JPH0987606A - Heat resisting adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat resisting adhesive excellent in soldering heat resistance, adhesivity, electric characteristics, chemical resistance, flexibility, etc., as a heat resisting thermoset-type adhesive free from phase separation, especially as a tape for tape-automated-bonding(TAB). 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 200-400, (c) 0.5-6 pts.wt. of an alcohol-soluble polyamide resin having an average amide group equivalent of 100-150, (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]

TECHNICAL FIELD The present invention relates to a heat-resistant thermosetting adhesive composition, particularly solder heat resistance, adhesiveness, electrical characteristics, for TAB (abbreviation of tape automated bonding).
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 composition used for electric / electronic applications, for example, as TAB which is one of means for mounting an IC chip on electric / electronic equipment, solder heat resistance, adhesiveness, electrical characteristics, resistance Although chemical properties and flexibility are required, there is still no adhesive that satisfies these properties at a high level at the same time.

For example, an epoxy resin has relatively high heat resistance, but lacks flexibility and has an adhesive property of 150 ° C.
It is pointed out that the peeling property in the above high temperature range is poor. In addition, it has been pointed out that polyimide resins and the like, which are known as heat resistant resins, also have poor peeling properties. It is known to mix a polyamide resin with an epoxy resin as a method for improving high temperature peelability while maintaining heat resistance. The inventors of the present invention have also disclosed JP-A-7-97555 and JP-A-7-75555.
No. 26238. However, there is a strong demand for improvement in heat resistance of the epoxy resin-polyamide resin composite adhesive composition, and further improvement is desired. In addition, epoxy resin-polyamide resin is added to acrylonitrile rubber (N
BR) is also included, but it is not preferable because it has drawbacks such as inferior high-temperature peelability and heat aging resistance.

Therefore, the inventors of the present invention have disclosed in Japanese Patent Application Laid-Open No. 7-1970
No. 00 discloses an epoxy resin-polyamide resin-based composite adhesive composition using a polyamide resin having an average amide group equivalent of 100 to 150 alone. However, in the adhesive composition, heat resistance, solder heat resistance, Although the adhesiveness, electrical characteristics, flexibility, high temperature peelability, chemical resistance, etc. were improved, phase separation occurred in the solution as an adhesive.

[0005]

SUMMARY OF THE INVENTION Therefore, the present invention is intended to ameliorate the above-mentioned drawbacks of causing minute phase separation, and an alcohol-soluble polyamide resin having an average amide group equivalent of 100 to 150 and an average amide group equivalent of 200. ~
By using two kinds of polyamide resins of 400 alcohol-soluble polyamide resins in combination, solder heat resistance, adhesiveness,
It aims to improve electrical properties, flexibility, high temperature peelability, chemical resistance and phase separation.

[0006]

MEANS FOR SOLVING THE PROBLEM AND BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have found that the epoxy resin and the average amide group equivalent which are conventionally used for solving the above problem are 100 to 1
An alcohol-soluble polyamide resin having an average amide group equivalent of 50, which has good compatibility with an epoxy resin, is 200 to 40.
It was found that phase separation does not occur when an alcohol-soluble polyamide resin of 0 is added and a styrene-based thermoplastic elastomer is added, and the kind of resin, composition ratio, etc. were studied in detail and the present invention was completed. 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 200 to 400, and c). Average amide group equivalent is 100-
Alcohol-soluble polyamide resin 0.5 to 150
6 parts by weight, d) styrene-based thermoplastic elastomer 5-1
A heat-resistant adhesive composition comprising 0 part by weight and e) a curing agent of 0.02 to 120 parts by weight.

Hereinafter, the present invention will be described in detail. The a) epoxy resin used in the present invention is an epoxy resin having at least two epoxy groups in one molecule, and examples thereof include bisphenol A type epoxy, bisphenol F type epoxy, phenol novolac type epoxy, cresol type epoxy, and 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., and these epoxy resins may be used alone or as necessary. You may combine 2 or more types according to it.

B) 6.66 as an alcohol-soluble polyamide resin having an average amide group equivalent of 100 to 150
Binary copolymers such as 6,66,610, 6,66,12
And ternary copolymers such as 6.66, 610 and 12, and the like. In particular, among the above-mentioned polyamide resins, those having 1 to 5 carbon atoms, preferably those soluble in lower alcohols such as methanol and ethanol, are preferable, and are ternary from the viewpoint of solder heat resistance, high-temperature peelability, and availability. Copolymers of alcohol soluble polyamide resins are used. Further, the melting point of these alcohol-soluble polyamide resins is 80 to 210 ° C, and among them, those having a melting point of 110 to 180 ° C are preferably used in the present invention. If the melting point exceeds 180 ° C., the high temperature peeling property tends to decrease, and if it is 110 ° C. or less, the solder heat resistance tends to decrease, which is not preferable. Ordinary polyamide resins, such as nylon 6 and nylon 66, have a high melting point of 210 ° C. or higher, are insoluble in organic solvents, and deteriorate in high temperature peelability, which is not preferable. As a concrete example, Amilan C
M4000 (Toray's 6.66.610 terpolymer polyamide resin), Amylan CM4001 (same as above), Amylan CM8000 (same as above), Platabond M995
(Nippon Rilsan Co., 6,66,12 terpolymer polyamide resin), Platabond M1276 (same, same) Daiamide T-171 (Daicel Huls, 6,66,12)
Ternary copolymer polyamide resin), Daiamide T-170
(The same, the same) and the like, and one kind or two as necessary.
You may combine 2 or more types.

C) The alcohol-soluble polyamide resin having an average amide group equivalent of 200 to 400 is based on dimer acid, for example, dimer acid which is a dimer of fatty acids such as soybean oil and tung oil and ethylene diamine, for example. , An alcohol-soluble polyamide resin which is a product obtained by the reaction of an alkyldiamine such as diethylenetriamine. The polyamide resin is preferably soluble in alcohol having 1 to 5 carbon atoms, and more preferably has a melting point of 80 to 210 ° C, preferably 110 to 180 ° C. If the melting point is less than 110 ° C, the soldering heat resistance will decrease, and if it exceeds 180 ° C, the high temperature peeling property will be poor, such being undesirable. Specifically, Macromelt 6
212 (polyamide resin manufactured by Henkel Hakusui Co., Ltd.), Macromelt 6238 (same), Macromelt (same), DPX92
7 (same), DPX1175 (same), DPX1196
(Same), Versamide 725 (same), Versamide 744
(The same), Versamide 940 (the same), and the like, and these polyamide resins may be used alone or in combination of two or more if necessary.

D) The styrene thermoplastic elastomer has a polystyrene phase in the terminal phase and a rubber phase which is polybutadiene, polyisobrene, ethylene-butylene or hydrogenated type polyolefin in the intermediate phase, and has a styrene phase and a rubber phase. Is used in a weight ratio of 13/87 to 50/50, and the molecular weight is preferably 50,000 to 200,000. As a concrete example, TR1101 (manufactured by Shell Japan, mesophase / molecular weight: butadiene / 10
0000-200000), D1111 (the same, isoprene / about 100,000), G1652 (the same, ethylene-butylene / about 100000), G1652 (the same, ethylene-butylene / about 100000), G1726 (the same, ethylene-butylene / about 100000). , FG1901X
(Same as above, ethylene-butylene / about 100,000) and the like, and one kind or a combination of two or more kinds may be used.

The mixing ratio of the above four components is such that the average amide group equivalent is 2 with respect to 100 parts by weight of the base epoxy resin.
When the alcohol-soluble polyamide resin of 00 to 400 is less than 10 parts by weight, the high temperature peelability and flexibility are deteriorated, and when it exceeds 25 parts by weight, the electrical properties are deteriorated due to the hygroscopicity of the polyamide resin and the heat resistance of soldering under wet heat is deteriorated. Is not preferable because it becomes remarkable. Also, the amide group equivalent is 100 to 15
When the alcohol-soluble polyamide resin which is 0 is less than 0.5 part by weight, the high temperature peeling property is deteriorated, and when it exceeds 6 parts by weight, the compatibility with the epoxy resin is deteriorated and minute phase separation occurs, which is not preferable. When the amount of the styrene-based thermoplastic elastomer exceeds 10 parts by weight, the high temperature peeling property is deteriorated, and when it is less than 5 parts by weight, the heat resistance is not improved, which is not preferable.

In the present invention, two kinds of alcohol-soluble polyamide resins are used. In the above composition, the polyamide resin having an amide group equivalent of 100 to 150 and the polyamide resin having an amide group equivalent of 200 to 400 are blended in proportions. It is preferable to be within the range.

Further, the curing agent e) used in the present invention is used in an amount of 0.02 to 120 parts by weight based on 100 parts by weight of the epoxy resin. As the curing agent, one type or a combination of two or more types of curing agents generally used for epoxy resins, such as amine type, organic acid anhydride type, phenol type, dicyandiamide type, amidoamino type and imidazole type can be used. Specific examples include diaminodiphenylmethane, diaminodiphenyl sulfone, methyl hydrophthalic anhydride, methyl tetraphthalic anhydride, dicyandiamide, 2-ethyl-4-methylimidazole, 4-methylimidazole, etc., but electrical characteristics, solder heat resistance It is preferable to use diaminodiphenylmethane or dicyandiamide from the viewpoint of excellent properties. Further, the addition amount of each curing agent is 0.02 to 120 parts by weight with respect to 100 parts by weight of the epoxy resin, but specifically, 5 to 30 parts by weight of an amine system, 50 to 120 parts by weight of an organic acid anhydride system, Phenolic system 1-8
0 parts by weight, dicyandiamide-based 1 to 30 parts by weight, amidoamino-based 10 to 70 parts by weight, and imidazole-based 0.0
2 to 10 parts by weight is preferable.

The adhesive composition of the present invention is produced, for example, by the following method. First, the average amide group equivalent is 100 to
Two kinds of alcohol-soluble polyamide resins of 150 and 200 to 400 are added in an alcohol having 1 to 5 carbon atoms.
The mixture is stirred and dissolved at 0 to 100 ° C., an epoxy resin is added thereto, the mixture is heated and stirred at 50 to 100 ° C., and mixed sufficiently. In this case, the epoxy resin to be charged is 50 to 10 in advance.
Preheat to 0 ° C or chlorinated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, trichlorethylene,
It is easy to mix when using those dissolved in tetrachloroethylene, etc.), ketone-based hydrocarbons (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), and aromatic hydrocarbons (benzene, toluene, xylene, etc.).

Next, the styrene thermoplastic elastomer is treated with a chlorinated hydrocarbon (methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc.),
Aromatic hydrocarbons (benzene, toluene, xylene, etc.)
The above-mentioned polyamide-epoxy solution is added after stirring and dissolving at 50-100 ° C.

It is desirable that the amount of the above-mentioned solvent is 100 to 400 parts by weight with respect to 100 parts by weight of the adhesive composition, and the amount of the solvent is appropriately adjusted.

These adhesive solutions are sufficiently stirred and mixed, and then cooled to 40 ° C. or lower, preferably 5 to 25 ° C., and then a curing agent is added thereto and 40 ° C. or lower, preferably 5 to 5 ° C.
After further stirring and mixing at 25 ° C., the mixture is allowed to stand for 30 to 60 minutes and deaerated.

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 leave the adhesive in a semi-cured state. Next, on the semi-cured adhesive layer, a metal foil (copper foil, aluminum foil, etc., 18 to 50 μm)
m) are laminated, thermocompression bonded (temperature 40 to 200 ° C., preferably 50 to 150 ° C., pressure 1 to 50 kg / cm ² ), and then, if necessary, in an oven at an atmosphere of 120 to 300 ° C. for 3 to 16 hours. After heat-curing, imaging (resist, exposure, phenomenon) etching, etc. is performed to form an electric circuit, which is used as a TAB tape.

[0019]

EXAMPLES The embodiments of the present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 6.66.610 Nylon Copolymer Resin Amilan CM4 having an average amide group equivalent of 125 and a melting point of 140 ° C.
000 (manufactured by Toray Industries, Inc.) 3 parts by weight, average amide group equivalent 230
Dimer Acid Pace Polyamide Resin Macromelt 62
38 (manufactured by Henkel Hakusui Co.) 15 parts by weight of methanol 23
0 parts by weight, and dissolved by stirring at 60 ° C., 100 parts by weight of bisphenol A type epoxy resin Epicoat 828 (manufactured by Yuka Shell Co., Ltd.) having an epoxy equivalent of 189 was added, and the mixture was heated and stirred, and sufficiently Mix. Then styrene-ethylene / butylene-with a styrene / rubber ratio of 28/72
Styrene-based thermoplastic elastomer, which is a styrene copolymer: 8 parts by weight of Kraton G-FG1901X (manufactured by Shell Japan Co.) was added to 230 parts by weight of toluene to obtain 80.
The mixture is stirred and dissolved at 0 ° C., added to the previously mixed polyamide-epoxy resin solution, and further stirred and mixed at 60 ° C. After sufficiently mixing, the mixture was cooled to 20 ° C. and 10 parts by weight of dicyandiamide was added to the cooled polyamide-epoxy-styrene-based thermoplastic elastomer mixed solution, which was further sufficiently stirred and mixed, and then left standing for 60 minutes to obtain an adhesive solution. Got This adhesive solution was added to a 75 μm thick polyimide resin film:
Coated on Ubilex S (manufactured by Ube Industries), 90 ° C x
After drying for 5 minutes to a semi-cured state, 1 ounce of copper foil (thickness 35 μm, rolled copper foil manufactured by Japan Energy Co., Ltd.) 1
The cured laminate (TAB tape) was obtained by thermocompression bonding at 60 ° C. × 50 kg / cm ² × 30 minutes. The physical property measurement results are shown in Table 1.

(Examples 2 to 5 and Comparative Examples 1 to 4) TAB tapes having the compositions shown in Table 1 were obtained in the same manner as in Example 1. Table 1 shows the results of measuring the respective physical properties.

[0021]

[Table 1]

(Physical property measuring method) 1) Solder heat resistance: A sample is cut into a 2.5 cm square according to JIS C6481 and floated in a solder bath for 30 seconds.
The maximum temperature at which there was no change in appearance such as blistering of the sample at each temperature was measured.

2) High temperature peeling property: The sample was cut into 1 cm × 20 cm width according to JIS C6481 and
The sample was fixed on a hot plate kept at 50 ° C., and 180 ° peel was measured using a tensile tester (AGS-500A) manufactured by Shimadzu Corporation.

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

4) Flexibility: An adhesive solution coated on a polyimide resin film having a thickness of 75 μm was used as a sample and dried in the open kept at 90 ° C. for 5 minutes to be a semi-cured state. As a sample, this was bent 180 ° with the adhesive on the outside and cracks were observed. ○: No cracking ×: Cracking

5) Volume resistance: After the sample was cut into 11 cm × 11 cm according to JIS C6481, 20 ° C. ×
80% diameter after leaving for 60 hours in 60% RH atmosphere
It was sandwiched between the upper and lower electrodes of and measured.

6) Phase separation: An adhesive solution coated on a polyester resin film having a thickness of 50 μm is dried for 5 minutes in an oven kept at 90 ° C. to evaporate the solvent,
A semi-cured sample was used as a sample, and the degree of separation was observed using a magnifying glass with a magnification of 50 (with a scale having a minimum scale of 50 μm). ○: No phase separation △: Phase separation size of 50 μm or less ×: Phase separation size of more than 50 μm

[0028]

[Effect] According to the present invention, a heat-resistant thermosetting adhesive having no phase separation, particularly solder heat resistance for a TAB tape,
A heat-resistant adhesive having excellent adhesiveness, electrical characteristics, chemical resistance, flexibility and the like can be obtained, and its industrial utility value is extremely high.

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 200 to 400, c). 0.5 to 6 parts by weight of an alcohol-soluble polyamide resin having an average amide group equivalent of 100 to 150, d) 5 to 10 parts by weight of a styrenic thermoplastic elastomer, and e) 0.02 to 120 parts by weight of a curing agent. A characteristic heat-resistant adhesive composition.