JP2002161261A - Thermosetting heat-resistant adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting heat-resistant adhesive film which can be heated, pressed into contact, and cured at a lower temperature and at a lower pressure than those of conventional films with a heated roller laminator a heated press or the like, has excellent processability, when semi-cured, has excellent adhesivity to films such as films of polyimides, metals, silicon metals, epoxy resin, ceramics or the like BOTH when cured or semi-cured, and further has excellent heat resistance when cured. SOLUTION: This thermosetting heat-resistant adhesive film is produced by coating a substrate film with an adhesive composition comprising 25 pts.wt. of an epoxy resin and a curing agent component, 50 to 70 pts.wt. of a siloxane- modified polyamideimide component, 10 to 30 pts. wt. of a rubber component having a mol.wt. of >=50,000, and 0.2 pt.wt. of a curing accelerator and then thermally treating the applied coating in a semi-cured state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive material for electronic parts and semiconductor parts, which can be thermocompression-bonded and cured at a lower temperature and lower pressure than ever before, by using a hot roll laminating, a hot press, etc., and has excellent workability during semi-curing. The present invention relates to a thermosetting heat-resistant adhesive film having excellent adhesiveness to film materials such as polyimid, metal, silicon, epoxy, ceramic, etc., both when cured and semi-cured, and also having excellent heat resistance when cured.

[0002]

2. Description of the Related Art Conventionally, as an adhesive for electronic parts and semiconductor parts, there has been used an adhesive sheet material obtained by adding various rubber components to glass epoxy resin or epoxy resin, or a method of applying and bonding a liquid adhesive. Have been. Here, when a glass epoxy reflector is used, there are problems that it is difficult to reduce the thickness of the adhesive layer, it is difficult to ensure adhesion after absorbing moisture, and cutting powder is generated during processing. In the case of adhesive sheet materials in which various rubbers are added to epoxy resin, glass epoxy reflectors have improved workability and adhesion, but the adhesive sheet itself tends to undergo cohesive failure, and the adhesive has heat resistance even after curing. There were drawbacks such as poor. In addition, if an adhesive containing a high Tg material such as polyimito or polyimito as a main component is used to improve heat resistance, bonding and curing at high temperature for a long time under high pressure are required, and the equipment used for bonding and curing is limited. Or with a liquid adhesive, the number of work steps is large, bleeding during application,
There were problems such as poor workability due to misalignment.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and as an adhesive material for electronic parts and semiconductor parts, can be adhesively cured at a lower temperature and in a shorter time than before, has excellent workability at the time of semi-curing, and It is an object of the present invention to provide a thermosetting heat-resistant adhesive film having excellent adhesiveness to film materials such as polyimid, metal, silicon, epoxy, ceramic, etc., both when hardened and semi-hardened, and also having excellent heat resistance when hardened. .

[0004]

The present invention relates to the following. (1) An adhesive composition containing 50 to 70 parts by weight of a siloxane-modified polyamitoimito component and 10 to 30 parts by weight of a rubber component having a molecular weight of 50,000 or more based on a total of 25 parts by weight of an epoxy resin and a curing agent. A thermosetting heat-resistant adhesive film that is applied to a film and heat-treated to a semi-cured state. (2) the ethoxy resin component has an ethoxy equivalent of 350 or more;
The thermosetting heat-resistant adhesive film according to claim 1, which is solid at room temperature of 23 ° C or lower. (3) The thermosetting heat-resistant adhesive film according to (1) or (2), wherein the rubber component having a molecular weight of 50,000 or more is an end group ethoxy-modified acrylonitrile-phthalic acid engine. (4) The thermosetting heat-resistant adhesive film according to any one of claims 1 to 3, wherein a curing rate in a semi-cured state by heat treatment after being applied to the base film is 30 to 60%.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The ethoxy resin used in the present invention is not particularly limited, but is preferably an ethoxy equivalent of 500 or more and a solid at room temperature of 23 ° C. or less, and an ethoxy resin having an ethoxy equivalent of 500 or more. By using a resin, no cutting powder is generated at the time of cutting even in an atmosphere of 10 ° C. As such an epoxy resin, E.coat 1
001, 1003 (manufactured by Yuka Shell Co., Ltd.), Edicron 900,
1050 (manufactured by Dainippon Ink and Chemicals, Inc.).

The curing agent is not particularly limited, and includes, for example, novolac phenol and amine. However, novolac phenol is more preferable in view of workability at the time of semi-curing, and an ethoxy group of an ethoxy resin and a functional group reactive therewith are preferred. It is desirable to add the (hydroxyl group) so as to have an equivalent ratio of 1: 1 to 1: 1.2. Examples of such a phenol novolac curing agent include LF-2882 (manufactured by Dainippon Ink and Chemicals, Inc.) and VP-6371 (manufactured by Hitachi Chemical Co., Ltd.).
Manufactured).

The addition of the siloxane-modified polyamitoimid component enables the adhesive to be cured at a lower temperature and a lower pressure in a shorter time as compared with the conventional ones, and aims at improving the heat resistance of the cured product. The general formula of the siloxane-modified polymer imidate component is shown below.

[0008]

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Here, the addition amount of the siloxane-modified polyamide imidate component is 5 parts by weight based on the total amount of 25 parts by weight of the epoxy resin and the curing agent.
If the amount is less than 0 parts by weight, a sufficient effect of improving heat resistance cannot be obtained. If the amount exceeds 70 parts by weight, the temperature and pressure required for bonding increase, making it difficult to cure the adhesive in a short time at low temperature. It is desirably about 70 parts by weight. Examples of such siloxane-modified polymer imito include PAI-28, PAI-37, and PAI-55 (manufactured by Hitachi Chemical Co., Ltd.).

Further, as the curing accelerator, it is preferable to use various imidazoles. Examples of the imidasole include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and the like, such as 2E4MZ, 2PZ, 2PZ-CN, and 2PZ-CNS (Shikoku Chemicals Co., Ltd.) There is. The curing accelerator is preferably used in a range of 0.02 to 5 parts by weight based on 25 parts by weight of the total amount of the epoxy resin and the curing agent.

The addition of a rubber component having a molecular weight of 50,000 or more is intended to improve the adhesion and moisture resistance of the cured product. Further, the film properties in a semi-cured state (processing Is difficult to secure. Here, if the addition amount is less than 10 parts by weight, a phenomenon of cracking occurs when peeled from the base film during semi-curing. Further, when the amount exceeds 30 parts by weight, there is a problem that the heat resistance of the cured product is rapidly lowered, and the addition amount is desirably 10 to 30 parts by weight. Further, as the rubber component, acrylonitrile-phthalic acid containing ethoxy group is preferable from the viewpoint of compatibility with ethoxy resin, and examples thereof include HTR860P-3 (manufactured by Teikoku Chemical Industry Co., Ltd.).

Further, as an adhesion improving component, a silane coupling agent or the like depending on the purpose may be added. Examples of silane coupling agents include NCUA-187, 189, 1100, 1160 (Nihon Unicar Co., Ltd.) and the like.

[0013] The thermosetting heat-resistant adhesive film is prepared by dissolving the above adhesive composition with an organic solvent such as MEK, toluene, DMF, and DMAC.
It is obtained by applying to a substrate and drying. At this time, the base material is PE
T, polyimid, copper foil, and the like are not particularly limited as long as they can withstand the drying temperature.

Although the drying conditions are not particularly limited, it is necessary to adjust the curing rate of the adhesive film to 30 to 60% depending on the drying conditions.

At this time, if the curing rate is less than 30%, 4%
At a temperature of 0 ° C. or higher, tackiness occurs, and adverse effects such as occurrence of blocking and deterioration of workability occur. Further, when the curing rate is 60% or more, the pressure bonding condition is 190 ° C. or more and the pressure condition is 3 MPa or more, so that it is difficult to bond at low temperature and low pressure. Therefore, the curing rate is desirably 30 to 60%.

Here, the curing rate is defined as follows. DSC calorific value of resin composition in uncured state = A (J / g) DSC calorific value of adhesive film cured by heating and semi-cured = B
(J / g) Curing rate (%) = (AB) / A × 100 This enables short-time pressure bonding at a low temperature and low pressure of 180 ° C (60 minutes) at 180 ° C. It is. It was possible to obtain a thermosetting heat-resistant adhesive film having excellent adhesiveness to film materials such as polyimid, metal, silicon, epoxy, ceramics, etc., both when cured and semi-cured, and also having excellent heat resistance when cured.

[0017]

EXAMPLES The present invention will be described below more specifically based on examples. Hereinafter, “parts” means “parts by weight”.

Example 1 15 parts of epoxy resin epicoat 1001 and curing agent LF
-2882, 10 parts of siloxane-modified polyamitoimito PAI-2
8, 50 parts of the rubber component HTR860P3, 0.2 parts of the curing accelerator 2PZ-CN, and 3 parts of the silane coupling agent A-187, and the mixture was stirred for 1 hour. 180 on PET film
After drying at 15 ° C. for 15 minutes, an adhesive film having a thickness of 25 μm and a curing rate of 30% was prepared.

The evaluation method is to determine whether the semi-cured adhesive film with a substrate has tackiness in a 40 ° C. atmosphere,
The presence or absence of cutting powder and the occurrence of cracks during 0 ° C. cutting were confirmed.

Further, regarding the evaluation of the adhesive product, the adhesive film was prepared using a polyirid film (Ubelex 50S matted product manufactured by Ube Industries) and an electrolytic copper foil (Nippon Electrolytic SLP 18 μm).
The roughened surface of the (copper foil) was pressed and cured at 180 ° C. under a pressure of 2 MPa for 1 hour to prepare a test piece, which was evaluated. As a result, it was found that the test sample according to Example 1 can be practically used as a heat-resistant adhesive film. These results are summarized in Table 1.

Example 2 An adhesive film having a film thickness of 25 μm and a curing rate of 45% was prepared in the same manner as in Example 1, except that the siloxane-modified polyamitoimito PAI-28 was changed to 60 parts and the rubber component HTR860P3 was changed to 20 parts. And evaluated. As a result, it was found that the test sample according to Example 2 can be practically used as a heat-resistant adhesive film. Table 1 summarizes the results as in Example 1.

Example 3 An adhesive film having a film thickness of 25 μm and a curing rate of 60% was prepared in the same manner as in Example 1 except that the siloxane-modified polyamitoimito PAI-28 was changed to 70 parts and the rubber component HTR860P3 was changed to 10 parts. And evaluated. As a result, it was found that the test sample according to Example 3 can be used practically as a heat-resistant adhesive film. Table 1 summarizes the results as in Example 1.

[0023]

[Table 1]

Comparative Example 1 An adhesive film having a curing rate of 20% was prepared in the same manner as in Example 1 except that the drying temperature of the adhesive film was changed to 170 ° C. In the evaluation of the adhesive film, the test sample according to Comparative Example 1 was found to have tackiness at 30 ° C., poor workability, and was not practical as a heat-resistant adhesive film. These results are summarized in Table-2.

Comparative Example 2 An adhesive film having a curing rate of 70% was prepared in the same manner as in Example 1 except that the drying temperature of the adhesive film was changed to 190 ° C. In the test sample according to Comparative Example 2, in the evaluation of the adhesive film, cutting powder was generated at the time of cutting the adhesive film at 10 ° C., cracks were generated at the ends, and the normal pressure conditions (2 MPa, (180 ° C.), there was a part that did not stick, and it was judged that it was not practical as a heat-resistant adhesive film. These results are summarized in Table 2 as in Comparative Example 1.

Comparative Example 3 An adhesive film having a film thickness of 25 μm and a curing rate of 45% was prepared in the same manner as in Example 1 except that the siloxane-modified polyamitoimito PAI-28 was changed to 40 parts and the rubber component HTR860P3 was changed to 40 parts. And evaluated. As a result, in the evaluation of the adhesive product, the test sample according to Comparative Example 3 had a 300 ° C.
Blistering occurred in seconds, and it was judged that it was not practical as a heat-resistant adhesive film. These results are summarized in Table 2 as in Comparative Example 1.

Comparative Example 4 An adhesive film having a thickness of 25 μm and a curing rate of 45% was prepared in the same manner as in Example 1 except that the siloxane-modified polyamitoimito PAI-28 was changed to 80 parts and the rubber component HTR860P3 was changed to 0 parts. And evaluated. As a result, in the evaluation of the adhesive product, the test sample according to Comparative Example 4 was subjected to the normal crimping conditions (2 MPa, 1 MPa
80 ° C.), no adhesion was found. These results are summarized in Table 2 as in Comparative Example 1.

Comparative Example 5 The conditions for bonding using the adhesive film prepared in Comparative Example 4 were examined. As a result, high temperature and high pressure of 210 ° C. and 4 MPa were required to secure the characteristics of the bonded product. It was found that the purpose of low temperature and low pressure bonding could not be achieved.
These results are summarized in Table 2 as in Comparative Example 1.

[0029]

[Table 2]

[0030]

According to the present invention, as a bonding material for electronic parts and semiconductor parts, it is possible to perform thermocompression bonding and hardening at a lower temperature and lower pressure than ever before by hot roll laminating, hot pressing, etc., and to improve workability (punching and cutting) at the time of semi-hardening. It is possible to provide a thermosetting heat-resistant adhesive film that is excellent and has excellent adhesiveness to film materials such as polyimid, metal, silicon, epoxy, ceramic, etc., both when cured and semi-cured, and also has excellent heat resistance when cured. became.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09J 163/08 C09J 163/08 F term (Reference) 4J004 AA02 AA05 AA11 AA13 AB05 BA02 CA06 CA08 CC02 FA05 FA08 4J040 EB032 EC002 EC212 EH031 EK111 HC01 JA09 JB02 KA16 LA01 LA08 MA01 MA02 MA04 MA10 NA19 NA20 PA18

Claims (4)

[Claims] 1. A siloxane-modified polyamitoimide component of 50 to 70 parts by weight based on a total of 25 parts by weight of an epoxy resin and a curing agent.
A thermosetting heat-resistant adhesive film obtained by applying an adhesive composition containing 10 to 30 parts by weight of a rubber component having a molecular weight of 50,000 or more to a base film and heat-treating it to a semi-cured state. 2. The heat-curable heat-resistant adhesive film according to claim 1, wherein the ethoxy resin component has an ethoxy equivalent of 350 or more and is solid at room temperature of 23 ° C. or less. 3. The heat-curable heat-resistant adhesive film according to claim 1, wherein the rubber component having a molecular weight of 50,000 or more is an end group ethoxy-modified acrylonitrile-phthalic acid engine. 4. A curing rate in a semi-cured state by heat treatment after being applied to a substrate film is 30 to 60%.
The thermosetting heat-resistant adhesive film according to any one of the above.