JPH05156231A - Heat-resistant adhesive composition - Google Patents

Abstract

PURPOSE:To provide an adhesive comprising a copolyimidesilaxane containing a specific diamine component, a difunctional epoxy compound, a glycidyl amine resin and a curing agent and giving laminates in which adhesive layers themselves have flexibility and which are not curled. CONSTITUTION:The adhesive comprises (A) 100 pts.wt. of a soluble copolyimidesiloxane produced from an aromatic tetraamine temperature consisting mainly of a biphenyltetracarboxylic acid and a diamine component consisting of 20-90mol.% of a diaminopolysiloxane of formula I (R is divalent hydrocarbon group; R1 to R4 are lover alkyl, phenyl; n is 3-60), 20-70mol.% of an aromatic diamine of formula II [X is -O-, -CH2-; Y is -SO2-, -C(CH3)-] and 1-20mol.% of a substituted aromatic diamine of formula III (R is carboxyl, lower alkoxycarbonyl; n is 1, 2; m is 0, 1), (B) 5-100 pts.wt. of a difunctional epoxy compound having two epoxy groups, (C) 10-79 pts.wt. of a polyfunctional glycidylamine resin having two epoxy groups, and (D) an epoxy-curing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to (a) a high molecular weight soluble copolyimide siloxane having no unsaturated group at the terminal, (b) a bifunctional epoxy compound, and (c) a polyfunctional glycidyl amine. The resin and the (d) epoxy curing agent are related to the heat-resistant adhesive composition containing a resin composition in a specific composition ratio.

The heat-resistant adhesive composition of the present invention can bond various metal foils such as copper foil and heat-resistant support materials (for example, heat-resistant film, inorganic sheet) at a relatively low temperature. At the same time, in the laminate laminated with the heat-resistant adhesive composition, since the adhesive layer exhibits sufficient adhesive force and excellent heat resistance, for example, a flexible wiring board, a TAB (Tape Automat) is used.
When used in the production of a copper clad substrate for ed bonding), each substrate obtained by using the heat resistant adhesive composition can safely perform various high temperature treatment steps such as the subsequent solder treatment. Can improve the quality of the final product,
The defect rate can be reduced.

[0003]

2. Description of the Related Art Conventionally, flexible wiring boards have often been manufactured by bonding an aromatic polyimide film and a copper foil together using an adhesive such as epoxy resin or urethane resin.

However, a flexible wiring board manufactured by using a known adhesive has a problem that when it is exposed to a high temperature in a subsequent soldering step, the adhesive layer causes swelling or peeling. It was desired to improve the heat resistance of.

As a heat-resistant adhesive, an imide resin adhesive has been proposed, for example, precondensation consisting of N, N '-(4,4'-diphenylmethane) bismaleimide and 4,4'-diaminodiphenylmethane. Things are known. However, since this precondensate itself is brittle, it is not suitable as an adhesive for flexible circuit boards.

As a method for improving the above drawbacks, an adhesive film (dry film) is formed from a resin composition obtained by mixing an aromatic polyimide obtained from benzophenonetetracarboxylic acid and an aromatic diamine and polybismaleimide, A method has been proposed in which the adhesive film is sandwiched between a heat resistant film such as a polyimide film and a copper foil and thermocompression bonding is performed. (See JP-A-62-232475 and JP-A-62-235382)

However, the above-mentioned adhesive film has a softening point of 180 ° C. or higher, and the adhesion between the polyimide film and the copper foil is maintained at a high temperature of about 260 to 280 ° C., and about 30 to 60 kg / It is necessary to carry out under a high pressure of about cm ^{2, and} under such adhesion conditions, it is extremely difficult to continuously laminate the polyimide film and the copper foil using a pressure roll made of an organic resin. It was a problem in terms of sex.

As a coating composition for electronic parts such as wiring boards, a resin solution (varnish) prepared by mixing an epoxy resin with an aromatic polyimide or the like is used as a heat resistant coating layer made of the resin cured product and a wiring board. Various proposals have been made to improve the adhesiveness of the.

However, the known composition has a high bonding or curing temperature as an "adhesive for bonding the copper foil and the aromatic polyimide film" in the production of the copper clad substrate as described above. However, there is a problem that the compatibility between the aromatic polyimide and the epoxy resin or the compatibility between the aromatic polyimide and the solvent is low, or the adhesive layer after adhesion and curing is not flexible. Could not be used as.

[0010]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The object of the present invention is to solve the above-mentioned problems in the known adhesives, and to apply the adhesive solution, dry, laminate copper foil, and form the adhesive layer. The purpose of the present invention is to provide a "heat-resistant adhesive composition showing high adhesiveness at high temperature", which can suitably bond a heat-resistant film and various metal foils through a step of curing. is there.

The object of the present invention is, in particular, that the adhesive layer (bonding sheet) itself has flexibility and tackiness, and is subjected to a step of laminating with a copper foil and curing the adhesive layer. , A heat-resistant adhesive composition capable of obtaining a laminate having excellent performance which is chemically resistant and does not cause curl by suitably laminating a heat-resistant film and various metal foils Is.

[0012]

The present invention is directed to (a) an aromatic tetracarboxylic acid component containing biphenyltetracarboxylic acids as a main component and a general formula (I).

[0013]

[Chemical 4]

[However, in the general formula (I), R is 2
Represents a valent hydrocarbon residue, R ₁ , R ₂ , R ₃ and R ₄ represent a lower alkyl group or a phenyl group, and n represents an integer of 3 to 60. ] Diaminopolysiloxane 20 represented by
~ 90 mol% (preferably 30-80 mol%), the general formula (II)

[0015]

[Chemical 5]

[However, in the general formula (II), X represents -O- or -CH _2- , and Y represents -SO _2- or-.
C _{(CH 3) 2} - shows a. ] 20-90 mol% of aromatic diamine shown by, and general formula (III)

[0017]

[Chemical 6]

[However, in the general formula (III), R
Represents a carboxyl group or a lower alkoxycarbonyl group, and n is 1 or 2. ] 100 parts by weight of a soluble copolyimide siloxane obtained from a diamine component consisting of 1 to 20 mol% (preferably 5 to 15 mol%) of an aromatic diamine having a substituent represented by

(B) 5 to 100 parts by weight of a bifunctional epoxy compound having two epoxy groups, and (c) two epoxy groups.
Multifunctional glycidyl amine resin having 10 or more
Parts by weight and (d) an epoxy curing agent (preferably 0.01 to 100 parts by weight of all epoxy compounds).
90 parts by weight) is contained as a resin component in the heat-resistant adhesive composition.

The soluble copolyimide siloxanes used in this invention are 3,3 ', 4,4'- or 2,3', 4 '.
3,3 ′, 4′-biphenyltetracarboxylic acid (preferably 2,3,3 ′, 4′-biphenyltetracarboxylic acid or an acid dianhydride or an acid esterified product thereof)
Aromatic tetracarboxylic acid component containing 60 mol% or more (particularly 80 mol% or more, particularly 80 to 100 mol%) as a main component, and diaminopolysiloxane 20 represented by the general formula (I).
90 mol% (preferably 25 to 85 mol%, especially 30 to
80 mol%), 20 to 70 mol% of the aromatic diamine represented by the general formula (II) (preferably 25 to 80 mol%,
1 to 20 mol% of an aromatic diamine having a substituent represented by the general formula (III), especially 30 to 70 mol%)
A high molecular weight copolyimide siloxane obtained by polymerizing and imidizing a diamine component composed of (preferably 2 to 18 mol%, particularly 5 to 15 mol%) is preferable.

The above-mentioned copolyimide siloxane has an inherent viscosity (measurement concentration; 0.5 g / 100 ml solvent, solvent; N-methyl-2-pyrrolidone, measurement temperature; 30 ° C.).
Is 0.05 to 7, particularly 0.07 to 4, more preferably about 0.1 to 3, and at least 3% by weight of any organic polar solvent (particularly an amide solvent), Particularly, it is preferable that the compound can be uniformly dissolved at a concentration of about 5 to 40% by weight.

The above copolyimide siloxane has an imidization ratio of 90% or more, particularly 95% or more, as measured by infrared absorption spectrum analysis, or has an absorption peak relating to the amide-acid bond of the polymer in infrared absorption spectrum analysis. It is preferable that the imidization ratio is high so that it is not substantially found and only the absorption peak related to the imide ring bond is seen.

Further, the above-mentioned copolyimide siloxane has an elastic modulus of 250 k when formed into a film.
g / mm ² or less, particularly 0.5 to 200 kg / mm ² , a thermal decomposition initiation temperature of 250 ° C. or more, particularly 300 ° C. or more, and a secondary transition temperature of −10 ° C. or more, especially 10 to 10. It is preferably about 250 ° C.

As a method for producing copolyimide siloxane,
For example, an aromatic tetracarboxylic acid component containing 2,3,3 ′, 4′-biphenyltetracarboxylic acids in an amount of about 60 mol% or more, and 20 to 90 mol% of the diaminopolysiloxane represented by the general formula (I), 20 to 70 mol% of the aromatic diamine represented by the general formula (II) and the aromatic diamine 1 having a substituent represented by the general formula (III)
At a high temperature (especially, in an organic polar solvent such as a phenolic solvent, an amide solvent, a solvent of a compound having a sulfur atom, a glycol solvent, or an alkylurea solvent) with a diamine component consisting of ˜20 mol%. A preferable method is to polymerize and imidize both monomer components at a temperature of preferably 140 ° C. or higher).

The above-mentioned biphenyltetracarboxylic acids are
Solubility of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) in an organic polar solvent in a copolyimide siloxane obtained by polymerization with the above-mentioned diamine component and phase with an epoxy compound Optimal in terms of solubility.

As the method for producing the copolyimide siloxane, the aromatic tetracarboxylic acid component and the diamine component are polymerized in an organic polar solvent at a low temperature of 0 to 80 ° C. to obtain a logarithmic viscosity of 0. It may be a method of producing a polyamic acid of 05 or more, and imidizing the polyamic acid by any known method to produce a soluble copolyimide siloxane.

Further, in the above-mentioned method for producing a copolyimide siloxane, an imide siloxane oligomer (component X: obtained by polymerizing an excess amount of the above-mentioned aromatic tetracarboxylic acid component and a diamine component consisting only of diaminopolysiloxane). The average degree of polymerization is about 1 to 10 and has an acid or an acid anhydride group at the terminal.), And a diamine component consisting only of the aromatic tetracarboxylic acid component and the aromatic diamine and the substituted aromatic diamine. An imide oligomer (Y component: the degree of polymerization is about 1 to 10 and having an amino group at the terminal) obtained by polymerizing an excess amount of the imide oligomer is prepared, and then the X component and the Y component are added to both of them. A method of producing a block-type copolyimide siloxane by mixing and reacting the acid component and the total diamine component so that the ratio becomes approximately equimolar It can be given to an appropriate.

In the heat resistant adhesive composition of the present invention,
When the copolyimide siloxane is produced by using other tetracarboxylic acids other than biphenyl tetracarboxylic acids as a main component, the copolyimide siloxane becomes insoluble in an organic polar solvent, or is not compatible with the epoxy resin. It is not suitable because the solubility will deteriorate.

A-BPDA as the aromatic tetracarboxylic acid component used in the production of the copolyimide siloxane.
Examples of the tetracarboxylic acid compound that can be used with, for example, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, and bis (3,3 4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, pyromellitic acid, or
Suitable examples thereof include acid dianhydrides and esterified products.

The polysiloxane represented by the general formula (I) used for producing the above copolyimide siloxane has R in the general formula I having 2 to 6 carbon atoms, particularly 3 to 5 carbon atoms.
Is a divalent hydrocarbon residue consisting of a plurality of methylene groups or phenylene groups, and R _{1 to} R ₄ are lower alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group, or It is preferably a phenyl group, and further, n
Is particularly preferably 5 to 20, more preferably about 5 to 15.

Examples of the aromatic diamine represented by the general formula (II) used for the production of the above-mentioned copolyimide siloxane include: 1) biphenyl diamine compounds, diphenyl ether diamine compounds, benzophenone diamine compounds, diphenyl sulfone compounds. Diamine compounds, diphenylmethane-based diamine compounds, diphenylalkane-based diamino compounds such as 2,2-bis (phenyl) propane,
2,2-bis (phenyl) hexafluoropropane-based diamine compound, diphenylene sulfone-based diamine compound,

2) di (phenoxy) benzene-based diamine compound, di (phenyl) benzene-based diamine compound, 3) di (phenoxyphenyl) hexafluoropropane-based diamine compound, bis (phenoxyphenyl) propane-based diamine compound, bis Aromatic diamines mainly containing "aromatic diamine compounds having two or more aromatic rings (benzene rings and the like), especially 2 to 5" such as (phenoxyphenyl) sulfone-based diamine compounds can be mentioned. They can be used alone or as a mixture.

As the aromatic diamine represented by the general formula (II), diphenyl ether type diamine compounds such as 1,4-diaminodiphenyl ether and 1,3-diaminodiphenyl ether, and 1,3-di (4-) are particularly preferable.
Aminophenoxy) benzene, di (phenoxy) benzene-based diamine compounds such as 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Screw [4-
(3-aminophenoxy) phenyl] propane and other bis (phenoxyphenyl) propane-based diamine-based compounds,
"Has 2 to 4 aromatic rings such as di (phenoxyphenyl) sulfone-based diamine compounds such as bis [4- (4-aminophenoxy) phenyl] sulfone and bis [4- (3-aminophenoxy) phenyl] sulfone. Aromatic diamines containing mainly (90 mol% or more) "aromatic diamine compound" can be preferably mentioned.

Examples of the organic polar solvent used in the production of the copolyimide siloxane include N, N-dimethylacetamide, N, N-diethylacetamide, N,
Amide-based solvents such as N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone and the like, and solvents containing a sulfur atom such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone and hexamethyl sulfolamide. , Cresol, phenol, phenolic solvents such as xylenol, acetone, methanol, ethanol, ethylene glycol, dioxane, solvents having an oxygen atom in the molecule such as tetrahydrofuran, pyridine, other solvents such as tetramethylurea. Further, if necessary, an aromatic hydrocarbon solvent such as benzene, toluene or xylene, or another type of organic solvent such as solvent naphtha or benzonitrile can be used together.

Epoxy group 2 used in the present invention
Examples of the bifunctional epoxy compound (b) having one group include "1 molecule of bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and the like. And an epoxy compound having two epoxy groups therein, and a plurality of the above-mentioned various bifunctional epoxy compounds may be used in combination. In the present invention, the bifunctional epoxy compound preferably has a melting point of 90 ° C. or lower, particularly about 0 to 80 ° C., or is a liquid at a temperature of 30 ° C. or lower.

As the polyfunctional glycidyl amine resin (C) used in the present invention, a reaction product of an aromatic diamine and an epoxy compound such as epichlorohydrin [eg, a reaction product of metaxylene diamine and epichlorohydrin (4 Polyfunctional epoxy resin having a glycidyl group, "Tetrad-X" manufactured by Mitsubishi Gas Chemical Co., Inc.), a reaction product of an aminophenol compound and an epoxy compound such as epichlorohydrin (polyfunctional having three glycidyl groups) "One kind of polyfunctional epoxy compound having three or more epoxy groups" such as epoxy resin, "ELM-100" manufactured by Sumitomo Chemical Co., Ltd., and the like, and various polyfunctional glycidyl compounds described above can be mentioned. A plurality of amine resins may be used in combination, and in the present invention, a polyfunctional glycidyl amine resin is used. It is a liquid at room temperature, the viscosity of 10000 cps or less at 25 ° C., particularly 100
Those of about 6000 centipoise are particularly preferable.

The epoxy curing agent (d) used in the heat resistant adhesive composition of the present invention includes imidazoles, tertiary amines, curing catalysts such as triphenylphosphines, dicyandiamides, hydrazine. And anionic polymerization type curing agents such as aromatic diamines, polyaddition type curing agents such as phenol novolac type curing agents having a hydroxyl group, and organic peroxides.

The above-mentioned epoxy curing agent can be used in an appropriate proportion, but the amount is 100 parts by weight of the epoxy resin comprising the bifunctional epoxy compound (b) and the polyfunctional glycidyl amine resin (c). , 0.01 to 90
It is preferable to use about 1 part by weight, especially about 0.03 to 80 parts by weight. When a polyaddition type curing agent is used as the epoxy curing agent, it is preferably used in an amount of 5 to 90 parts by weight, particularly 10 to 80 parts by weight, based on 100 parts by weight of the epoxy resin.

The heat-resistant adhesive composition of the present invention comprises a copolyimide siloxane (a), a difunctional epoxy compound (b), a polyfunctional epoxy compound (c), and an epoxy curing agent (d). Any heat-resistant adhesive composition may be used as long as it is a heat-resistant adhesive composition containing as a main component (particularly 90% by weight or more, more preferably about 95 to 100% by weight) a resin component having a specific composition ratio consisting of It may be a heat-resistant adhesive solution composition in which the resin component is uniformly dissolved in a suitable organic polar solvent, particularly at a concentration of 3 to 50% by weight, more preferably 5 to 40% by weight. .. The solution composition of the heat-resistant adhesive has a solution viscosity (30 ° C.) of about 0.1 to 10000 poise, particularly 0.2 to 5000 poise, and more preferably 0.3 to 1000 poise. Is preferred.

The heat-resistant adhesive composition of the present invention is
Softening point (temperature at which softening starts on the hot plate) of a composition containing only an uncured resin component (a composition containing substantially no solvent)
Is about 150 ° C. or lower, particularly 120 ° C. or lower, and more preferably about 0 to 100 ° C. The heat-resistant adhesive composition of the present invention has a temperature of 130 to 400 ° C, especially 14
It is preferably one that can be thermally cured by heating to a curing temperature of 0 to 350 ° C.

As the organic polar solvent used in preparing the solution composition of the heat-resistant adhesive, the organic polar solvent used in the production of the copolyimide siloxane can be used as it is. Organic polar solvents having an oxygen atom in the molecule such as dioxane and tetrahydrofuran can be preferably used.

The heat-resistant adhesive composition of the present invention comprises a solution composition of the heat-resistant adhesive in which all of the above resin components are uniformly dissolved in an organic polar solvent, and a suitable metal foil or aromatic polyimide film. And the like, or a thermoplastic resin film surface such as polyester or polyethylene, and the coating layer is dried at a temperature of 80 to 200 ° C. for 0.5 seconds to 100 minutes to obtain a solvent. Is removed to 1% by weight or less (preferably the residual solvent ratio is particularly 0.5% by weight or less), a thin film of the uncured heat-resistant adhesive composition (dry having a thickness of about 1 to 200 μm). A film or a bonding sheet) can be formed.

The thin film (bonding sheet etc.) of the uncured heat-resistant adhesive composition produced as described above is
It has suitable flexibility and can be wrapped around a paper tube,
It is also possible to do punching such as punching,
Further, for example, a laminated sheet in which a thin layer of the uncured heat-resistant adhesive composition is formed on the heat-resistant or thermoplastic film is overlaid with a metal foil or a heat-resistant film for a transfer destination. By passing between a pair of rolls (laminate rolls) heated to a temperature of about 20 to 200 ° C., it is also possible to transfer onto a metal foil or a heat resistant film for a transfer destination.

In order to form a laminate such as a copper clad substrate by joining a heat resistant film and a metal foil or the like using the heat resistant adhesive composition of the present invention, for example, it is formed as described above. The heat resistant film and the metal foil are placed at 80 to 200 ° C., particularly 100 to 180 ° C., through the thin film heat resistant adhesive layer.
Laminated under pressure at the temperature of
Furthermore, about 80-350 of the laminated product
By heating at 30 ° C., particularly 100 to 250 ° C., for 30 minutes to 40 hours, especially 1 to 30 hours to heat-cure the heat-resistant adhesive layer, the above-mentioned laminate can be easily prepared without any trouble. Can be manufactured continuously.

The heat-resistant adhesive composition of the present invention comprises a heat-resistant film such as an aromatic polyimide film, a polyamide film, a polyetheretherketone, a PEEK film and a polyethersulfone film, and a suitable metal foil such as a copper foil. It can be preferably used for joining.

[0046]

EXAMPLES The present invention will be described in more detail with reference to the following examples. In the following examples, the copolyimide siloxane has a logarithmic viscosity (η) of N-, so that the resin component concentration is 0.5 g / 100 ml of solvent.
It is a value calculated by the following calculation formula by uniformly dissolving the resin solution in methyl-2-pyrrolidone to prepare a resin solution, measuring the solution viscosity of the solution and the solution viscosity of only the solvent at 30 ° C.

[0047]

[Formula 1]

The tackiness of the bonding sheet is
A bonding sheet is sandwiched between polyester films (PET films) and observed by roll-laminating at 40 ° C., which indicates that they are in close contact with each other, and x indicates that they are spontaneously peeled off. The bonding strength of the bonding sheet was 90 ° and 180 at a peeling speed of 50 mm / min using a tensile tester manufactured by Intesco.
The results are obtained by performing a peel test.

The radius of curvature showing the curl property of a wiring board after forming a copper-clad substrate using a heat resistant adhesive composition and removing the copper foil by etching treatment is JIS standard C501.
The calculation formula shown in FIG. 2 [radius of curvature (mm) = L ² / 8h
(L: sample length, h: sled height)]. Furthermore, the chemical resistance of the copper laminate was determined by observing the surface of the copper laminate visually after immersing the sample used for the curl property test in acetone, and Indicates that the surface is whitened.

[Production of Copolyimide Siloxane A] Reference Example 1 In a glass flask having a capacity of 500 ml, the polysiloxane diamine represented by the general formula (I) (R is —CH
₂ -CH ₂ -CH ₂ - and _is, R 1 to R ₄ is a -CH _3, is at L 9. ) 18.73 g (molar ratio in diamine component: 50 mol%) was added to 200 g of N-methyl-2-pyrrolidone (NMP), and stirred at room temperature under a nitrogen stream (0.5 liter / min) for 30 minutes. And dissolved.

The solution was added with 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) 12.
Add 53 g (molar ratio: equimolar to diamine component) and add 5
After stirring at 0 ° C. for 2 hours to dissolve, the mixture was further added to 2,2-
6.12 g of bis [4- (4-diaminophenoxy) phenyl] propane (BAPP) (molar ratio in diamine component: 35 mol%) and diaminobenzoic acid (DABA)
0.97 g (molar ratio in the diamine component: 15 mol%) was added and stirred at 50 ° C. for 1 hour, then the solution was heated to 200 ° C. and stirred for 3 hours to obtain copolyimide siloxane A. Of 18% by weight was uniformly dissolved to prepare a polymer solution. This copolyimide siloxane A has an imidization ratio of substantially 100% and a logarithmic viscosity (3
(0 ° C.) was 2.5.

Reference Example 2 [Production of Copolyimide Siloxane B] a-
11.83 g (42 mmol) of BPDA was used, and 17.6 g (20 mmol) of diaminopolysiloxane used in Reference Example (1) as a diamine component, BA
In the same manner as in Reference Example 1, except that 8.2 g (20 mmol) of PP and 0.31 g (2 mmol) of diaminobenzoic acid were used and 160 g of NMP was used as a polymerization solvent, the copolyimide siloxane B was 18% by weight. A polymer solution that was uniformly dissolved was prepared. This copolyimide siloxane B had an imidization ratio of substantially 100% and an inherent viscosity (30 ° C.) of 1.8.

Reference Example 3 [Production of Copolyimide Siloxane C] a-
11.77 g (40 mmol) of BPDA and 17.6 g (20 mmol) of the diaminopolysiloxane used in Reference Example 1 as the diamine component and BAPP
Reference Example 1 except that 8.2 g (20 mmol) was used
18% by weight of copolyimide siloxane C in the same manner as
A polymer solution that was uniformly dissolved was prepared. This copolyimide siloxane C has an imidization ratio of substantially 10
It was 0% and the inherent viscosity (30 ° C) was 2.2.

Example 1 [Preparation of Solution Composition of Heat-Resistant Adhesive] In a glass flask having a capacity of 500 ml, (a) 55 parts by weight of the copolyimide siloxane A produced in Reference Example 1, (b)
Bifunctional epoxy compound having an epoxy group (Okaka Shell Epoxy Co., Ltd., trade name: Epicoat 807) 3
0 parts by weight, (c) 10 parts by weight of a polyfunctional glycidylamine resin having an epoxy group (trade name: Tetrad X, manufactured by Mitsubishi Gas Chemical Co., Inc.), (d) a polyaddition type curing agent as an epoxy curing agent (Meiwa Kasei) Co., Ltd., 18 parts by weight of phenol novolac type curing agent H-1 and 0.01 parts by weight of anionic type curing agent: 2-phenylimidazole (2PZ), 200 parts by weight of tetrahydrofuran (THF) as a solvent, and room temperature (25 Solution composition of heat resistant adhesive (viscosity at 25 ° C .: 12 poise) by stirring for about 2 hours.
Was prepared. This solution composition maintained a uniform solution state even when left at room temperature for 1 week.

[Production of Laminated Body by Heat-Resistant Adhesive] The solution composition of the heat-resistant adhesive described above was applied onto a polyimide film (manufactured by Ube Industries, Ltd., trade name: UPILEX-S type, thickness 75 μm). Coating with a doctor blade to a thickness of 175 μm, then coating the coating layer at 60 ° C. for 10 minutes,
A sheet layer of a heat-resistant adhesive composition having a thickness of 25 μm is formed on a polyimide film by heating at 100 ° C. for 10 minutes and further at 120 ° C. for 10 minutes (bonding sheet layer of an uncured dried heat-resistant adhesive composition). , Softening point: 95 ° C.).

Polyimide film having a bonding sheet layer of this heat resistant adhesive composition and copper foil (35 μm)
And 80 ° C. for 2 hours, 100 ° C. for 2 hours, 120 ° C. for 1 hour, 140 Additional 160 for 1 hour at ℃
The bonding sheet layer was cured by heating in a nitrogen stream at 10 ° C. for 10 hours to produce a laminate. The adhesive strength of the obtained laminate was measured, and the results are shown in Table 1.

Examples 2 to 4 and Comparative Example 1 As shown in Table 1, the copolyimide siloxanes produced in Reference Examples 1 to 3 were used, and the composition of each component was as shown in Table 1. In the same manner as in Example 1, a heat-resistant adhesive solution composition was prepared. A laminate was produced in the same manner as in Example 1 except that each of the solution compositions described above was used. The performance of those laminates is shown in Table 1.

[0058]

[Table 1]

[0059]

The heat-resistant adhesive composition of the present invention is roughly composed of (a) a specific copolyimide siloxane,
The present invention relates to a heat-resistant adhesive composition containing (b) a bifunctional epoxy compound, (c) a polyfunctional glycidylamine resin, and (d) an epoxy curing agent as resin components in a specific composition ratio.

The heat-resistant adhesive composition of the present invention can bond various metal foils such as copper foil and heat-resistant supporting materials such as heat-resistant films and inorganic sheets at a relatively low temperature. A bonding sheet can be easily formed from a solution composition of the heat-resistant adhesive composition, and the laminated body bonded via the bonding sheet has an adhesive layer with sufficient adhesive strength. Since it shows excellent flexibility and heat resistance, it can be used in the manufacture of flexible materials such as flexible wiring boards and copper-clad boards for TAB, etc. without worrying about various high-temperature processing steps such as solder processing after that. It is possible to improve the quality of the product and reduce the defective rate.

Further, the heat-resistant adhesive composition of the present invention is heat-resistant (excellent in adhesiveness at a temperature of 180 ° C. or higher), flexible (flexible) even after being used as an adhesive and cured by heating. Therefore, it can be suitably used as an adhesive for flexible wiring boards, copper-clad boards for TAB, and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenji Sonoyama 3-10 Nakamiyakitamachi, Hirakata-shi, Osaka Ube Industries Ltd. Hirakata Laboratory

Claims (1)

[Claims] 1. An aromatic tetracarboxylic acid component comprising (a) a biphenyltetracarboxylic acid as a main component, and a compound represented by the general formula (I): [However, in the general formula (I), R represents a divalent hydrocarbon residue, R ₁ , R ₂ , R ₃ and R ₄ represent a lower alkyl group or a phenyl group, and n is an integer of 3 to 60. Indicates. 20 to 90 mol% of a diaminopolysiloxane represented by the following general formula (II) [However, in the general formula (II), X is -O- or-
CH ₂ - indicates, Y is, -SO ₂ - or -C _(CH 3)
₂ − is shown. 20 to 70 mol% of an aromatic diamine represented by the following general formula (III) [However, in the general formula (III), R represents a carboxyl group or a lower alkoxycarbonyl group, n is 1 or 2, and m is 0 or 1. ] 100 parts by weight of a soluble copolyimide siloxane obtained from a diamine component consisting of 1 to 20 mol% of an aromatic diamine having a substituent represented by: (b) a bifunctional epoxy compound having 2 epoxy groups 5 100 parts by weight, (c) 10 to 70 parts by weight of a polyfunctional glycidyl amine resin having two or more epoxy groups, and (d) an epoxy curing agent are contained as resin components, and heat resistance. Adhesive composition.