JP3031027B2 - Heat resistant adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to (a) a high molecular weight soluble copolyimide siloxane having no terminal unsaturated group, (b) a bifunctional epoxy compound, and (c) a polyfunctional glycidylamine. The present invention relates to a heat-resistant adhesive composition containing a resin and (d) an epoxy curing agent in a specific composition ratio as a resin component.

The heat-resistant adhesive composition of the present invention can bond various metal foils such as a copper foil to a heat-resistant support material (eg, a heat-resistant film, an inorganic sheet, etc.) at a relatively low temperature. At the same time, in the laminate bonded with the heat-resistant adhesive composition, the adhesive layer exhibits a sufficient adhesive strength and excellent heat resistance, and thus, for example, a flexible wiring board, TAB (Tape Automat)
When used for the production of copper-clad substrates for ed bonding, etc., each substrate obtained using the heat-resistant adhesive composition can safely perform various high-temperature processing steps such as soldering. To improve the quality of the final product,
Or lower the defective rate.

[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 using an adhesive such as an epoxy resin or a urethane resin.

However, a flexible wiring board manufactured using a known adhesive has a problem that, when exposed to a high temperature in a subsequent soldering process, the adhesive layer is blistered or peeled off. There has been a demand for improved heat resistance.

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

As a method for improving the above-mentioned disadvantage, 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 of sandwiching the adhesive film between a heat-resistant film such as a polyimide film and a copper foil and performing thermocompression bonding has been proposed. (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 can bond the polyimide film and the copper foil at a high temperature of about 260 to 280 ° C. and at a temperature of about 30 to 60 kg / cm 2. It is necessary to perform the bonding under a high pressure of about ² cm. Under such bonding 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 gender.

[0008] As a coating composition for electronic parts such as wiring boards, a resin solution (varnish) in which an epoxy resin is mixed with aromatic polyimide or the like is coated with a heat-resistant coating layer made of the cured resin and a wiring board or the like. Various proposals have been made to improve the adhesiveness of.

[0009] However, the known composition may be used as an “adhesive for bonding a copper foil and an aromatic polyimide film” in the production of a copper-clad substrate as described above, because the bonding or curing temperature may be high. 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 bonding and curing is not flexible. It could not be used as.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the known adhesives by applying an adhesive solution, drying, laminating a copper foil, and forming an adhesive layer. Through a step of curing, it is intended to provide a "heat-resistant adhesive composition showing high adhesion at high temperature" that can suitably bond a heat-resistant film and various metal foils. is there.

An object of the present invention is to provide an adhesive layer (bonding sheet) which has flexibility and tackiness, and has a lamination with a copper foil and a step of curing the adhesive layer. An object of the present invention is to provide a heat-resistant adhesive composition capable of suitably bonding a heat-resistant film and various metal foils to obtain a laminate having excellent chemical resistance and curl-free performance. It is.

[0012]

[Means for Solving the Problems] The present invention provides (a) 2,
3,3 ′, 4′-biphenyltetracarboxylic acid or 3,3 ′, 4,4′-biphenyltetracarboxylic acid, a dianhydride of the acid, or an ester of the acid
100 mol% and 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether
Tertetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, pyromellitic acid, dianhydride of these acids, or esters of these acids 0 And an aromatic tetracarboxylic acid component consisting of

H ₂ N—R— [Si (R ₁ ) (R ₂ ) —O—] n—Si (R
_{3) (R 4) -R-} NH 2 (I)

(Wherein R in the formula represents a divalent hydrocarbon residue comprising a methylene group or a phenylene group having 2 to 6 carbon atoms, and R ₁ , R ₂ , R ₃ and R _{4 each} have 1 carbon atom) Represents 5 to 5 lower alkyl groups or phenyl groups, and n represents an integer of 3 to 60.
90 mol% (preferably 30 to 80 mol%) and the following general formula II

H ₂ N-Bz-X-Bz-Y-Bz-X-Bz-NH
₂ (II)

Wherein, in the formula, Bz represents a benzene ring having a 4,4 ′ bond, X is —O— or —CH ₂ —,
Y represents —SO ₂ — or —CH (CH ₃ ) ₂ —; an aromatic diamine of 20 to 70 mol%;

H ₂ N—Bz (R _n ) — [CH ₂ —Bz (R _n )] _m —NH ₂
(III)

Wherein, in the formula, Bz represents a benzene ring having a 4,4 ′ bond, and R represents a carboxyl group or a carbon number of 1 to 5;
N lower alkoxycarbonyl groups, wherein 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 comprising 1 to 20 mol% (preferably 5 to 15 mol%) of an aromatic diamine represented by the following formula:

(B) 5 to 100 parts by weight of a bifunctional epoxy compound having two epoxy groups, (c) a polyfunctional epoxy compound having three or more epoxy groups (hereinafter also referred to as a polyfunctional glycidylamine resin) And (d) an epoxy curing agent (preferably 0.01 to 90 parts by weight with respect to 100 parts by weight of all epoxy compounds) as resin components. To a heat-resistant resin adhesive composition.

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

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

The above-mentioned copolyimidesiloxane has an imidization ratio of at least 90%, particularly at least 95%, as measured by an infrared absorption spectrum analysis method, or has an absorption peak relating to an amide-acid bond of a polymer in the infrared absorption spectrum analysis. It is preferable that the imidation ratio is so high that substantially no absorption is found and only an absorption peak relating to the imide ring bond is observed.

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 rearrangement temperature of −10 ° C. or more, particularly 10 to 10 ° C. The temperature is preferably about 250 ° C.

The production method of copolyimide siloxane is as follows.
For example, an aromatic tetracarboxylic acid component containing about 60 mol% or more of 2,3,3 ′, 4′-biphenyltetracarboxylic acid and 20 to 90 mol% of the diaminopolysiloxane represented by the general formula (I); 20 to 70 mol% of an aromatic diamine represented by the general formula (II) and an aromatic diamine 1 having a substituent represented by the general formula (III) 1
~ 20 mol% with a diamine component in an organic polar solvent such as a phenol solvent, an amide solvent, a solvent for a compound having a sulfur atom, a glycol solvent, or an alkyl urea solvent at a high temperature (particularly, (Preferably at a temperature of 140 ° C. or more)), a polymerization method in which both monomer components are polymerized and imidized.

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

The above-mentioned copolyimide siloxane can be produced by polymerizing the aromatic tetracarboxylic acid component and the diamine component in an organic polar solvent at a low temperature of 0 to 80 ° C. to have a logarithmic viscosity of 0.1. A method in which a polyamic acid having a molecular weight of at least 05 is produced, and the polyamic acid is imidized 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 obtained by polymerizing an excess amount of the above-mentioned aromatic tetracarboxylic acid component and a diamine component comprising only diaminopolysiloxane (X component: 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 comprising only the aromatic tetracarboxylic acid component, the aromatic diamine and the substituted aromatic diamine. An imide oligomer (Y component: having a degree of polymerization of about 1 to 10 and having an amino group at a terminal) obtained by polymerizing the excess component is prepared. A method of producing a block-type copolyimide siloxane by mixing and reacting so that the ratio of the acid component and the total diamine component is substantially equimolar is also known. It can be given to an appropriate.

In the heat-resistant adhesive composition of the present invention,
If the copolyimide siloxane is manufactured using a tetracarboxylic acid other than biphenyltetracarboxylic acid as a main component, the copolyimide siloxane becomes hardly soluble in an organic polar solvent or has a poor compatibility with an epoxy resin. It is not appropriate because the solubility is deteriorated.

A-BPDA is used as the aromatic tetracarboxylic acid component used in the production of the copolyimidesiloxane.
Examples of the tetracarboxylic acid compound that can be used together with, for example, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, bis (3, 4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, pyromellitic acid, or
Preferable examples thereof include acid dianhydrides and esterified products.

The polysiloxane represented by the general formula (I) used for the production of the copolyimide siloxane is preferably a compound represented by the general formula I wherein R has 2 to 6 carbon atoms, particularly 3 to 5 carbon atoms.
A plurality of methylene groups or a divalent hydrocarbon residue comprising a phenylene group, wherein R _{1 to} R ₄ are a lower alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group or the like; It is preferably a phenyl group.
Is particularly preferably about 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) a biphenyl diamine compound, a diphenyl ether diamine compound, a benzophenone diamine compound, a diphenyl sulfone Diphenyl compounds, diphenylmethane diamine compounds, diphenylalkane diamino compounds such as 2,2-bis (phenyl) propane,
2,2-bis (phenyl) hexafluoropropane diamine compound, diphenylene sulfone diamine compound,

2) di (phenoxy) benzene diamine compound, di (phenyl) benzene diamine compound, 3) di (phenoxyphenyl) hexafluoropropane diamine compound, bis (phenoxyphenyl) propane diamine compound, bis (phenoxyphenyl) propane diamine compound Aromatic diamines mainly containing "aromatic diamine compounds having two or more aromatic rings (benzene rings or the like), particularly 2 to 5 aromatic rings" such as (phenoxyphenyl) sulfone 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 diamine compounds such as 1,4-diaminodiphenyl ether and 1,3-diaminodiphenyl ether, and 1,3-di (4-
Di (phenoxy) benzene-based diamine compounds such as aminophenoxy) benzene and 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Screw [4-
Bis (phenoxyphenyl) propane diamine compounds such as (3-aminophenoxy) phenyl] propane;
"Having 2 to 4 aromatic rings" such as di (phenoxyphenyl) sulfone diamine compound such as bis [4- (4-aminophenoxy) phenyl] sulfone and bis [4- (3-aminophenoxy) phenyl] sulfone Aromatic diamines containing mainly (aromatic diamine compound) (90 mol% or more) can be suitably mentioned.

As the organic polar solvent used in the production of the copolyimide siloxane, for example, N, N-dimethylacetamide, N, N-diethylacetamide, N, N
Amide solvents such as N-dimethylformamide, N, N-diethylformamide and N-methyl-2-pyrrolidone; and solvents containing sulfur atoms such as dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone and hexamethylsulfonamide Phenol solvents such as cresol, phenol and xylenol; solvents having an oxygen atom in the molecule such as acetone, methanol, ethanol, ethylene glycol, dioxane and tetrahydrofuran; and other solvents such as pyridine and tetramethylurea. Further, if necessary, an aromatic hydrocarbon solvent such as benzene, toluene and xylene, and another kind of organic solvent such as solvent naphtha and benzonitrile can be used in combination.

Epoxy group 2 used in the present invention
Examples of the bifunctional epoxy compound (b) having a single molecule include “one molecule” such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, and glycidylamine type epoxy resin. Epoxy compound having two epoxy groups therein ", and a plurality of the above-mentioned various bifunctional epoxy compounds can 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 a liquid at a temperature of 30 ° C. or lower.

The polyfunctional glycidylamine resin (C) used in the present invention includes a reaction product of an aromatic diamine and an epoxy compound such as epichlorohydrin [for example, a reaction product of metaxylenediamine and epichlorohydrin (4 reactants). Polyfunctional epoxy resin having a glycidyl group, "Tetrad-X" manufactured by Mitsubishi Gas Chemical Co., Ltd.), a reaction product of an aminophenol compound and an epoxy compound such as epichlorohydrin (a polyfunctional compound having three glycidyl groups) Epoxy resin, "ELM-100" manufactured by Sumitomo Chemical Co., Ltd.] and the like, and one kind of multifunctional epoxy compound having three or more epoxy groups. In the present invention, a polyfunctional glycidylamine resin may be used in combination. It is a liquid at room temperature, the viscosity of 10000 cps or less at 25 ° C., particularly 100
Those having about 6,000 centipoise are particularly preferred.

The epoxy curing agent (d) used in the heat-resistant adhesive composition of the present invention includes curing catalysts such as imidals, tertiary amines and triphenylphosphine, dicyandiamides and hydrazine. , Anionic polymerization type hardeners such as aromatic diamines, polyaddition type hardeners such as phenol novolak type hardeners having a hydroxyl group, and organic peroxides.

The amount of the epoxy curing agent to be used can be determined as appropriate, but is based on 100 parts by weight of the epoxy resin comprising the bifunctional epoxy compound (b) and the polyfunctional glycidylamine resin (c). , 0.01-90
It is preferable to use the parts by weight, particularly 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 about 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 the copolyimidesiloxane (a), the bifunctional epoxy compound (b), the polyfunctional epoxy compound (c), and the epoxy curing agent (d). A heat-resistant adhesive composition containing a resin component having a specific composition ratio of the following as a main component (especially 90% by weight or more, more preferably about 95 to 100% by weight) may be used. The resin composition may be a solution composition of a heat-resistant adhesive 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 10,000 poise, particularly 0.2 to 5000 poise, and more preferably about 0.3 to 1000 poise. Is preferred.

The heat-resistant adhesive composition of the present invention comprises:
Softening point of composition containing only uncured resin component (composition substantially not containing solvent) (temperature at which softening starts on the hot plate)
However, it is preferably about 150 ° C. or lower, particularly 120 ° C. or lower, 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 ° C.
It is preferable that the material can be thermally cured by heating to a curing temperature of 0 to 350 ° C.

As the organic polar solvent used for preparing the solution composition of the heat-resistant adhesive, the organic polar solvent used for producing the above-mentioned 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 suitably used.

The heat-resistant adhesive composition of the present invention is obtained by mixing a solution composition of a heat-resistant adhesive in which all of the above-mentioned resin components are uniformly dissolved in an organic polar solvent with a suitable metal foil, an aromatic polyimide film. By applying on a heat-resistant film surface such as, or a thermoplastic resin film surface such as polyester or polyethylene, and drying the applied layer at a temperature of 80 to 200 ° C. for 0.5 seconds to 100 minutes, a solvent is obtained. Of a heat-resistant adhesive composition in an uncured state (preferably having a solvent remaining ratio of not more than 0.5% by weight) having a thickness of about 1 to 200 μm. Film or bonding sheet).

The thin film (such as a bonding sheet) of the uncured heat-resistant adhesive composition produced as described above is
It has suitable flexibility and can be wound around a paper tube,
You can also make holes such as punching,
Furthermore, for example, a laminated sheet in which a thin layer of an uncured heat-resistant adhesive composition is formed on the above-mentioned heat-resistant or thermoplastic film, and a metal foil or a heat-resistant film for transfer are laminated. It is also possible to transfer onto a transfer destination metal foil or heat resistant film by passing between a pair of rolls (lamination rolls) heated to a temperature of about 20 to 200 ° C.

In order to form a laminate such as a copper-clad substrate by bonding a heat-resistant film and a metal foil or the like using the heat-resistant adhesive composition of the present invention, for example, the above-described method is used. A heat-resistant film and a metal foil are interposed at 80 to 200 ° C., particularly 100 to 180 ° C., via a thin heat-resistant adhesive layer.
At a temperature of, under pressure, laminate (lamination)
Further, the laminated product is used for about 80 to 350
C., in particular, at a temperature of 100 to 250 ° C., for 30 minutes to 40 hours, particularly 1 to 30 hours, and heat-curing of the heat-resistant adhesive layer facilitates the above-mentioned laminate 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, a polyethersulfone film, and a suitable metal foil such as a copper foil. It can be suitably used for joining.

[0046]

The present invention will be described in more detail with reference to the following examples. In the following examples, the logarithmic viscosity (η) is determined by adding copolyimide siloxane to N-solvent so that the resin component concentration becomes 0.5 g / 100 ml solvent.
A resin solution was prepared by uniformly dissolving it in methyl-2-pyrrolidone, and the solution viscosity of the solution and the solution viscosity of only the solvent were measured at 30 ° C., and the value was calculated by the following formula.

[0047]

(Equation 1)

The tackiness of the bonding sheet is as follows:
Observed by sandwiching the bonding sheet between polyester films (PET film) and performing roll lamination at 40 ° C., it is shown that there is considerable adhesion, and x indicates spontaneous peeling. The bonding strength of the bonding sheet was measured at 90 ° and 180 ° using a tensile tester manufactured by Intesco Corporation at a peeling speed of 50 mm / min.
° It is the result measured by performing a peeling test.

A copper-clad substrate is formed using a heat-resistant adhesive composition, and the copper foil is etched and removed. The radius of curvature showing the curl of the wiring board is JIS C501.
2 [curvature radius (mm) = L ² / 8h
(L: sample length, h: warpage height)]. Furthermore, the chemical resistance of the copper laminate, after immersing the sample used for the curl test in acetone, visually observing the surface of the copper laminate, showed that no change was observed. Indicates that the surface is whitened.

[Production of Copolyimide Siloxane A] Reference Example 1 A 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 the diamine component: 50 mol%) was added to 200 g of N-methyl-2-pyrrolidone (NMP), and the mixture was stirred at room temperature under a nitrogen stream (0.5 L / min) for 30 minutes. And dissolved.

In the solution, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) 12.
53 g (molar ratio: equimolar to the diamine component) was added, and 5
After dissolving by stirring at 0 ° C. for 2 hours, 2,2-
6.12 g of bis [4- (4-diaminophenoxy) phenyl] propane (BAPP) (molar ratio in the diamine component: 35 mol%) and diaminobenzoic acid (DABA)
0.97 g (molar ratio in the diamine component: 15 mol%) was added, and the mixture was stirred at 50 ° C. for 1 hour. Thereafter, the solution was heated to 200 ° C. and stirred for 3 hours to obtain copolyimidesiloxane A. Was uniformly dissolved at 18% by weight 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 copolyimidesiloxane B] a-
11.83 g (42 mmol) of BPDA was used, and as a diamine component, 17.6 g (20 mmol) of diaminopolysiloxane used in Reference Example (1), BA
In the same manner as in Reference Example 1, except that 8.2 g (20 mmol) of PP, 0.31 g (2 mmol) of diaminobenzoic acid, and 160 g of NMP were used as a polymerization solvent, 18% by weight of copolyimidesiloxane B was used. A uniformly dissolved polymer solution was prepared. This copolyimide siloxane B had an imidization ratio of substantially 100% and an intrinsic viscosity (30 ° C.) of 1.8.

Reference Example 3 [Production of copolyimidesiloxane C]
11.77 g (40 mmol) of BPDA were used, and 17.6 g (20 mmol) of diaminopolysiloxane used in Reference Example 1 as a diamine component and BAPP
Reference Example 1 except that 8.2 g (20 mmol) was used.
18% by weight of copolyimidesiloxane C
A uniformly dissolved polymer solution was prepared. This copolyimide siloxane C has an imidization ratio of substantially 10
0% and the logarithmic 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 and (b)
Bifunctional epoxy compound having an epoxy group (product name: Epicoat 807, manufactured by Yuka Shell Epoxy Co., Ltd.) 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 Company, Ltd.), and (d) a polyaddition-type curing agent (Meiwa Kasei Co., Ltd.) as an epoxy curing agent 18 parts by weight of a phenol novolak type curing agent H-1) and 0.01 part by weight of an anionic type curing agent: 2-phenylimidazole (2PZ), and 200 parts by weight of tetrahydrofuran (THF) as a solvent were charged at room temperature (25%). ℃), and stirred for about 2 hours to prepare a solution composition of a heat-resistant adhesive (viscosity at 25 ° C .: 12 poise).
Was prepared. This solution composition maintained a uniform solution state even when left at room temperature for one week.

[Production of Laminate Using Heat-Resistant Adhesive] A solution composition of the above-mentioned heat-resistant adhesive was applied on a polyimide film (Ube Industries, Ltd., trade name: UPILEX-S type, thickness 75 μm). Apply with a doctor blade to a thickness of 175 μm, then apply the applied layer at 60 ° C. for 10 minutes
After heating at 100 ° C. for 10 minutes and drying at 120 ° C. for 10 minutes, a sheet layer of a heat-resistant adhesive composition having a thickness of 25 μm (a bonding sheet layer of an uncured and dried heat-resistant adhesive composition) was formed on a polyimide film. , Softening point: 95 ° C).

A polyimide film having a bonding sheet layer of this heat-resistant adhesive composition and a copper foil (35 μm)
Are laminated by applying pressure while passing between laminating rolls heated to 130 ° C., and the laminated body is pressed at 80 ° C. for 2 hours, at 100 ° C. for 2 hours, at 120 ° C. for 1 hour, 140 ° C. 160 ° C. for 1 hour
Heat treatment was performed in a nitrogen stream at 10 ° C. for 10 hours to cure the bonding sheet layer, thereby producing 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 prepared 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 solution composition of the heat-resistant adhesive was prepared. Laminates were produced in the same manner as in Example 1 except that each of the above solution compositions was used. Table 1 shows the performance of these laminates.

[0058]

[Table 1]

[0059]

The heat-resistant adhesive composition according to the present invention comprises: (a) a specific copolyimidesiloxane;
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 a resin component in a specific composition ratio.

The heat-resistant adhesive composition of the present invention can bond various metal foils such as copper foil to heat-resistant support materials such as heat-resistant films and inorganic sheets at a relatively low temperature. A bonding sheet can be easily formed from the solution composition of the heat-resistant adhesive composition, and the laminated body bonded via the bonding sheet has an adhesive layer exhibiting 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 TAB copper-clad boards. And finally the quality of the product can be improved and the defect rate can be reduced.

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

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-25453 (JP, A) JP-A-60-130666 (JP, A) JP-A-2-158681 (JP, A) JP-A-1- 121325 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 1/00-201/10 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] (A) 2,3,3 ', 4'-biphenyltetracarboxylic acid or 3,3', 4,4'-biphenyltetracarboxylic acid, a dianhydride of the acid, or an ester of the acid 60 to 100 mol% and 3,3 ', 4
4'-benzophenonetetracarboxylic acid, 3,3 ',
4,4'-diphenylethertetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, pyromellitic acid, dianhydride of these acids objects, or an aromatic tetracarboxylic acid component consisting of ester 0-40 mol%, their acids, formula _{I H 2 n-R- [Si} (R 1) (R 2) -O-] n-Si ( R
₃ ) (R ₄ ) —R—NH ₂ (I) (where R represents a divalent hydrocarbon residue comprising a methylene group or a phenylene group having 2 to 6 carbon atoms;
₁ , R ₂ , R ₃ and R ₄ each represent a lower alkyl group having 1 to 5 carbon atoms or a phenyl group, and n represents an integer of 3 to 60. )
Diaminopolysiloxane 20-90 mol% and the following general formula _{II H 2 N-Bz-X} -Bz-Y-Bz-X-Bz-NH shown in
₂ (II) [wherein, Bz represents a benzene ring having a 4,4 ′ bond, X represents —O— or —CH ₂ —, and Y represents —SO ₂
-, or -CH (CH _{3) 2} - Aromatic diamine 20 to 70 mol% and the following formula represented by the _{indicating] III H 2 N-Bz (} R n) - [CH 2 -Bz (R n) ] _m -NH ₂
(III) [wherein, Bz represents a benzene ring having a 4,4 ′ bond, R represents a carboxyl group or a lower alkoxycarbonyl group having 1 to 5 carbon atoms, n represents 1 or 2, and m represents Is 0 or 1. Aromatic diamines 1 to 20 represented by the formula:
100 parts by weight of a soluble copolyimide siloxane obtained from a diamine component consisting of mol%, and (b) a bifunctional epoxy compound 5 having two epoxy groups.
(C) 10 to 70 parts by weight of a polyfunctional epoxy compound having three or more epoxy groups, and (d) an epoxy curing agent as a resin component. Resin adhesive composition.