agent for the epoxy resin, those generally used as a curing agent for the epoxy resin can be used, and amine, polyamide, acid anhydride, polysulfide, boron trifluoride and phenolic hydroxyl group are contained in 2 molecules per molecule. Bisphenol A, bisphenol F, which is a compound having one or more
Examples include bisphenol S and the like. In particular, it is preferable to use a phenol resin such as phenol novolac resin, bisphenol novolac resin, cresol novolac resin or the like because it has excellent resistance to electrolytic corrosion when absorbing moisture.

Such a preferred curing agent is Phenolite LF28 from Dainippon Ink and Chemicals, Inc.
82, Phenolite LF2822, Phenolite TD-
2090, Phenolite TD-2149, Phenolite VH4150, and Phenolite VH4170 are commercially available. Further, as a curing agent, tetrabromobisphenol A which is a brominated phenol compound (trade name Fireguard FG-200 manufactured by Teijin Chemicals Ltd.)
0) etc. can be used.

It is preferable to use a curing accelerator together with the curing agent, and it is preferable to use various imidazoles as the curing accelerator. As the imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole,
1-Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate and the like can be mentioned.

Imidazoles are commercially available from Shikoku Chemicals Co., Ltd. under the trade names of 2E4MZ, 2PZ-CN and 2PZ-CNS.

As the high molecular weight resin which is compatible with the epoxy resin and has a weight average molecular weight of 30,000 or more, a phenoxy resin, a high molecular weight epoxy resin, an ultra high molecular weight epoxy resin, a functional group-containing rubber having a large polarity, and a large polarity. Examples thereof include functional group-containing reactive rubber. The weight average molecular weight is set to 30,000 or more in order to reduce tackiness of the adhesive in the B stage and improve flexibility at the time of curing. Examples of the functional group-containing reactive rubber having a large polarity include a rubber obtained by adding a functional group having a large polarity such as a carboxyl group to acrylic rubber. Here, having compatibility with epoxy resin means
It refers to the property of forming a homogenous mixture without being separated from the epoxy resin after curing and separating into two or more phases.

Phenoxy resins are available from Tohto Kasei Co., Ltd. as Phenotote YP-40 and Phenotote YP-5.
It is marketed under the trade name of No. 0, Phenothote YP-60 and the like. The high molecular weight epoxy resin is a high molecular weight epoxy resin having a molecular weight of 30,000 to 80,000, and further, an ultra high molecular weight epoxy resin having a molecular weight of more than 80,000 (Japanese Patent Publication No. 7-59617, Japanese Patent Publication No. 7-59618, Japanese Patent Publication No. 7-59619, Japanese Patent Publication No. 7-59620, Japanese Patent Publication No. 7-64911, and Japanese Patent Publication No. 7-68327), all of which are manufactured by Hitachi Chemical Co., Ltd. As a functional group-containing reactive rubber having a large polarity, a carboxyl group-containing acrylic rubber is
It is marketed by Teikoku Chemical Industry Co., Ltd. under the trade name of HTR-860P.

The addition amount of the high molecular weight resin which is compatible with the above-mentioned epoxy resin and has a weight average molecular weight of 30,000 or more means that the phase containing the epoxy resin as a main component (hereinafter referred to as the epoxy resin phase) lacks flexibility. The amount is 10 parts by weight or more in order to prevent the decrease in tackiness and the decrease in insulating property due to cracks and the like, and is 40 parts by weight or less in order to prevent the decrease in Tg of the epoxy resin phase.

An epoxy group-containing acrylic copolymer containing 2 to 6% by weight of glycidyl (meth) acrylate and having a Tg of -10 ° C or more and a weight average molecular weight of 800,000 or more is commercially available from Teikoku Chemical Industry Co., Ltd. Product name H
TR-860P-3 can be used. When the functional group monomer is a carboxylic acid type acrylic acid or a hydroxyl group type hydroxymethyl (meth) acrylate, the crosslinking reaction easily proceeds, and gelation in a varnish state occurs,
There is a problem such as a decrease in adhesive strength due to an increase in curing degree in the B stage state, which is not preferable. The amount of glycidyl (meth) acrylate used as the functional group monomer is
The copolymer ratio is 2 to 6% by weight. To get the adhesive strength,
The content is 2% by weight or more, and 6% by weight or less to prevent gelation of rubber. The balance may be ethyl (meth) acrylate, butyl (meth) acrylate, or a mixture of both, and the mixing ratio is determined in consideration of the Tg of the copolymer. If the Tg is less than -10 ° C, the tackiness of the adhesive film in the B-stage state becomes large and the handleability deteriorates. Examples of the polymerization method include pearl polymerization and solution polymerization, which can be obtained.

The weight average molecular weight of the epoxy group-containing acrylic copolymer is set to 800,000 or more. In this range, the strength and flexibility of the sheet or film are not significantly reduced and the tackiness is not increased. is there.

The amount of the epoxy group-containing acrylic copolymer added is 100 parts by weight or more in order to prevent the strength of the film from decreasing and the tackiness of the film to increase. When the amount of the epoxy group-containing acrylic rubber added increases. Since the amount of the rubber component is increased and the amount of the epoxy resin phase is reduced, the handling property at high temperature is deteriorated, so that the amount is 300 parts by weight or less.

A coupling agent may be added to the adhesive in order to improve interfacial bonding between different materials.
A silane coupling agent is preferable as the coupling agent.

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

As the silane coupling agent described above, γ-glycidoxypropyltrimethoxysilane is NUC A-
187, γ-mercaptopropyltrimethoxysilane is NUC A-189, γ-aminopropyltriethoxysilane is NUC A-1100, and γ-ureidopropyltriethoxysilane is NUC A-1160, N-β-.
Aminoethyl-γ-aminopropyltrimethoxysilane, which is a product name of NUC A-1120, is commercially available from Nippon Unicar Co., Ltd. and can be preferably used.

From the effect of addition, heat resistance and cost, it is preferable to add 0.1 to 10 parts by weight of the coupling agent to 100 parts by weight of the resin.

Further, in order to adsorb ionic impurities and improve insulation reliability when absorbing moisture, an ion trapping agent can be added. The compounding amount of the ion scavenger is preferably 5 to 10 parts by weight from the effects of addition, heat resistance, and cost. As the ion scavenger, a compound known as a copper damage inhibitor, such as a triazine thiol compound or a bisphenol-based reducing agent, may be added to prevent copper from being ionized and dissolved. Examples of the bisphenol-based reducing agent include 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 of Disnet DB. 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 of Yoshinox BB.

Further, for the purpose of improving the handleability and heat conductivity of the adhesive, imparting flame retardancy, adjusting melt viscosity, imparting thixotropic property, improving surface hardness, etc. It is preferable to mix 2 to 20 parts by volume of the inorganic filler with respect to 100 parts by volume of the adhesive resin component. From the viewpoint of the effect of compounding, if the compounding amount is 2 parts by volume or more, and if the compounding amount is increased, problems such as an increase in the storage elastic modulus of the adhesive, a decrease in the adhesiveness, and a decrease in the electrical properties due to the remaining voids will occur. It is considered as follows.

As the inorganic filler, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina powder, aluminum nitride powder, aluminum borate whiskers, boron nitride powder. , Crystalline silica, amorphous silica and the like.

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

Of these, alumina is preferable because it has good heat dissipation, heat resistance, and insulation. In addition, crystalline silica or amorphous silica is inferior to alumina in terms of heat dissipation, but since it has less ionic impurities, it has high insulation during PCT treatment and corrosion of copper foil, aluminum wire, aluminum plate, etc. It is suitable because of its small number.

Aluminum hydroxide, magnesium hydroxide, antimony trioxide and the like are preferable for imparting flame retardancy.

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

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

In the adhesive film of the present invention, each component of the adhesive is dissolved or dispersed in a solvent to form a varnish, which is applied onto the base film and heated to remove the solvent to form an adhesive layer on the base film. Obtained. As the base film, polytetrafluoroethylene film,
A plastic film such as a polyethylene terephthalate film, a release-treated polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, or a polyimide film can be used. The base film can be peeled off at the time of use and the adhesive film alone can be used, or can be used together with the base film and removed later.

Examples of the plastic film used in the present invention include polyimide films such as Kapton (trade name, manufactured by DuPont Co., Ltd. Toray), Apical (trade name, manufactured by Kanegafuchi Chemical Industry Co., Ltd.), and Lumirror (Toray, DuPont Co., Ltd.). Polyethylene terephthalate film such as PUREX (trade name, manufactured by Teijin Limited) and the like can be used.

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

When the dispersion of the inorganic filler is taken into consideration, the production of the varnish can be carried out by using a raider, a three-roll mill, a bead mill or the like, or a combination thereof. After pre-mixing the filler and low molecular weight material,
By blending a high molecular weight substance, it becomes possible to shorten the time required for mixing. Further, after forming the varnish, it is preferable to remove air bubbles in the varnish by vacuum deaeration.

An adhesive varnish is applied on the base film such as the plastic film and dried by heating to remove the solvent. The adhesive thus obtained has a total calorific value of 10 to 10 which is measured by DSC. It is assumed that the heat generation of 40% has been completed. When the solvent is removed, it is heated. At this time, the curing reaction of the adhesive composition proceeds and gelation occurs.
The cured state at that time affects the fluidity of the adhesive, and optimizes the adhesiveness and handleability. DSC (Differential Scanning Calorimetry)
The principle of measurement is the zero method, which supplies or removes the amount of heat so as to cancel out the temperature difference from a standard sample that does not generate heat or absorb heat within the measurement temperature range. Can be measured. The reaction of the resin composition is an exothermic reaction, and when the temperature of the sample is raised at a constant temperature rising rate, the sample reacts to generate heat. The amount of heat generated is output to a chart, the heat generation curve and the area surrounded by the baseline are obtained with the baseline as the reference, and this is taken as the amount of heat generated. The heating value is measured from room temperature to 250 ° C. at a temperature rising rate of 5 to 10 ° C./min, and the calorific value is obtained. Some of these are fully automatic and can be easily performed using them. Next, the calorific value of the adhesive obtained by coating and drying the base film is obtained as follows.
First, the total calorific value of the uncured sample obtained by drying the solvent at 25 ° C. using a vacuum dryer is measured, and this is designated as A (J / g). Next, the calorific value of the coated and dried sample is measured and designated as B. The degree of cure C (%) of the sample (a state in which heat generation has ended by heating and drying) is given by the following mathematical expression (1).

C (%) = (A−B) × 100 / A (1) The storage elastic modulus of the adhesive of the present invention measured by a dynamic viscoelasticity measuring device is 20 to 2,000 MPa at 25 ° C. 260 ° C
It must have a low elastic modulus of 3 to 50 MPa.
The storage elastic modulus is measured by applying a tensile load to an adhesive cured product (an adhesive that has finished generating heat of 95 to 100% of the total curing calorific value when measured using DSC), and a frequency of 10 Hz,
The measurement was performed in the temperature dependence measurement mode in which the temperature was raised from -50 ° C to 300 ° C at a heating rate of 5 to 10 ° C / min. If the storage elastic modulus at 25 ° C. exceeds 2,000 MPa, the effect of alleviating the stress generated at the time of reflow due to the difference in the thermal expansion coefficient between the semiconductor chip and the printed wiring board becomes small, so that cracks occur. On the other hand, the storage elastic modulus is 20
When it is less than MPa, the handling property of the adhesive is deteriorated. It is preferably 50 to 1000 MPa.

The present invention is characterized in that the epoxy group-containing acrylic copolymer and the epoxy resin adhesive have a low elastic modulus near room temperature. Since the epoxy group-containing acrylic copolymer has a low elastic modulus near room temperature, increasing the mixing ratio of the epoxy group-containing acrylic copolymer reduces the difference in thermal expansion coefficient between the semiconductor chip and the printed wiring board. Due to this, cracks can be suppressed by the effect of relaxing the stress generated in the heating and cooling process during reflow. Further, since the epoxy group-containing acrylic copolymer is excellent in reactivity with the epoxy resin, the cured adhesive is chemically and physically stable, and therefore exhibits excellent performance in a moisture resistance test represented by PCT treatment. . Also, by the following method
It has solved problems in handling such as reduction in strength, reduction in flexibility, and increase in tackiness of conventional adhesive films. 1) By using the epoxy group-containing acrylic copolymer specified in the present invention, it is possible to suppress the occurrence of cracks during reflow. 2) By using an acrylic copolymer having a large molecular weight, the film strength and flexibility of the adhesive film can be secured even when the amount of the copolymer added is small. 3) Weight average molecular weight 3 compatible with epoxy resin
The tackiness can be reduced by adding more than 10,000 high molecular weight resins.

Further, in the adhesive of the present invention, the epoxy resin and the high molecular weight resin have good compatibility and are uniform,
The epoxy group contained in the acrylic copolymer partially reacts with them, and the whole epoxy resin including unreacted epoxy resin crosslinks and gels. Even when a large amount is contained, the handleability is not impaired. In addition, since a large amount of unreacted epoxy resin remains in the gel, when pressure is applied, unreacted components seep out from the gel, and even if the whole gels, there is less deterioration in adhesiveness. .

When the adhesive is dried, the epoxy group and the epoxy resin contained in the epoxy group-containing acrylic copolymer react with each other. However, the epoxy group-containing acrylic copolymer has a large molecular weight and the epoxy group in one molecular chain is large. Since it contains many groups, it gels even if the reaction proceeds slightly. Generally, the total curing heat value of 10 when measured using DSC
Gelation occurs in the state where heat generation of 40% to 40% is finished, that is, in the first half of the A or B stage. Therefore, gelation occurs in a state where a large amount of unreacted components such as epoxy resin are contained, and the melt viscosity is significantly increased as compared with the case where gelation is not performed, and handleability is not impaired. Further, when pressure is applied, unreacted components exude from the gel, so that even when gelled, the adhesiveness is not significantly reduced. Further, since the adhesive can be formed into a film in a state where it contains 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 adhesive, since the 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, the fluidity is low. Even when pressure is applied, the amount of unreacted components exuding is lower than that in the gel, and the adhesiveness is reduced.

Although the reactivity of the epoxy groups contained in the acrylic copolymer with the epoxy groups of the low molecular weight epoxy resin is not clear, it is sufficient that they have at least the same reactivity. It is not necessary that only the epoxy groups contained in the acrylic copolymer react selectively.

In this case, the A, B and C stages show the degree of curing of the adhesive. The A stage is in a substantially uncured state and has not gelled, and is in a state in which heat generation of 0 to 20% of the total heat generation amount of curing when measured using DSC is finished. The B stage is in a state where it is slightly cured and gelled, and the heat generation of 20 to 60% of the total curing heat value is finished. The C stage is in a state in which the curing has progressed considerably and has gelled, and the heat generation of 60 to 100% of the total curing heat value has finished.

Regarding the determination of gelation, after immersing the adhesive in a solvent having a high permeability such as THF (tetrahydrofuran) and allowing it to stand at 25 ° C. for 20 hours, the adhesive is not completely dissolved and is in a swollen state. It was determined that the product gelled. In addition, it experimentally determined as follows.

Dip the adhesive (weight W1) in THF and
After standing at 5 ° C. for 20 hours, the non-dissolved content was 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 mathematical expression (2). Those with a THF extraction rate of more than 80% by weight were determined not to be gelled, and those with a THF extraction rate of 80% by weight or less were determined to be gelled.

In the present invention, by adding a filler, the melt viscosity can be increased and the thixotropic property can be exhibited, so that the above effect can be further increased.

Further, in addition to the above effects, properties such as improvement of heat dissipation of the adhesive, imparting flame retardancy to the adhesive, giving proper viscosity at the temperature at the time of adhesion, and improving surface hardness can be imparted. . A semiconductor device obtained by adhering a semiconductor chip and a wiring board using the adhesive film of the present invention has reflow resistance, temperature cycle test, electrolytic corrosion resistance, and moisture resistance (PCT resistance).
It was excellent in sex.

The heat-resistant thermoplastic film used as the core material in the present invention is preferably a film using a polymer or a liquid crystal polymer having a glass transition temperature Tg of 200 ° C. or higher, such as polyimide, polyether sulfone, polyamide imide, Polyetherimide or wholly aromatic polyester is preferably used. The film thickness is 5
It is preferably used within the range of 200 μm, but not limited thereto. When a thermoplastic film having a Tg of 200 ° C. or less is used as the core material, plastic deformation may occur at high temperatures such as solder reflow, which is not preferable.

The adhesive formed on both sides of the core material in the present invention is a varnish prepared by dissolving or dispersing each component of the adhesive in a solvent, and coating it on a heat-resistant thermoplastic film as the core material.
It can be produced by heating and removing the solvent,
A double-sided adhesive film having a three-layer structure can be obtained by forming the adhesive layer on the heat-resistant thermoplastic film serving as the core material. The thickness of the adhesive is used in the range of 2 to 150 μm, and if it is thinner than this, adhesiveness and thermal stress buffering effect are poor, and if it is thicker, it is not economical, but it is not limited.

Further, each component of the adhesive is dissolved or dispersed in a solvent to form a varnish, and the varnish is applied on a base film and heated to remove the solvent to produce an adhesive film consisting of only the adhesive component. It is also possible to obtain a double-sided adhesive film having a three-layer structure by bonding the adhesive film consisting of this adhesive component alone to both sides of the heat-resistant thermoplastic film serving as the core material. Here, as the base film for producing an adhesive film consisting only of the adhesive component, a polytetrafluoroethylene film, a polyethylene terephthalate film, a release-treated polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, A plastic film such as a polyimide film can be used. Examples of the plastic film include polyimide films such as Kapton (Toray, a product name manufactured by DuPont), Apical (a product name manufactured by Kanegafuchi Chemical Co., Ltd.), Lumirror (Toray, a product name manufactured by DuPont), Purex Polyethylene terephthalate film such as (Teijin Co., Ltd. product name) can be used.

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

The production of the varnish can be carried out by using a mill, a three-roll mill, a bead mill and the like, or a combination thereof, in consideration of the dispersion of the inorganic filler. After pre-mixing the filler and low molecular weight material,
By blending a high molecular weight substance, it becomes possible to shorten the time required for mixing. Further, after forming the varnish, it is preferable to remove air bubbles in the varnish by vacuum deaeration.

The above-mentioned adhesive can be obtained by applying an adhesive varnish on a base film such as a heat-resistant thermoplastic film or a plastic film as a core material, and heating and drying to remove the solvent. The adhesive used has a total calorific value of 10 to 4 which is measured by DSC.
It is preferable that the heat generation of 0% is completed. When the solvent is removed, it is heated. At this time, the curing reaction of the adhesive composition proceeds and gelation occurs. The cured state at that time affects the fluidity of the adhesive, and optimizes the adhesiveness and handleability. D
SC (Differential Scanning Calorimetry) is a method of generating heat within the measurement temperature range.
The principle of measurement is the zero-position method in which the amount of heat is supplied or removed so as to constantly cancel out the temperature difference from the standard sample having no endotherm, and a measuring device is commercially available and can be used for measurement. The reaction of the resin composition is an exothermic reaction, and when the temperature of the sample is raised at a constant temperature rising rate, the sample reacts to generate heat. The amount of heat generated is output to a chart, the heat generation curve and the area surrounded by the baseline are obtained with the baseline as the reference, and this is taken as the amount of heat generated. From room temperature to 250 ° C 5
The heating value is measured at a temperature rising rate of -10 ° C / min to obtain the above-mentioned calorific value. Some of these are fully automatic and can be easily performed using them.

The calorific value of the adhesive obtained by coating and drying the heat-resistant thermoplastic film or base film as the core material is determined as follows. First, only the adhesive component was taken out, and the total calorific value of the uncured sample obtained by drying the solvent at 25 ° C. using a vacuum dryer was measured.
/ G). Next, the calorific value of the coated and dried sample is measured and designated as B. The degree of cure C (%) of the sample (a state in which heat generation has ended by heating and drying) is given by the following mathematical expression (1).

C (%) = (A−B) × 100 / A (1) The storage elastic modulus of the adhesive component of the present invention measured by a dynamic viscoelasticity measuring device is 20 to 2,000 MPa at 25 ° C. So 26
It is preferable that the elastic modulus is as low as 3 to 50 MPa at 0 ° C. The storage elastic modulus was measured in a temperature-dependent measurement mode in which a tensile load was applied to the cured adhesive, and the temperature was measured from −50 ° C. to 300 ° C. at a heating rate of 5 to 10 ° C./min. Storage elastic modulus at 25 ° C is 2,000 MPa
If it exceeds, the effect of alleviating the stress generated at the time of reflow due to the difference in thermal expansion coefficient between the semiconductor chip and the printed wiring board becomes small, and cracks are generated. On the other hand, when the storage elastic modulus is less than 20 MPa, handleability becomes poor.

In the present invention, by adopting a three-layer structure in which a heat resistant thermoplastic film is used as the core material, the epoxy group-containing acrylic copolymer and the epoxy resin adhesive have a low elastic modulus near room temperature. Is characterized by facilitating handling of the adhesive film. That is, with the three-layer structure of the present invention, it is possible to easily automate the work such as alignment of the non-rigid adhesive film near room temperature, and yet to exhibit the excellent thermal stress relaxation effect of the present adhesive system. be able to. In the present invention, the following method has solved the problem in handleability due to the decrease in rigidity of the conventional low elastic modulus adhesive film. 1) By adopting a three-layer structure in which a heat resistant thermoplastic film is arranged on a core material, an adhesive having a low elastic modulus can be easily handled in a film form. 2) By using the heat-resistant thermoplastic film as the core material defined in the present invention, plastic deformation of the adhesive film during reflow can be suppressed.

Furthermore, in the present invention, the epoxy resin and the high molecular weight resin have good compatibility and are uniform, and the epoxy groups contained in the acrylic copolymer partially react with them to form an unreacted epoxy resin. Since the whole including the resin crosslinks and gels, it suppresses the fluidity and does not impair the handleability even when it contains a large amount of epoxy resin and the like. In addition, since a large amount of unreacted epoxy resin remains in the gel, when pressure is applied, unreacted components seep out from the gel, and even if the whole gels, there is less deterioration in adhesiveness. .

When the adhesive is dried, the epoxy group and the epoxy resin contained in the epoxy group-containing acrylic copolymer react with each other. However, the epoxy group-containing acrylic copolymer has a large molecular weight and the epoxy resin in one molecular chain is large. Since it contains many groups, it gels even if the reaction proceeds slightly. Generally, the total curing heat value of 10 when measured using DSC
Gelation occurs in the state where heat generation of 40% to 40% is finished, that is, in the first half of the A or B stage. Therefore, gelation occurs in a state where a large amount of unreacted components such as epoxy resin are contained, and the melt viscosity is significantly increased as compared with the case where gelation is not performed, and handleability is not impaired. Further, when pressure is applied, unreacted components exude from the gel, so that even when gelled, the adhesiveness is not significantly reduced. Further, since the adhesive can be formed into a film in a state where it contains 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 from the latter half of the B stage for the first time in the C stage state, and the unreacted components such as the epoxy resin at the stage where the gelation occurs are low in fluidity. Even when pressure is applied, the amount of unreacted components exuding is lower than that in the gel, and the adhesiveness is reduced.

Although it is not clear how easily the epoxy groups contained in the acrylic copolymer react with the epoxy groups of the low molecular weight epoxy resin, it is sufficient that they have at least the same reactivity. It is not necessary that only the epoxy groups contained in the acrylic copolymer react selectively.

In this case, the A, B and C stages show the degree of curing of the adhesive. The A stage is in a substantially uncured state and has not gelled, and is in a state in which heat generation of 0 to 20% of the total heat generation amount of curing when measured using DSC is finished. The B stage is in a state where it is slightly cured and gelled, and the heat generation of 20 to 60% of the total curing heat value is finished. The C stage is in a state in which the curing has progressed considerably and has gelled, and the heat generation of 60 to 100% of the total curing heat value has finished.

Regarding the determination of gelation, after immersing the adhesive in a solvent having high permeability such as THF (tetrahydrofuran) and allowing it to stand at 25 ° C. for 20 hours, the adhesive is not completely dissolved and is in a swollen state. It was determined that the product gelled. In addition, it experimentally determined as follows.

Immerse the adhesive (weight W1) in THF,
After standing at 5 ° C. for 20 hours, the non-dissolved content was 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 mathematical expression (2). Those with a THF extraction rate of more than 80% by weight were determined not to be gelled, and those with a THF extraction rate of 80% by weight or less were determined to be gelled.

In the present invention, by adding a filler, the melt viscosity can be increased and the thixotropic property can be exhibited, so that the above effect can be further increased.

Further, in addition to the above effects, properties such as improvement of heat dissipation of the adhesive, imparting of flame retardancy to the adhesive, giving proper viscosity at the temperature at the time of adhesion, and improvement of surface hardness can be imparted. . (Brief Description of Drawings) FIG. 1A is a sectional view of a single-layer thermosetting adhesive film according to the present invention, and FIG. 1B is a sectional view of a three-layer adhesive film according to the present invention.

FIG. 2 is a sectional view of a semiconductor mounting substrate in which an adhesive member is thermocompression bonded to an organic wiring substrate.

FIG. 3 is a sectional view of a semiconductor mounting substrate in which an adhesive member is thermocompression bonded to an organic wiring substrate.

FIG. 4 is a sectional view of the semiconductor device of the present invention.

FIG. 5 is a sectional view of another example of the semiconductor device of the present invention.

FIG. 6 is a sectional view showing a manufacturing process of an embodiment of a semiconductor mounting substrate and a semiconductor device.

FIG. 7 is a sectional view showing a manufacturing process of another embodiment of the semiconductor mounting substrate and the semiconductor device.

FIG. 8 is a sectional view of another example of the semiconductor device of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION Various embodiments of the present invention will be described below with reference to the drawings. <Example 1> Fig. 1 (a) is a cross-sectional view of a single-layer thermosetting adhesive film, and the cured product has a modulus of elasticity at 25 ° C of 10 to 2000 MPa as measured by a dynamic viscoelastic device. And an elastic modulus at 260 ° C. of 3 to 50
It is composed of a thermosetting adhesive 1 in a semi-cured state, which is defined in the range of MPa and has finished generating 10 to 40% of the total amount of heat generated by curing when measured using a DSC (differential calorimeter). An epoxy group-containing acrylic copolymer film which was dried so that the amount of solvent remaining in the thermosetting adhesive film was 2% or less was used.

FIG. 1B shows a sectional view of a three-layer adhesive film in which the thermosetting adhesive 1 is applied to both sides of the polyimide film 2. In this example, Upilex (trade name) with a thickness of 50 μm manufactured by Ube Industries, Ltd. was used as the polyimide film.

FIG. 2 is a sectional view of a semiconductor mounting substrate in which an adhesive member 3 is thermocompression bonded to an organic wiring substrate 4, which is suitable for connecting a semiconductor terminal portion and a wiring substrate side terminal portion by a wire bonding method. Is suitable for connecting the semiconductor terminal portion and the wiring board side terminal portion by the TAB inner bonding method.
6 is a cross-sectional view of a semiconductor mounting substrate in which the adhesive member 3 is thermocompression bonded to the tape-shaped wiring substrate 5. FIG. 4 shows a semiconductor device in which a chip 6 is face-up adhered to the semiconductor mounting substrate of FIG. 2 and a semiconductor terminal portion and a wiring board side terminal portion are wire-bonded with a wire 7 and sealed with a sealing material. Cross section,
In FIG. 5, the chip 6 is bonded face down to the semiconductor mounting substrate of FIG. 3 and then the semiconductor terminal portion and the substrate side terminal portion are connected by the TAB inner bonding method.
FIG. 6 is a cross-sectional view of a semiconductor device having an end surface sealed with a liquid sealing material 8. As shown in FIG. 8, the wiring 9 may be formed on the side of the substrate opposite to the side where the semiconductor chips are mounted. In this case, the external connection terminal 12 is formed on the surface of the wiring 9 formed on the side opposite to the semiconductor chip mounting side. The exposed portion of the wiring 9 is covered with the resist 11.

FIG. 6 shows a manufacturing process of a semiconductor mounting substrate and a semiconductor device.

The cured product has a modulus of elasticity at 25 ° C. in the range of 10 to 2000 MPa and a modulus of elasticity at 260 ° C. of 3 to 50 MPa as measured by a dynamic viscoelasticity apparatus.
The thermosetting adhesive tape (adhesive which is defined in the range of a and is composed of the thermosetting adhesive 1 in a semi-cured state in which the heat generation of 10 to 40% of the total heat value for curing when measured using DSC is finished. The member 3 is cut into a predetermined size by a cutting press (FIG. 6A).

The cut thermosetting adhesive tape 3 is provided with a single layer of Cu wiring, and a polyimide film substrate (organic wiring substrate) 4 is formed with through holes for external solder terminals.
After precisely aligning with the upper surface, thermocompression bonding is performed with a hot press to obtain a semiconductor mounting substrate (FIG. 6B).

In this example, the cutting of the thermosetting adhesive film, the precise positioning mounting and temporary fixing on the polyimide film substrate are individually performed, and then the mounted thermosetting adhesive films are collectively pressed by a hot press. Seven frames of frame-shaped semiconductor mounting substrates were obtained by pressure bonding. Further, in this example, before the step of cutting the thermosetting adhesive film 3, an eliminostat (static electricity removal) step of blowing charged air is performed, and the charged insulating film is attached to the jig during the cutting step. Prevented from sticking. In addition, the upper mold of the heat press that contacts the thermosetting adhesive film 3 for temporary adhesion and batch main adhesion is subjected to Teflon or silicon release surface treatment, so that the thermosetting film becomes the upper mold. Prevented sticking. A semiconductor chip 6 is precisely positioned and mounted face-up on the thus-obtained multiple semiconductor mounting frame substrate, and a chip mounting process is performed in which the semiconductor chip 6 is pressed and bonded by a hot press. In this example, the heating temperature on the semiconductor chip side was set at least higher than that on the semiconductor mounting substrate side, and heating / press bonding was performed from both sides.

After that, a wire bonding step of wire-bonding the semiconductor chip side terminal portion and the substrate side terminal portion with a gold wire (FIG. 6C), and transfer molding using an epoxy type encapsulant and sealing. The semiconductor device according to the present invention is obtained through the encapsulating step (FIG. 6D) and the solder ball forming step of forming the external terminals 9 by mounting the solder balls and performing the reflow step (FIG. 6).
(E)). As the sealing material 8, a biphenyl epoxy sealing material CEL-9200 (trade name) manufactured by Hitachi Chemical was used. <Comparative Example 1> An epoxy resin was used as a main component on the upper surface of a polyimide film wiring substrate (the same as that used in Example 11) on which one layer of Cu wiring was formed and through holes for external solder terminals were formed. The elastic modulus at 25 ° C. of the cured product measured by DMA (Dynamic Viscoelasticity Measuring Device) is 3000 MPa.
The insulative liquid adhesive of was dropped and applied by a die bonder, and the semiconductor chip was precisely positioned and mounted. Then, after a predetermined curing time in a clean oven,
A semiconductor device was obtained through the same wire bonding process, sealing process, and solder ball forming process as in Example 1. Comparative Example 2 The same polyimide wiring board as that used in Example 1 was prepared by using a silicone resin as a main component and a cured product thereof.
An insulating liquid adhesive having a modulus of elasticity at 10 ° C. of 10 MPa and a modulus of elasticity at 260 ° C. that is too small to measure is dropped and applied by a die bonder, a semiconductor chip is mounted, and then, as in Example 1. A semiconductor device was obtained through the same steps. <Embodiment 2> FIG. 7 shows a manufacturing process of a semiconductor mounting substrate and a semiconductor device.

The elastic modulus of the cured product at 25 ° C. measured by a dynamic viscoelastic device is in the range of 10 to 2000 MPa, and the elastic modulus at 260 ° C. is 3 to 50 MPa.
The thermosetting adhesive tape (adhesive which is defined in the range of a and is composed of the thermosetting adhesive 1 in a semi-cured state in which the heat generation of 10 to 40% of the total heat value for curing when measured using DSC is finished. The member 3 is cut into a predetermined size by a cutting press (FIG. 7A).

The cut thermosetting adhesive tape 3 is precisely formed on the upper surface of the polyimide film substrate 5 on which one layer of Cu wiring is provided and inner lead portions and through holes for external solder terminals similar to those of the TAB tape are formed. Then, the semiconductor mounting substrate was obtained by thermocompression bonding with a hot press (FIG. 7 (b)).

In this example, the multiple semiconductor mounting frame substrate was subjected to the static electricity removing step before the cutting step described in Example 1 and the same step of releasing surface treatment on the upper surface of the hot press. Obtained.

After that, the semiconductor chips 6 were precisely mounted face down on the semiconductor mounting frame substrate, sequentially mounted, and thermocompression bonded by a heat press (FIG. 7C). After that, the Cu inner lead portions 10 that are the terminals on the substrate side are individually subjected to inner lead bonding using the TAB inner lead bonder (in this example, a single point bonder) to connect to the terminal portion on the chip side (FIG. 7).
(D)), the chip end surface and the upper surface of the polyimide film substrate 5 are covered with an epoxy liquid encapsulating material 8 by dispensing (FIG. 7E), and a semiconductor device is obtained after a predetermined heating / curing time. (Fig. 7 (f)). In this example, the inner lead portion was made of Cu and Sn-plated, and the semiconductor terminal portion was made of Au-plated bump to be connected by Au / Sn bonding. <Comparative Example 3> An epoxy resin was used as the main component on the upper surface of the same polyimide film substrate as in Example 2 in which one layer of Cu wiring was provided and inner leads of the TAB tape and through holes for external solder terminals were formed. , Its cured product DMA
An insulating liquid adhesive having an elastic modulus of 3000 MPa at 25 ° C. measured in 1. was dropped and applied by a die bonder, and a semiconductor chip was precisely positioned and mounted. However, the resin flowed to the inner bonding portion, and the inner bonding could not be performed thereafter. However, as in Example 2, the end face of the chip was sealed with a liquid sealing material mainly containing epoxy resin to form a solder ball. A comparative product was obtained. <Comparative Example 4> On the upper surface of the same polyimide film substrate as in Example 2 in which a single layer of Cu wiring was provided, and the inner lead portion of the TAB tape and the through hole for the external solder terminal were formed, the main component was silicon resin. An insulating liquid adhesive having an elastic modulus at 25 ° C. of 10 MPa at 25 ° C. and an elastic modulus at 260 ° C. which is too small to be measured was dropped and applied with a die bonder to obtain a semiconductor as in Example 2. Equipped with a chip. However, the resin flowed to the inner bonding portion, and the inner bonding could not be performed thereafter. However, as in Example 2, the end face of the chip was sealed with a liquid sealing material mainly containing epoxy resin to form a solder ball. A comparative product was obtained. <Comparative example 5> Silicone resin as a main component and its cured product 2
An insulating liquid adhesive having a modulus of elasticity at 5 ° C. of 10 MPa and a modulus of elasticity at 260 ° C. that is too small to measure is cast on a Teflon plate, and then cured at a predetermined heating temperature / time to lower the temperature. An elastic film was obtained. A thermosetting adhesive mainly composed of the epoxy resin described in Comparative Example 3 was applied to both surfaces of this film, and one layer of Cu wiring was applied to the inner leads of the TAB tape and through holes for external solder terminals. On the upper surface of the same polyimide film substrate as that of Example 2 in which is formed, thermocompression bonding is performed by hot pressing, and then the semiconductor chip is bonded face down, and then the inner lead bonding step and the sealing step described in Example 2 are performed. A comparative product having solder balls formed thereon was obtained. With respect to the semiconductor devices of Examples 1 and 2 and Comparative Examples 1 to 5, a moisture absorption reflow test was conducted and FR-4 was used.
Table 1 shows the results of the temperature cycle test conducted on each semiconductor device reflow-mounted on the wiring board. Regarding the moisture absorption reflow test, the maximum temperature was 2 after absorbing moisture for 24 hours and 48 hours under the condition of 85 ° C and 85% RH before moisture absorption.
The results of examining peeling and cracks in a test product subjected to IR reflow at 40 ° C. by SAT (ultrasonic probe) are displayed. In addition, the temperature resistance cycle test of each sample is performed at -25 ° C (30 minutes, air) to 150 ° C (3
After performing a temperature cycle of 0 minutes for the air), the connection resistance of the solder balls of the package external terminals was measured by the 4-terminal method, and those having a resistance of 50 mΩ or more were determined to be defective.

(Note) Reflow resistance ◯: Peeling and voids are extremely small at the interface between the chip 6 and the organic wiring substrates 4, 5 and the thermosetting adhesive 3, and SA
It cannot be detected by T (ultrasonic probe). Δ: When the thermosetting adhesive 3 was applied, embedding between the wirings of the organic wiring board was not sufficient, and voids were observed, and peeling progressed from that location.
3. Poor: The peeling described above reaches the outside of the package, and after reflow, the package is swollen and cracks are observed. It can be observed that the wire is peeled and the wire bonding portion or the inner lead portion is broken. Resistance to temperature cycle ○: The connection resistance of the solder ball connection does not change. X: There is at least one terminal having a connection resistance of the solder ball connection portion exceeding 50 mΩ. -: Inner bonding cannot be performed and connection resistance cannot be measured. Cannot be evaluated. <Example 3> 45 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent 200, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) was used as an epoxy resin, and a cresol novolac type epoxy resin (epoxy equivalent 22).
0, using ESCN001 manufactured by Sumitomo Chemical Co., Ltd.)
15 parts by weight, 40 parts by weight of phenol novolac resin (using Priofen LF2882 manufactured by Dainippon Ink and Chemicals, Inc.) as a curing agent for epoxy resin, compatible with epoxy resin and having a weight average molecular weight of 30,000 or more. Phenoxy resin as a molecular weight resin (molecular weight 50,000, using Phenotote YP-50 manufactured by Tohto Kasei Co., Ltd.) 15
150 parts by weight of epoxy group-containing acrylic rubber (molecular weight 1,000,000, HTR-860P-3 manufactured by Teikoku Chemical Industry Co., Ltd.) as epoxy group-containing acrylic rubber,
As a curing accelerator, a curing accelerator 1-cyanoethyl-2-phenylimidazole (Curazole 2PZ-CN) 0.
Methyl ethyl ketone was added to a composition consisting of 5 parts by weight and 0.7 parts by weight of γ-glycidoxypropyltrimethoxysilane (using NUC A-187 manufactured by Nippon Unicar Co., Ltd.) as a silane coupling agent, and the mixture was stirred and mixed. , Vacuum degassed. The obtained varnish is applied on a release-treated polyethylene terephthalate film having a thickness of 75 μm, and dried by heating at 140 ° C. for 5 minutes to form a coating film in a B stage state having a thickness of 80 μm to prepare an adhesive film. did.

The degree of curing of the adhesive in this state is DS
As a result of measurement (temperature rising rate, 10 ° C./min) using C (912 type DSC manufactured by DuPont), it was in a state in which heat generation of 15% of the total curing heat value was finished. Further, the adhesive (weight W1) was immersed in THF, allowed to stand at 25 ° C. for 20 hours, then the non-dissolved portion was filtered through a 200-mesh nylon cloth, and the weight after drying was measured (weight W2). , The THF extraction rate (= (W1-W2) × 100 / W1) was calculated,
The THF extraction rate was 35% by weight. In addition, the storage elastic modulus of the cured adhesive is measured by a dynamic viscoelasticity measuring device (Rheology,
DVE-V4) (sample size length 2
0 mm, width 4 mm, film thickness 80 μm, heating rate 5 ° C./min,
As a result of pulling mode automatic static load), 360 at 25 ° C
It was 4 MPa at 260 ° C. <Example 4> The phenoxy resin used in Example 3 was changed to a carboxyl group-containing acrylonitrile butadiene rubber (molecular weight of 400,000, PNR-1 manufactured by Japan Synthetic Rubber Co., Ltd.) was used, and the same as in Example 1. To produce an adhesive film. The degree of cure of the adhesive in this state is
As a result of measurement using DSC, it was in a state where heat generation of 20% of the total heat generation amount for curing was completed. The THF extraction rate was 35% by weight. Furthermore, the storage elastic modulus of the cured product of the adhesive was measured using a dynamic viscoelasticity measuring device, and was found to be 300 at 25 ° C.
It was 3 MPa at 260 ° C. <Example 5> Adhesive solid content 1 of the adhesive varnish of Example 3
10 parts by volume of silica was added to 00 parts by volume, and an adhesive film was produced in the same manner as in Example 1 using a varnish kneaded with a bead mill for 60 minutes. As a result of measurement using DSC, it was in a state where heat generation of 15% of the total heat generation for curing was completed. The THF extraction rate was 30% by weight. further,
As a result of measuring the storage elastic modulus of the cured adhesive with a dynamic viscoelasticity measuring device, it was 1,500 MPa at 25 ° C. and 260 ° C.
Was 10 MPa. <Example 6> An adhesive film was produced in the same manner as in Example 1 except that the phenoxy resin used in Example 3 was not used. As a result of measurement using DSC, the total heating value for curing was 15
It was in the state of having finished the fever of%. The THF extraction rate is 35
% By weight. Furthermore, the storage elastic modulus of the cured product of the adhesive was measured using a dynamic viscoelasticity measuring device, and was found to be 3 at 25 ° C.
It was 4 MPa at 50 MPa and 260 ° C. Comparative Example 6 An adhesive film was produced in the same manner as in Example 1 except that the amount of the epoxy group-containing acrylic rubber of Example 3 was changed from 150 parts by weight to 50 parts by weight. As a result of measurement using DSC, it was in a state where heat generation of 20% of the total heat generation amount for curing was completed. The THF extraction rate was 40% by weight. Furthermore, the storage elastic modulus of the cured adhesive was measured using a dynamic viscoelasticity measuring device, and as a result, it was 3,000 M at 25 ° C.
Pa was 5 MPa at 260 ° C. Comparative Example 7 An adhesive film was produced in the same manner as in Example 1 except that the amount of the epoxy group-containing acrylic rubber of Example 3 was changed from 150 parts by weight to 400 parts by weight. As a result of measurement using DSC, it was in a state where heat generation of 20% of the total heat generation amount for curing was completed. The THF extraction rate was 30% by weight. Furthermore, as a result of measuring the storage elastic modulus of the cured adhesive using a dynamic viscoelasticity measuring device, 200 MPa at 25 ° C.,
It was 1 MPa at 260 ° C. Comparative Example 8 An adhesive film was produced in the same manner as in Example 1 except that 150 parts by weight of the epoxy group-containing acrylic rubber of Example 3 was changed to phenoxy resin (160 parts by weight of phenoxy resin). The total heating value of this adhesive film is 2
It was 0%, and the THF extraction rate was 90% by weight. Further, the storage elastic modulus at 25 ° C. is 3,400 MPa, 260
It was 3 MPa at ° C. Comparative Example 9 An adhesive film was produced in the same manner as in Example 1 except that the epoxy group-containing acrylic rubber of Example 3 was changed to acrylonitrile butadiene rubber. This adhesive film has a total heating value of 20% and a THF extraction rate of 9%.
It was 0% by weight. The storage elastic modulus is 50 at 25 ° C.
It was 0 MPa and 2 MPa at 260 ° C. A semiconductor device manufactured using the obtained adhesive film was examined for heat resistance, electrolytic corrosion resistance, and moisture resistance. The heat resistance was evaluated by the reflow crack resistance of a semiconductor device sample (a solder ball is formed on one surface) in which a semiconductor chip and a flexible printed wiring board using a polyimide film having a thickness of 25 μm as a base material are bonded with an adhesive film. A temperature cycle test was applied. The evaluation of the reflow crack resistance is performed by passing the sample through an IR (infrared) reflow furnace in which the maximum temperature of the sample surface is 240 ° C. and maintaining this temperature for 20 seconds, and cooling the sample by leaving it at room temperature. The crack was observed twice in the sample. Those without cracks were rated as good, and those with cracks were rated as bad. In the temperature cycle test, the sample was left in an atmosphere of -55 ° C for 30 minutes, and then 125 ° C.
The process of leaving it in the atmosphere of 30 minutes as one cycle,
The number of cycles until destruction occurs is shown. In addition, the evaluation of the electrolytic corrosion resistance is as follows: Line / Space = 75 /
A sample in which a comb-shaped pattern of 75 μm is formed and an adhesive film is adhered thereon is prepared, and the temperature is 85 ° C./85%.
The measurement was performed by measuring the insulation resistance value after 1,000 hours under the condition of applying RH / DC6V. Insulation resistance value is 10
Those showing Ω or more were regarded as good, and those less than 10 Ω were regarded as defective. The moisture resistance was evaluated by observing the peeling and discoloration of the adhesive film after the semiconductor device sample was treated for 96 hours (PCT treatment) in a pressure cooker tester. The case where no peeling or discoloration of the adhesive film was observed was regarded as good, and the case where there was peeling or discoloration was regarded as poor. The results are shown in Table 2.

Examples 3, 4 and 5 are adhesives containing both an epoxy resin and its curing agent, a high molecular weight resin compatible with the epoxy resin, an epoxy group-containing acrylic copolymer and a curing accelerator. Example 6 is an adhesive containing both an epoxy resin and a curing agent thereof, an epoxy group-containing acrylic copolymer, and a curing accelerator, and has storage elastic modulus at 25 ° C. and 260 ° C. defined in the present invention. Shows. These had good reflow crack resistance, temperature cycle test, electrolytic corrosion resistance, and PCT resistance.

In Comparative Example 6, since the amount of the epoxy group-containing acrylic copolymer specified in the present invention is small, the storage elastic modulus is high, the stress cannot be relaxed, and the reflow crack resistance and the result in the temperature cycle test are poor. Unreliable. In Comparative Example 7, the storage elastic modulus is low and good because the amount of the epoxy group-containing acrylic copolymer specified in the present invention is too large, but the handleability of the adhesive film is poor. Comparative Example 8 has a high storage elastic modulus because it does not contain the epoxy group-containing acrylic copolymer specified in the present invention, and like Comparative Example 1, stress cannot be relaxed and reflow crack resistance and temperature cycle test are performed. The result in is bad. Comparative Example 9 did not contain the epoxy group-containing acrylic copolymer specified in the present invention, contained the other rubber components, and had a low storage elastic modulus at 25 ° C., but showed poor electrolytic corrosion resistance. <Example 7> 45 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent 200, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) as an epoxy resin, cresol novolac type epoxy resin (epoxy equivalent 220, Sumitomo Chemical Co., Ltd.) Product name ESCN0
15 parts by weight, as a curing agent for epoxy resin, phenol novolac resin (using Priofen LF2882 manufactured by Dainippon Ink and Chemicals, Inc.)
40 parts by weight, 15 parts by weight of a phenoxy resin (a molecular weight of 50,000, Phenototo YP-50 manufactured by Toto Kasei Co., Ltd. is used) as a high molecular weight resin having compatibility with an epoxy resin and a weight average molecular weight of 30,000 or more. , Epoxy group-containing acrylic rubber as epoxy group-containing acrylic copolymer (molecular weight 1 million, HTR manufactured by Teikoku Chemical Industry Co., Ltd.
-860P-3) 150 parts by weight, curing accelerator 1-cyanoethyl-2-phenylimidazole (Curazole 2PZ-CN) 0.5 parts by weight as a curing accelerator, γ-glycidoxypropyl trisilane as a silane coupling agent. Methoxysilane (NU under the trade name of Nippon Unicar Co., Ltd.
Methyl ethyl ketone was added to a composition of 0.7 part by weight (using CA-187), and the mixture was stirred and mixed, and degassed in vacuum. The obtained varnish was applied onto a plasma-treated polyimide film having a thickness of 50 μm, and the coating was performed at 130 ° C. for 5 minutes.
After heat-drying for a minute, a coating film in a B stage state having a film thickness of 50 μm was formed to prepare a single-sided adhesive film. Next, the same varnish was applied to the surface of the polyimide film of this single-sided adhesive film on which the adhesive was not applied, and the film was heated and dried at 140 ° C. for 5 minutes to form a coating film in a B stage state having a thickness of 50 μm. A double-sided adhesive film having a three-layer structure was produced.

The degree of curing of the adhesive component of the adhesive film in this state is DSC (trade name 912 type D manufactured by DuPont).
As a result of measurement using SC) (heating rate, 10 ° C./min), it was in a state where heat generation of 15% of the total heat generation amount for curing was completed. Also, soak the adhesive (weight W1) in THF, and
After left at 20 ° C. for 20 hours, the non-dissolved content was filtered through a 200-mesh nylon cloth, and the weight after drying was measured (weight W2), and the THF extraction rate (= (W1-W2) × 1
00 / W1), the THF extraction rate was 35% by weight. Further, the storage elastic modulus of the cured product of the adhesive was measured using a dynamic viscoelasticity measuring device, and as a result, 360 ° at 25 ° C.
It was 4 MPa at 260 ° C. <Example 8> The phenoxy resin used in Example 7 was replaced by a carboxyl group-containing acrylonitrile butadiene rubber (molecular weight 400,000, PNR-1 manufactured by Nippon Synthetic Rubber Co., Ltd., trade name).
Was used), and a double-sided adhesive film having a three-layer structure was produced in the same manner as in Example 1. The degree of cure of the adhesive component of the adhesive film in this state was measured by DSC, and as a result, it was in a state where heat generation of 20% of the total heat generation for curing was finished. The THF extraction rate was 35% by weight. Further, the storage elastic modulus of the cured adhesive was measured using a dynamic viscoelasticity measuring device.
It was 3 MPa at ° C. <Example 9> The adhesive varnish used in Example 7 was applied to a thickness of 50.
Adhesion for application on a μm polyethylene terephthalate film, heating and drying at 140 ° C. for 5 minutes to form a B-stage coating film with a film thickness of 50 μm, and attaching it to a heat-resistant thermoplastic film as a core material. A film was made. Using a vacuum laminator on both surfaces of a polyimide film having a thickness of 50 μm, which was subjected to plasma treatment, this adhesive film was used, the laminator roll temperature was 80 ° C., and the feed rate was 0.
A double-sided adhesive film having a three-layer structure was produced by laminating them under a laminating condition of 2 m / min and a linear pressure of 5 kg. The degree of cure of the adhesive component of the adhesive film in this state was 20% of the total curing heat value as measured by DSC.
It was in the state of having finished the fever. The THF extraction rate was 35% by weight. Furthermore, the storage elastic modulus of the cured product of the adhesive was measured using a dynamic viscoelasticity measuring device.
It was 4 MPa at 0 MPa and 260 ° C. <Comparative Example 10> The adhesive varnish used in Example 7 has a thickness of 5
It was applied on a polyethylene terephthalate film having a thickness of 0 μm and dried by heating at 140 ° C. for 5 minutes to form a coating film in a B-stage state having a thickness of 75 μm to prepare an adhesive film. Two of these adhesive films were used and laminated under the same laminating conditions as in Example 3 to produce an adhesive film that does not use a core material. The total curing heat value of the adhesive component of the obtained adhesive film was 20%, and the THF extraction rate was 35% by weight. Also, the storage modulus is 360M at 25 ° C.
Pa was 4 MPa at 260 ° C. <Comparative Example 11> A double-sided adhesive film having a three-layer structure was produced in the same manner as in Example 1 except that the polyimide film used as the heat-resistant thermoplastic film serving as the core material of Example 7 was changed to a polypropylene film. The total exothermic heat of curing of the adhesive component of this adhesive film was 20%, and the THF extraction rate was 35% by weight. The storage elastic modulus is 25
It was 360 MPa at 0 ° C and 4 MPa at 260 ° C. Comparative Example 12 A double-sided adhesive film having a three-layer structure was produced in the same manner as in Example 1 except that the epoxy group-containing acrylic copolymer of Example 7 was changed to a phenoxy resin (phenoxy resin 165 parts by weight). The total heat of curing of the adhesive component of this adhesive film was 20%, and the THF extraction rate was 9%.
It was 0% by weight. The storage modulus at 25 ° C is 3,
It was 400 MPa and 3 MPa at 260 ° C. Comparative Example 13 A double-sided adhesive film having a three-layer structure was produced in the same manner as in Example 1 except that the epoxy group-containing acrylic copolymer of Example 7 was changed to acrylonitrile butadiene rubber. The total exothermic heat of curing of this adhesive film adhesive component was 20%, and the THF extraction rate was 90% by weight.
Further, the storage elastic modulus is 500 MPa at 25 ° C., 260 ° C.
Was 2 MPa.

With respect to the obtained adhesive film, heat resistance,
The 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 a double-sided adhesive film having a three-layer structure were applied. To evaluate the resistance to reflow cracking, the sample was passed through an IR reflow furnace where the maximum temperature of the sample surface was 240 ° C and the temperature was set to maintain this temperature for 20 seconds, and the sample was allowed to stand at room temperature and cooled twice. The cracks in the sample were observed. Those without cracks were rated as good, and those with cracks were rated as bad. In the temperature cycle test, the sample was left in an atmosphere of -55 ° C for 30 minutes, and then 125 ° C.
The process of leaving it in the atmosphere of 30 minutes as one cycle,
The number of cycles until destruction occurs is shown. In addition, the evaluation of the electrolytic corrosion resistance is as follows: Line / Space = 75 /
A sample with a comb pattern of 75 μm formed and an adhesive film attached on top of this is prepared, and 85 ° C./85% R
It was performed by measuring the insulation resistance value after 1,000 hours under the condition of H / DC6V application. Insulation resistance value is 10Ω
Those showing the above were regarded as good, and those having less than 10Ω were regarded as bad. The moisture resistance was evaluated by observing the peeling and discoloration of the adhesive film after the heat resistance evaluation sample was treated for 96 hours (PCT treatment) in a pressure cooker tester. The case where no peeling or discoloration of the adhesive film was observed was regarded as good, and the case where there was peeling or discoloration was regarded as poor. The results are shown in Table 3.

Each of Examples 7, 8 and 9 is a double-sided adhesive film having a three-layer structure in which a heat resistant thermoplastic film is used as a core material, and an epoxy resin and its curing agent, an epoxy resin are used as an adhesive component. Since both the compatible high molecular weight resin and the epoxy group-containing acrylic copolymer are contained, the storage elastic modulus at 25 ° C. and 260 ° C. specified in the present invention is shown.
These are excellent in handleability, reflow crack resistance,
The temperature cycle test, the electrolytic corrosion resistance and the PCT resistance were good.

Comparative Example 10 was inferior in handleability since it was not a three-layer double-sided adhesive film using a heat-resistant thermoplastic film as the core material specified in the present invention. In Comparative Example 11, a polypropylene film having poor heat resistance was used as the core material, and therefore the reflow resistance and the temperature cycle test result were poor. Comparative Example 12 was a composition not containing the epoxy group-containing acrylic copolymer specified in the present invention, and therefore exhibited a high value exceeding the specified storage elastic modulus at 25 ° C., and reflow crack resistance. And the results of the temperature cycle test were inferior. Comparative Example 13 is 25 ° C. defined without the epoxy group-containing acrylic rubber specified in the present invention.
Since it was adjusted to the storage elastic modulus at
The result was inferior in CT property. (Industrial Applicability) According to the present invention, it is possible to manufacture a semiconductor package having excellent moisture absorption reflow resistance and temperature cycle resistance when mounted on a mother board.

Since the adhesive and the adhesive film of the present invention have a low elastic modulus near room temperature, when a semiconductor chip is mounted on a rigid printed wiring board or a flexible printed wiring board typified by a glass epoxy substrate or a polyimide substrate. The thermal stress at the time of heating / cooling caused by the difference in the thermal expansion coefficient of can be relaxed. Therefore, no cracks are observed during reflow and the heat resistance is excellent. Also, it contains an epoxy group-containing acrylic copolymer as a low elastic modulus component, and has excellent characteristics such as electrolytic corrosion resistance, moisture resistance, and little deterioration when a humidity resistance test is performed under severe conditions such as PCT treatment. Material can be provided.

The three-layer double-sided adhesive film using the heat-resistant thermoplastic film as the core material of the present invention is excellent in handleability even though the elastic modulus of the adhesive layer near room temperature is low, and It is possible to relieve thermal stress during heating and cooling caused by a difference in thermal expansion coefficient when a semiconductor chip is mounted on a rigid printed wiring board or a flexible printed wiring board typified by a glass epoxy substrate or a polyimide substrate. Therefore, no cracks are observed during reflow and the heat resistance is excellent. Also, it contains an epoxy group-containing acrylic copolymer as a low elastic modulus component, and has excellent characteristics such as electrolytic corrosion resistance, moisture resistance, and little deterioration when a humidity resistance test is performed under severe conditions such as PCT treatment. Material can be provided.

The semiconductor package of the present invention in which the external terminals are arranged on the back surface of the substrate in the form of an area array is particularly suitable for being mounted on a portable electronic device or a small electronic device for PDA use.

[Brief description of drawings]

FIG. 1 (a) is a sectional view of a single-layer thermosetting adhesive film according to the present invention, and FIG. 1 (b) is a sectional view of a three-layer adhesive film according to the present invention.

FIG. 2 is a cross-sectional view of a semiconductor mounting substrate in which an adhesive member is thermocompression bonded to an organic wiring substrate.

FIG. 3 is a cross-sectional view of a semiconductor mounting substrate in which an adhesive member is thermocompression bonded to an organic wiring substrate.

FIG. 4 is a sectional view of a semiconductor device of the present invention.

FIG. 5 is a cross-sectional view of another example of the semiconductor device of the present invention.

FIG. 6 is a cross-sectional view showing a manufacturing process of an embodiment of a semiconductor mounting substrate and a semiconductor device.

FIG. 7 is a cross-sectional view showing the manufacturing process of another embodiment of the semiconductor mounting substrate and the semiconductor device.

FIG. 8 is a cross-sectional view of another example of the semiconductor device of the present invention.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09J 163/00 C09J 163/00 171/10 171/10 201/00 201/00 H01L 21/52 H01L 21 / 52 E (72) Inventor Sadakazu Inada 248 Onnakata, Shimodate, Ibaraki 248 Kawashima House 4-103 (72) Inventor Hiroyuki Kuritani 3-28-12 Sachimachi, Shimodate, Ibaraki Inventor Aizo Kaneda Yokohama, Kanagawa 2456-47, Kamiyabe-cho, Totsuka-ku (72) Inventor Takeo Toyama 3-4-1 Matsushiro Tsukuba, Ibaraki Prefecture Hitachi Matsushiro House B408 (72) Inventor Yoshihiro Nomura 1-4-9, Sakuradai, Ichihara, Chiba (72) Inventor Yoichi Hosokawa 1-4-86 Sakuradai, Ichihara City, Chiba Prefecture (72) Inventor Hiroshi Kirihara 173 Iinuma, Ichihara City, Chiba Hitachi Chemical Iinuma Dormitory No. 122 (72) Akira Kageyama 5-5, Nodera, Niiza City, Saitama Prefecture 8-303 F term (see ) 4J004 AA10 AA12 AA13 CA03 CA06 CB03 CC02 EA05 FA05 FA08 4J040 DF041 DF051 DF061 EB032 EC001 EE062 EG002 GA11 HA116 HA306 HB22 HB38 HC01 HD05 HD39 JA09 JB02 KA16 KA42 LA02 PA23 5F047 AA17 BA21 BB03 BB16

Claims (49)

[Claims] 1. A semiconductor device in which a semiconductor chip is mounted on an organic supporting substrate via an adhesive member, wherein the side of the organic supporting substrate on which the semiconductor chip is mounted,
A predetermined wiring is formed on at least one side of the side opposite to the side on which the semiconductor chip is mounted, and an external connection is formed on the side opposite to the side on which the semiconductor chip of the organic support substrate is mounted. Terminals are formed in an area array shape, the predetermined wiring is connected to the semiconductor chip terminal and the external connection terminal, and at least a connecting portion between the semiconductor chip terminal and the predetermined wiring is resin-sealed. The adhesive member includes an adhesive layer, and the storage elastic modulus at 25 ° C. measured by a dynamic viscoelasticity measuring device of the adhesive is 10 to 2000 MPa and the storage elastic modulus at 260 ° C. is 3 to. A semiconductor device having a pressure of 50 MPa. 2. The semiconductor device according to claim 1, wherein the predetermined wiring and the semiconductor chip terminal are connected by wire bonding or directly. 3. The semiconductor device according to claim 1, wherein the adhesive member is in the form of a film. 4. The semiconductor device according to claim 1, wherein the resin component of the adhesive contains an epoxy resin, an epoxy group-containing acrylic copolymer, an epoxy resin curing agent, and an epoxy resin curing accelerator. 5. The semiconductor device according to claim 1, wherein the adhesive member has a structure in which adhesive layers are formed on both surfaces of a core material. 6. The semiconductor device according to claim 5, wherein the core material is a heat resistant thermoplastic film. 7. The semiconductor device according to claim 6, wherein the heat-resistant thermoplastic film has a glass transition temperature of 200 ° C. or higher. 8. The semiconductor device according to claim 7, wherein the heat-resistant thermoplastic film having a glass transition temperature of 200 ° C. or higher is polyimide, polyether sulfone, polyamide imide or polyether imide. 9. The semiconductor device according to claim 7, wherein the heat-resistant thermoplastic film is a liquid crystal polymer. 10. The semiconductor device according to claim 1, wherein the residual solvent amount in the adhesive layer is 5% by weight or less. 11. A semiconductor chip mounting substrate of an organic substrate on which a semiconductor chip is mounted via an adhesive member, the semiconductor substrate mounting side of the organic substrate and the semiconductor chip mounting side of the organic substrate. A predetermined wiring is formed on at least one side of the opposite side, and an external connection terminal is formed in an area array shape on the opposite side of the side where the semiconductor chip of the organic substrate is mounted, The adhesive member includes an adhesive layer, and is measured by a dynamic viscoelasticity measuring device of the cured adhesive product.
Storage elastic modulus at 5 ° C is 10 to 2000 MPa and 260 ° C
The storage elastic modulus is 3 to 50 MPa, and the adhesive member has a predetermined size and is formed at a predetermined location on the organic substrate. 12. The adhesive member is in the form of a film.
The semiconductor chip mounting substrate as described above. 13. The resin component of the adhesive contains an epoxy resin, an epoxy group-containing acrylic copolymer, an epoxy resin curing agent and an epoxy resin curing accelerator.
2. The semiconductor chip mounting substrate according to 2. 14. The substrate for mounting a semiconductor chip according to claim 11, wherein the adhesive member has a structure in which an adhesive layer is formed on both surfaces of a core material. 15. The semiconductor chip mounting substrate according to claim 14, wherein the core material is a heat resistant thermoplastic film. 16. The substrate for mounting a semiconductor chip according to claim 15, wherein the glass transition temperature of the heat resistant thermoplastic film is 200 ° C. or higher. 17. The semiconductor chip mounting substrate according to claim 16, wherein the heat resistant thermoplastic film having a glass transition temperature of 200 ° C. or higher is polyimide, polyether sulfone, polyamide imide or polyether imide. 18. The semiconductor chip mounting substrate according to claim 15, wherein the heat resistant thermoplastic film is a liquid crystal polymer. 19. The semiconductor chip mounting substrate according to claim 11, wherein the residual solvent amount in the adhesive layer is 5% by weight or less. 20. The semiconductor chip mounting according to claim 11, wherein the adhesive member formed at a predetermined location on the organic substrate is a film punched to a predetermined size by a punching die. Substrate. 21. An adhesive member formed at a predetermined position on an organic substrate generates 10 to 40% of the total curing heat value when the adhesive of the adhesive member is measured using a differential calorimeter. The semiconductor chip mounting substrate according to any one of claims 11 to 20, which is a film in a semi-cured state that has been finished, and is a film that is thermocompression-bonded to the organic substrate after being cut into a predetermined size. 22. A predetermined wiring is formed on the side on which the semiconductor chip is mounted, and an external connection terminal is formed on the organic substrate on the side opposite to the side on which the semiconductor chip is mounted in an area array form. Of cured products measured by dynamic viscoelasticity measuring device
An adhesive member comprising an adhesive layer having a storage elastic modulus at 10 ° C to 2000 MPa and a storage elastic modulus at 260 ° C of 3 to 50 MPa, wherein the adhesive has a total curing calorific value when measured using a differential calorimeter. For mounting a semiconductor chip, which comprises cutting an adhesive member film in a semi-cured state in which 10 to 40% of heat generation has been cut into a predetermined size and thermocompression-bonded onto the organic substrate. Substrate manufacturing method. 23. The adhesive member films according to claim 22, which have been cut, are individually precisely positioned, and then temporarily bonded by a hot press,
The semiconductor chip mounting device according to claim 22, wherein a plurality of adhesive member films are placed on a plurality of organic substrate according to claim 22 and then adhered together by pressing with a heated release surface treatment die. Substrate manufacturing method. 24. The method for producing a substrate for mounting a semiconductor chip according to claim 23, wherein the surface release material of the mold for surface treatment for release is at least one of Teflon (registered trademark) and silicone. 25. The manufacturing of a semiconductor mounting substrate according to claim 22, wherein at least one step of removing the static electricity generated during transport of the adhesive member film is added before the adhesive member film cutting step. Law. 26. A predetermined wiring is formed on at least one of the side on which the semiconductor chip is mounted and the side opposite to the side on which the semiconductor chip is mounted, and the side opposite to the side on which the semiconductor chip is mounted. When the storage elastic modulus at 25 ° C. of a cured product measured by a dynamic viscoelasticity measuring device is 10 to 2000 MPa and 260 ° C. on a semiconductor chip mounting substrate of an organic substrate on which external connection terminals are formed in an area array shape. A step of adhering an adhesive member including an adhesive layer having a storage elastic modulus of 3 to 50 MPa, a step of mounting a semiconductor chip via the adhesive member, and connecting the predetermined wiring to the semiconductor chip terminal and the external connection terminal And a step of sealing at least a connecting portion between the semiconductor chip terminal and a predetermined wiring with a resin. 27. The method of manufacturing a semiconductor device according to claim 26, comprising the step of heating both the lower surface side and the semiconductor chip side of the semiconductor chip mounting substrate to raise the temperature of at least the chip side. 28. (1) Epoxy resin and its curing agent 1
And an epoxy group-containing acrylic copolymer having a Tg (glass transition temperature) of −10 ° C. or higher and a weight average molecular weight of 800,000 or higher, containing 2 parts by weight of (2) glycidyl (meth) acrylate and 2 parts by weight. An adhesive containing 100 to 300 parts by weight and (3) 0.1 to 5 parts by weight of a curing accelerator. 29. (1) Epoxy resin and its curing agent 1
Tg containing 00 parts by weight, (2) 10 to 40 parts by weight of a high molecular weight resin compatible with an epoxy resin and having a weight average molecular weight of 30,000 or more, and (3) 2 to 6% by weight of glycidyl (meth) acrylate.
100 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a (glass transition temperature) of -10 ° C or more and a weight average molecular weight of 800,000 or more, and (4) curing accelerator 0.
An adhesive containing 1 to 5 parts by weight. 30. (1) Tg containing 100 parts by weight of an epoxy resin and a phenol resin, and (2) 2 to 6% by weight of glycidyl (meth) acrylate is -10 ° C. or higher and the weight average molecular weight is 800,000 or higher. Epoxy group-containing acrylic copolymer 100-
An adhesive containing 300 parts by weight and 0.1 to 5 parts by weight of (3) a curing accelerator. 31. A Tg containing (1) 100 parts by weight of an epoxy resin and its phenolic resin, (2) 10 to 40 parts by weight of a phenoxy resin, and (3) 2 to 6% by weight of glycidyl (meth) acrylate.
An adhesive containing 100 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a weight average molecular weight of 800,000 or more and 10 ° C. or more, and (4) a curing accelerator of 0.1 to 5 parts by weight. 32. The adhesive according to any one of claims 27 to 31, wherein the adhesive is in a state in which the heat generation of 10 to 40% of the total curing heat value when measured using a differential calorimeter is finished. 33. The storage elastic modulus of the cured product of the adhesive is 10 to 200 at 25 ° C. when measured using a dynamic viscoelasticity measuring device.
The adhesive according to any one of claims 27 to 32, which has a pressure of 0 MPa and a pressure of 3 to 50 MPa at 260 ° C. 34. An inorganic resin is used as an adhesive resin component 100.
The adhesive according to any one of claims 27 to 32, which contains 2 to 20 parts by volume with respect to the parts by volume. 35. The inorganic filler is alumina.
4. The adhesive according to 4. 36. The inorganic filler is silica.
Adhesive described. 37. An adhesive film obtained by forming the adhesive according to any one of claims 27 to 36 on a base film. 38. A semiconductor device in which a semiconductor chip and a wiring board are bonded together by using the adhesive film according to claim 37. 39. A heat-resistant thermoplastic film is used as a core material, and (1) 100 parts by weight of an epoxy resin and a curing agent therefor, and (2) 2 to 6% by weight of glycidyl (meth) acrylate are used on both surfaces of the core material. 100 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a Tg (glass transition temperature) of -10 ° C or more and a weight average molecular weight of 800,000 or more, and (3) a curing accelerator of 0.1 to 5 parts by weight. A double-sided adhesive film having a three-layer structure having an adhesive including and. 40. A heat-resistant thermoplastic film is used as a core material, and (1) 100 parts by weight of an epoxy resin and a curing agent therefor, and (2) a weight average molecular weight compatible with the epoxy resin on both sides of the core material. Containing 10 to 40 parts by weight of a high molecular weight resin of 30,000 or more and 2 to 6% by weight of (3) glycidyl (meth) acrylate.
100 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a (glass transition temperature) of -10 ° C or more and a weight average molecular weight of 800,000 or more, and (4) curing accelerator 0.
A three-layer double-sided adhesive film having an adhesive containing 1 to 5 parts by weight. 41. A heat-resistant thermoplastic film is used as a core material, and (1) 100 parts by weight of an epoxy resin and a phenol resin and (2) 2 to 6% by weight of glycidyl (meth) acrylate are used on both sides of the core material. Epoxy group-containing acrylic copolymer 100 having Tg of −10 ° C. or more and a weight average molecular weight of 800,000 or more
A three-sided double-sided adhesive film having an adhesive containing 300 parts by weight and (3) 0.1 to 5 parts by weight of a curing accelerator. 42. A heat-resistant thermoplastic film is used as a core material, and (1) 100 parts by weight of an epoxy resin and a phenol resin, (2) 10 to 40 parts by weight of a phenoxy resin, and (3) glycidyl on both sides of the core material. Tg containing 2 to 6% by weight of (meth) acrylate is-
Three layers having an adhesive containing 100 to 300 parts by weight of an epoxy group-containing acrylic copolymer having a weight average molecular weight of 800,000 or more at 10 ° C. or more and (4) 0.1 to 5 parts by weight of a curing accelerator. Double-sided adhesive film with a structure. 43. The adhesive according to any one of claims 39 to 42, wherein the adhesive is in a state in which the heat generation of 10 to 40% of the total curing heat value when measured using a differential calorimeter is finished. A double-sided adhesive film having a three-layer structure. 44. The storage elastic modulus of the cured product of the adhesive is 10 to 200 at 25 ° C. when measured using a dynamic viscoelasticity measuring device.
The double-sided adhesive film having a three-layer structure having the adhesive according to any one of claims 39 to 43, which has a pressure of 0 MPa and a pressure of 3 to 50 MPa at 260 ° C. 45. An inorganic filler is used as an adhesive resin component 100.
The double-sided adhesive film having a three-layer structure having the adhesive according to any one of claims 39 to 44, wherein the double-sided adhesive film contains 2 to 20 parts by volume with respect to the parts by volume. 46. A double-sided adhesive film having a three-layer structure having an adhesive according to claim 45, wherein the inorganic filler is alumina or silica. 47. The heat-resistant thermoplastic film used as the core material has a glass transition temperature of 200 ° C. or higher.
A double-sided adhesive film having a three-layer structure according to any one of 1. 48. The glass transition temperature used for the core material is 200 ° C.
43. The double-sided adhesive 00 lum with a three-layer structure according to any one of claims 39 to 42, wherein the heat resistant thermoplastic film is polyimide, polyether sulfone, polyamide imide or polyether imide. 49. The double-sided adhesive film having a three-layer structure according to claim 39, wherein the heat-resistant thermoplastic film used as the core material is a liquid crystal polymer.