JPH0987605A - Heat resisting adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat resisting adhesive excellent in soldering heat resistance, heat aging resistance, high temperature adhesivity, electric characteristics, flexibility, etc., as a tape for tape-automated-bonding(TAB) and further having widely improved solution stability. SOLUTION: This composition is composed of (a) 100 pts.wt. of an epoxy resin having at least two epoxy groups in a molecule, (b) 10-25 pts.wt. of an alcohol-soluble polyamide resin having an average amide group equivalent of 100-400, (c) 10-50 pts.wt. of a phenol resin, (d) 5-10 pts.wt. of a styrene thermoplastic elastomer and (e) 0.02-120 pts.wt. of a curing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant thermosetting adhesive, especially for TAB (abbreviation of Tape Automated Bonding) solder heat resistance, adhesiveness, electrical characteristics,
The present invention relates to a heat resistant adhesive composition having excellent chemical resistance and flexibility.

[0002]

2. Description of the Related Art As an adhesive used for electrical and electronic applications, for example, as TAB which is a means for mounting an IC chip on an electrical device, solder heat resistance, adhesiveness, electrical characteristics,
Although some require chemical resistance, flexibility, etc., no adhesive yet satisfies these properties at a high level.
For example, it has been pointed out that an epoxy resin has relatively high heat resistance, but lacks flexibility, and also has poor adhesiveness, particularly in peelability in a high temperature range of 150 ° C. or higher.

It is known to mix a polyamide resin with an epoxy resin as a method for improving the high temperature peelability, and the inventors of the present invention have also disclosed JP-A-7-097555 and JP-A-7-97555.
-0226238 introduced an example of improvement. However, there is a strong demand for improvement in heat resistance of epoxy resin-polyamide resin composite adhesives, and further improvement is desired.

There is also an adhesive composition in which an acrylonitrile rubber (NBR) is blended with an epoxy resin-polyamide resin, but it is not preferable because of its drawbacks such as mainly inferior high temperature peelability and heat aging resistance.

Therefore, the present inventor firstly found that the epoxy resin-
An application was made for an adhesive composed of a polyamide resin-styrene elastomer (Japanese Patent Laid-Open No. 197000/1995).
Although the solder heat resistance and the high temperature peelability are improved, it is not preferable from the viewpoint of solution stability of the adhesive solution.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides heat resistance, solder heat resistance, adhesiveness, electrical properties, flexibility, high temperature peelability, chemical resistance, etc. of conventional epoxy resin-polyamide resin composite adhesives. It is an object of the present invention to provide a practical heat-resistant adhesive having improved and further improved solution stability of the adhesive solution.

[0007]

Means for Solving the Problems and Modes for Carrying Out the Invention In order to solve the above problems, the present inventors have proposed a combination of an epoxy resin, an alcohol-soluble polyamide resin, and a styrene-based thermoplastic elastomer that have been conventionally used. Further, it was found that the solution stability of the adhesive solution is improved by further adding a phenol resin, and the present invention was completed by carefully examining the resin type, composition ratio, and the like. Therefore, the gist of the present invention is: a) 100 parts by weight of an epoxy resin having at least two epoxy groups in one molecule, b) 10 to 25 parts by weight of an alcohol-soluble polyamide resin having an average amide group equivalent of 100 to 400. , C) 5 to 10 parts by weight of styrene-based thermoplastic elastomer, d) 10 to 50 parts by weight of phenolic resin, and e) 0.02 to 120 parts by weight of a curing agent, which is a heat-resistant adhesive composition. .

The a) epoxy resin used in the present invention is an epoxy resin having at least two epoxy groups in one molecule, and for example, bisphenol A type epoxy, bisphenol F type epoxy, phenol novolac type epoxy, cresol type epoxy, Examples include brominated bisphenol type epoxy, brominated novolac type epoxy, alcohol modified phenol type epoxy, dimer acid / trimer acid modified epoxy, polyethylene glycol modified epoxy, alicyclic epoxy, naphthalene type epoxy, etc. Alternatively, two or more kinds may be combined as required, and they are selected according to properties such as coating workability, heat resistance, and adhesiveness.

Examples of the alcohol-soluble polyamide resin b) include alcohol-soluble polyamide resins having an average amide group equivalent of 100 to less than 200 and alcohol-soluble polyamide resins having an average amide group equivalent of 200 to 400.

Polyamide resin having an average amide group equivalent of 100 to less than 200 is a copolymer such as a binary copolymer base of 6.66, and a terpolymer such as 6.66.610, 6.66.12. Or a quaternary copolymer such as 6,66,610,12 and the like. These polyamide resins may be used alone or in combination of two or more. In particular, among the above-mentioned polyamide resins, those soluble in alcohol having 1 to 5 carbon atoms are preferable, and ternary copolymers can be preferably used in terms of solder heat resistance and high-temperature peelability. Furthermore, the melting point of a polyamide resin having an average amide group equivalent of 100 to less than 200 is 80 to 2
It has a melting point of 110 to 180 ° C, preferably 10 ° C. If the melting point exceeds 180 ° C., the high temperature peeling property deteriorates, and if it is less than 110 ° C., the solder heat resistance decreases, which is not preferable. Common polyamide resins such as nylon 6 and nylon 66 have a high melting point of 210 ° C. or higher and are insoluble in organic solvents, which is not preferable. Specific examples of commercially available products are Amilan CM4000 (Toray's 6.66.610 terpolymer polyamide resin), Amilan CM4001 (the same) Amiran CM8000.
(Same as above), Platabond M995 (6,66,12 terpolymer polyamide resin manufactured by Nippon Rilsan Co., Ltd.), Platabond M1276 (same as above), Daiamide T-171.
(6,66,12 terpolymer manufactured by Daicel Huls)
And the like.

As the polyamide resin having an average amide group equivalent of 200 to 400, a polyamide resin having an average amide group equivalent of 200 to 400 based on dimer acid is used. More preferable polyamide resin has an amide equivalent of 230 to 330. Specifically, for example, it is an alcohol-soluble polyamide resin which is a product obtained by the reaction of dimer acid which is a dimer of fatty acid such as soybean oil and tung oil and alkyldiamine such as ethylenediamine and diethylenetriamine. The polyamide resin is preferably soluble in alcohol having 1 to 5 carbon atoms, and further has a melting point of 80 to 210 ° C., preferably 11
The thing of 0-180 degreeC is preferable. If the melting point exceeds 180 ° C., the high temperature peeling property deteriorates, and if it is less than 110 ° C., the solder heat resistance becomes poor, which is not preferable. Specific examples of commercially available products are Macromelt 6212 (Henkel Hakusui polyamide resin), Macromelt 6238 (same as above), Macromelt 6900 (same as above), DPX927 (same as above), DPX.
1175 (same as above), DPX1196 (same as above), Versamide 725 (same as above), Versamide 744 (same as above), Versamide 940 (same as above) and the like.

These alcohol-soluble polyamide resins are epoxy resin 100 obtained by combining one or more of the above-mentioned polyamide resins or, if necessary, two or more kinds.
It is advisable to add 10 to 25 parts by weight to parts by weight.

C) The styrene thermoplastic elastomer has a polystyrene phase in both terminal phases, a rubber phase which is a polybutadiene, polyisoprene, ethylene-butylene, or a hydrogenation type polyolefin in an intermediate phase, and a styrene phase. A rubber phase having a weight ratio of 13/87 to 50/50 is used and has a molecular weight of 50,000 to 200,000.
0 is preferable. As a concrete example, TR110
1 (trade name of Shell Japan Co., mesophase / molecular weight: butadiene / 100,000 to 200,000), D111
1 (same as above, isoprene / about 100,000), G165
0 (same as above, ethylene-butylene / about 100,000),
G1652 (Same as above, ethylene-butylene / about 100,0
00), G1726 (same as above, ethylene-butylene / about 1
100,000), FG1901X (same as above, ethylene-butylene / about 100,000) and the like, and it is advisable to mix 5 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin by combining one kind or two or more kinds.

As the d) phenolic resin, either a resol type phenolic resin or a novolac type phenolic resin can be used, and one type or a resol type or novolac type may be used in combination if necessary. Further, the phenol resin used in the present invention is preferably one in which the unreacted phenol content is contained in the phenol resin in the range of 0.1 to 1% by weight. Particularly, if it exceeds 1% by weight, the solder heat resistance is lowered, which is not preferable. Further, if it is less than 0.1% by weight, the compatibility with the polyamide resin and the epoxy resin is deteriorated. The phenol resin may be mixed in an amount of 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the epoxy resin.

E) As the curing agent, amine type, organic acid anhydride, phenol type, dicyandiamide type, amidoamino type, imidazole type and the like, which are generally used for epoxy resins, may be used alone or in combination of two or more. be able to. Specifically, diaminodiphenylmethane, diaminodiphenyl sulfone, methyl hydrophthalic anhydride, methyl tetraphthalic anhydride, dicyandiamide, 2-ethyl-4-methylimidazole, 4-methylimidazole and the like can be mentioned, but especially electrical characteristics, solder It is preferable to use an amine type or dicyandiamide in view of excellent heat resistance, and specifically, diaminodiphenylmethane and dicyandiamide are preferable. The curing agent is 0.1 part with respect to 100 parts by weight of the epoxy resin.
02 to 120 parts by weight are used.

The amount of each curing agent added is 100% epoxy resin.
The content is 0.02 to 120 parts by weight with respect to parts by weight, but the blending amount is appropriately adjusted depending on the type of curing agent used. Specifically, 5 to 30 parts by weight of amine system and 5 to 120 of organic acid anhydride system
1 part by weight to 80 parts by weight, 1 to 30 parts by weight of dicyandiamide, 10 to 70 parts by weight of amidoamino and 0.02 to 10 parts by weight of imidazole are preferred.

The adhesive composition of the present invention comprises a) an epoxy resin 10 having at least two epoxy groups in one molecule.
0 parts by weight, b) 10 to 25 parts by weight of an alcohol-soluble polyamide resin having an average amide group equivalent of 100 to 400,
c) 5 to 10 parts by weight of styrene-based thermoplastic elastomer,
d) Phenolic resin 10 to 50 parts by weight and e) 0.02 to 120 parts by weight of a curing agent, but when the polyamide resin is less than 10 parts by weight with respect to 100 parts by weight of the epoxy resin, high temperature peelability and flexibility. On the other hand, when it exceeds 25 parts by weight, the electrical properties and solder heat resistance are remarkably deteriorated due to the hygroscopicity of the polyamide resin, and it cannot be put to practical use. When the amount of the styrene-based thermoplastic elastomer is less than 5 parts by weight, the heat resistance is not improved, and when it exceeds 10 parts by weight, the high temperature peeling property is deteriorated, which is not preferable. When the amount of the phenol resin is less than 10 parts by weight, the solution stability of the adhesive solution is not improved, and when it exceeds 50 parts by weight, the flexibility is lowered, which is not preferable. The amount of the curing agent added varies depending on the type, but if it is less than 0.02 parts by weight, the uncured portion of the resin remains due to insufficient curing agent and the heat resistance decreases, and if it exceeds 120 parts by weight, the curing agent is excessive and unreacted. The curing agent remains and the heat resistance decreases.

The adhesive of the present invention is manufactured, for example, by the following method. First, an alcohol-soluble polyamide resin is stirred and dissolved in a lower alcohol having 1 to 5 carbon atoms, preferably isopropanol, at 50 to 100 ° C., and a phenol resin and an epoxy resin are added to the mixture to obtain 50 to 1
Stir with warming at 00 ° C and mix well. In this case, the epoxy resin to be charged is previously heated to 50 to 100 ° C., or chlorinated hydrocarbon (methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc.), ketone hydrocarbon (acetone, methyl ethyl ketone). , Methyl isobutyl ketone, etc.) and aromatic hydrocarbons (benzene, toluene, xylene, etc.) dissolved in them are easily mixed.

Next, the styrene thermoplastic elastomer is treated with chlorinated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc.) and aromatic hydrocarbons (benzene, toluene, xylene, etc.) at 50 to 100 ° C. The previously dissolved by stirring is added to the mixture of the alcohol-soluble polyamide resin, the phenol resin and the epoxy resin with stirring.

The amount of the solvent used in the adhesive is 100 to 4 with respect to 100 parts by weight (solid content) of the adhesive composition.
It is advisable to mix and adjust the amount in the range of 00 parts by weight.

After thoroughly stirring and mixing these, 40
C. or less, preferably cooled to 5 to 25.degree. C., after which a curing agent is added and further stirred and mixed at 40.degree. C. or less, preferably 5 to 25.degree. C., and in that state, for 30 to 120 minutes, preferably 30.degree. Let stand for 60 minutes to degas.

The adhesive solution thus obtained is applied to a heat-resistant plastic film of, for example, polyimide or polyester so as to have a thickness after drying of 5 to 40 μm, and then 60 to 60 μm.
Dry at 150 ° C., preferably 80-120 ° C. to remove the solvent and bring it to a semi-cured state. Next, a metal foil (copper foil, aluminum foil, etc.) having a thickness of 19 to 50 μm is laminated on the semi-cured adhesive layer, and thermocompression bonding (temperature 40 to 200 ° C., preferably 50 to 150 ° C., pressure 1 to 50 kg / cm ² ), and then heat curing treatment in an oven at 120 to 300 ° C. for 3 to 16 hours, if necessary, and then imaging (resist, exposure, development), etching, etc. to form an electric circuit. And used as TAB.

[0023]

EXAMPLES The embodiments of the present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. Example 1 CM4000 with an average amide group equivalent of 125
18 parts by weight of (Toray's alcohol-soluble polyamide resin) was added to 230 parts by weight of methanol, and the mixture was stirred and dissolved at 60 ° C., and then Phenolite TD2131 containing 0.14% by weight of an unreacted phenol component with respect to the phenol resin. Novolak-type phenol resin manufactured by Dainippon Ink and Chemicals, Inc. 20
100 parts by weight of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Co., Ltd.) having an epoxy equivalent of 189 are added, and the mixture is stirred and mixed at 60 ° C. Separately, Clayton G-FG1901X having a styrene / rubber ratio of 28/72
(Shell Japan styrene-ethylene / butylene-
8 parts by weight of a styrene copolymer) is added to 230 parts by weight of toluene and dissolved by stirring at 80 ° C. This is mixed with the polyamide-phenol resin-epoxy resin solution, which has been mixed in advance, little by little so as to prevent the styrene-based thermoplastic elastomer from precipitating into the solution, and then sufficiently stirred and mixed at 60 ° C. Further, the mixed solution was cooled to 20 ° C., 10 parts of dicyandiamide was added, the mixture was stirred and mixed again, and in that state, the mixture was allowed to stand for 60 minutes for deaeration to obtain an adhesive solution. This adhesive solution is applied to a 75 μm thick polyimide resin film (Upilex S manufactured by Ube Industries, Ltd.) so that the thickness when dried is 20 μm, and dried at 90 ° C. for 5 minutes to remove the solvent and semi-cure. Then, a rolled copper foil having a thickness of 35 μm (manufactured by Japan Energy Co., Ltd.) is laminated on this and 160
The cured laminate (carrier tape for TAB) was obtained by thermocompression bonding at 50 ° C. × 50 kg / cm ² × 30 minutes. The results of measuring the physical properties are shown in Table 1.

Example 2 An adhesive was prepared in the same manner as in Example 1 except that 40 parts by weight of phenol resin was used to obtain a cured laminate of polyimide film resin film-adhesive-copper foil. The physical property measurement results are shown in Table 1.

(Comparative Examples 1 to 3) An adhesive was prepared in the same manner as in Example 1 except that the amount of the phenol resin was 0, 5, and 80 parts by weight, and a cured laminate of polyimide resin film-adhesive-copper foil. I got a thing. The physical property measurement results are shown in Table 1.

(Examples 3 to 4, Comparative Examples 4 to 6) In Examples 1 and 2 and Comparative Examples 1 to 3, the average amide group equivalent was 12
CM400, which is an alcohol-soluble polyamide resin of 5
An adhesive was prepared in the same manner except that an alcohol-soluble polyamide resin having an average amide group equivalent of 135, Platabond M995 (manufactured by Rilsan Japan Co., Ltd.) was used instead of 0, and curing was made of polyimide resin film-adhesive-copper foil. A laminate was obtained. The physical property measurement results are shown in Table 1.

(Example 5) An adhesive was prepared in the same manner as in Example 1 except that Macromellt 6238 (alcohol-soluble polyamide resin manufactured by Henkel Hakusui Co., Ltd.) having an average amide group equivalent of 230 was used as the polyamide resin. A cured laminate of the agent-copper foil was obtained. The physical property measurement results are shown in Table 2.

Example 6 An adhesive was prepared in the same manner as in Example 5 except that 40 parts by weight of the phenol resin was used to obtain a cured laminate of polyimide film resin film-adhesive-copper foil. The physical property measurement results are shown in Table 2.

(Comparative Examples 7 to 9) An adhesive was prepared in the same manner as in Example 6 except that the amount of the phenol resin was changed to 0, 5, and 80 parts by weight, and a cured laminate comprising polyimide resin film-adhesive-copper foil. I got a thing. The physical property measurement results are shown in Table 1.

(Examples 7 to 8 and Comparative Examples 10 to 12) In Examples 5 to 6 and Comparative Examples 7 to 9, the average amide group equivalent was 2
Macromelt 621, which is an alcohol-soluble polyamide resin having an average amide group equivalent of 320, instead of Macromelt 6238, which is an alcohol-soluble polyamide resin of 30
An adhesive was prepared in the same manner except that 2 (manufactured by Henkel Hakusui Co., Ltd.) was used to obtain a cured laminate composed of a polyimide resin film-adhesive-copper foil. The physical property measurement results are shown in Table 2.

[0031]

[Table 1]

[0032]

[Table 2]

(Physical property measuring method) For physical property measurement, a TAB tape made of polyimide resin-adhesive-copper foil was used as a sample. 1) Solder heat resistance: According to JIS C6481, the sample was cut into 2.5 cm square and floated in a solder bath for 30 seconds, and the maximum temperature at which the sample did not change in appearance such as blister was measured.

2) High temperature peelability: The sample was cut into a length of 1 cm × 20 cm according to JIS C6481,
The sample was fixed on a hot plate kept at 150 ° C., and then 180 ° using a tensile tester (AGS-500A) manufactured by Shimadzu Corporation.
The peel was measured.

3) Thermal aging resistance: The sample was left for 240 hours in an oven kept at 150 ° C. to be aged and cut into a sample with a width of 1 cm × 20 cm and a tensile tester manufactured by Shimadzu Corporation. (AGS-500A),
The 90 ° peel at room temperature was measured.

4) Flexibility: A 75 μm thick polyimide resin film coated with an adhesive solution was dried in an oven maintained at 90 ° C. for 5 minutes to be a semi-cured state. 180 ° with this adhesive on the outside
Bending was observed for cracks. ○: Not broken ×: Broken

5) Volume resistance: After the sample was cut into 11 cm × 11 cm according to JIS C6481, 20 ° C. ×
Diameter 80 after being left in an atmosphere of 60% RH for 96 hours
The measurement was performed by sandwiching it between φ upper and lower electrodes.

6) Solution stability: After stirring and mixing the adhesive solution at 20 ° C. for 60 minutes, the time from when the stirring was stopped to when the phase separation of the solution started was measured visually.

[0039]

INDUSTRIAL APPLICABILITY According to the present invention, a heat-resistant thermosetting adhesive, particularly a TAB tape, is excellent in solder heat resistance, heat aging resistance, high temperature adhesiveness, electrical characteristics, flexibility and the like, and is stable in solution. A heat-resistant adhesive with significantly improved properties is obtained,
The industrial utility value is extremely high.

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Claims (1)

[Claims] 1. A) 100 parts by weight of an epoxy resin having at least two epoxy groups in one molecule, b) 10 to 25 parts by weight of an alcohol-soluble polyamide resin having an average amide group equivalent of 100 to 400, and c). 5-10 parts by weight of styrene thermoplastic elastomer, d) phenol resin 1
A heat resistant adhesive composition comprising 0 to 50 parts by weight and e) a curing agent of 0.02 to 120 parts by weight.