JP3039818B2 - Heat resistant adhesive - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermosetting resin comprising (A) a specific soluble polyimide siloxane, (B) a bismaleimide-triazine resin, a bismaleimide resin, a cyanate compound resin and / or an acrylate compound resin. A heat-resistant adhesive in which a water-soluble resin and (C) an epoxy compound having an epoxy group (epoxy resin) are contained at a specific composition ratio as a resin component, or (a) a specific soluble polyimide siloxane; The present invention relates to a heat-resistant adhesive containing b) an epoxy compound (epoxy resin) and (c) a polyaddition type epoxy curing agent as a resin component at a specific composition ratio.

The heat-resistant adhesive of the present invention can bond various metal foils such as a copper foil to a heat-resistant supporting material (eg, a heat-resistant film, an inorganic sheet, etc.) at a relatively low temperature. In the laminate bonded with the heat-resistant adhesive, the adhesive layer exhibits a sufficient adhesive strength and excellent heat resistance. For example, a flexible wiring board, TAB (Tape Automated Bo),
If it is used for the production of copper-clad substrates for nding, etc., each substrate obtained using the heat-resistant adhesive can perform various high-temperature processing steps such as soldering with confidence. It can improve the quality of the final product and reduce the defect 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, when the flexible wiring board manufactured using a known adhesive is exposed to a high temperature in a subsequent soldering process, there is a problem that the adhesive layer causes blistering or peeling, and the heat resistance of the adhesive is high. There was a desire for improvement.

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 to 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 under a high pressure of about ² cm ^2. 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. That was a problem.

[0007] As a coating composition for electronic parts such as wiring boards, a resin solution (varnish) in which an epoxy resin is blended with aromatic polyimide or the like is coated with a heat-resistant coating layer composed of the cured resin and a wiring board. Various proposals have been made to improve the adhesiveness of. However, a known composition is 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, such that the temperature of lamination or curing becomes high, There is a problem that the compatibility between the 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, and can be used as an actual adhesive. It was not something.

[0008]

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. It is an object of the present invention to provide a “heat-resistant adhesive exhibiting high adhesiveness at high temperatures” that can suitably bond a heat-resistant film and various metal foils through a curing step.

[0009]

[Means for Solving the Problems] The first invention of this application relates to (A) 3,3 ', 4,4'-benzophenonetetracarboxylic acid or 3,3', 4,4'-diphenyl ether
Tertetracarboxylic acid, dianhydride of these acids, or esters of these acids 90 to 100 mol% and 2,3,
3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′,
An aromatic tetracarboxylic acid component comprising 4,4'-biphenyltetracarboxylic acid, pyromellitic acid, a dianhydride of the acid, or an ester of the acid in an amount of 0 to 10 mol%;

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 plurality of methylene groups or phenylene groups having 2 to 6 carbon atoms, and R ₁ , R ₂ , R ₃ and R ₄ represent carbon atoms) Numbers 1-5
Lower alkyl groups or phenyl groups, and n is 3 to 6
0, preferably an integer of 5 to 50. 10) to 80 mol% of a diaminopolysiloxane represented by the following general formula:

H ₂ N-Bz-O-Bz-C ₃ H ₆ -Bz-O
-Bz-NH ₂

(Bz represents a benzene ring.) A diamine component comprising from 20 to 90 mol% of an aromatic diamine represented by the following formula: When a film is formed, the film is softened at an elastic modulus of 150 kg / mm ² or less. 100 parts by weight of a soluble polyimide siloxane having a temperature of 5 ° C. or higher,

(B) at least one thermosetting resin selected from the group consisting of a bismaleimide-triazine resin, a bismaleimide resin, a cyanate compound, and an acrylate compound, in an amount of 10 to 500 parts by weight, particularly 12 To 150 parts by weight, and (C) 5 to 300 parts by weight, particularly 5 to 40 parts by weight of an epoxy compound having an epoxy group are contained as resin components, and a solution composition of these resin components and an organic polar solvent is heat-resistant. The present invention relates to a heat-resistant adhesive characterized by having good tackiness and punching property with a protective film of an uncured thin film applied to a support material and dried.

The second invention of this application is characterized in that 100 parts by weight of the soluble polyimide siloxane, (b) 5 to 300 parts by weight of an epoxy compound having an epoxy group, and
(c) 10 to 100 parts by weight of an epoxy curing agent that is an aromatic compound having a plurality of hydroxyl groups is contained as a resin component, and a solution composition of these resin components and an organic polar solvent is applied to a heat-resistant support material, and dried. The present invention relates to a heat-resistant adhesive characterized by having good tackiness and punching property with an uncured thin film protective film. Further, the third invention of this application is to apply a solution composition of any one of the above resin components and an organic polar solvent to a heat-resistant support material, and to provide a protective film on a dried uncured thin film, The present invention relates to a laminated sheet-like heat-resistant adhesive characterized by good tackiness and punching properties.

The polyimide siloxane used in the present invention includes 3,3 ', 4,4'-benzophenonetetracarboxylic acid or 3,3', 4,4'-diphenylethertetracarboxylic acid, and diacids of these acids. Anhydrides or esters of these acids, for example, 90 to 100 mol% of lower alkyl esters such as methyl, ethyl, propyl, butyl and the like, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4, 4'-biphenyltetracarboxylic acid, pyromellitic acid, dianhydrides of these acids, or esters of these acids, for example, methyl, ethyl, propyl,
An aromatic tetracarboxylic acid component comprising 0 to 10 mol% of a lower alkyl ester such as butyl;

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 plurality of methylene groups or phenylene groups having 2 to 6 carbon atoms, and R ₁ , R ₂ , R ₃ and R ₄ represent carbon atoms) Numbers 1-5
Lower alkyl groups or phenyl groups, and n is 3 to 6
Indicates an integer of 0. 10) to 80% by mol (particularly 20 to 70% by mol, more preferably 20 to 60% by mol) represented by the following general formula:

H ₂ N-Bz-O-Bz-C ₃ H ₆ -Bz-O
-Bz-NH ₂ (however, Bz represents a benzene ring.) Aromatic diamine from 20 to 90 mol% of the formula (in particular 30 to 80 mol%,
And more preferably 40 to 80 mol%), and a high molecular weight obtained by polymerizing and imidizing a diamine component having a modulus of 150 k when forming a film.
Soluble polyimide siloxane having a softening temperature of 5 ° C. or more at g / mm ² or less is used.

The above-mentioned polyimidesiloxane 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 in one of organic polar solvents (especially an amide solvent), especially Preferably, it can be uniformly dissolved at a concentration of about 5 to 40% by weight.

The polyimide siloxane has an imidation ratio of at least 90%, particularly at least 95%, as measured by infrared absorption spectroscopy, or has an absorption peak relating to an amide-acid bond of the polymer substantially in infrared absorption spectroscopy. It is preferable to have a high imidization ratio such that only the absorption peak relating to the imide ring bond is not found, and is only found.

Further, the above-mentioned polyimidesiloxane is
When formed into a film, its elastic modulus is 250 kg /
mm ² or less, in particular 0.1～200Kg / mm ² approximately, the thermal decomposition initiation temperature of 250 ° C. or higher, particularly 300 ° C. or higher, and, second order transition temperature of -10 ° C. or higher, particularly 5 to 250 It is preferable that the temperature is about ° C.

As a method for producing the polyimide siloxane, for example, an aromatic tetracarboxylic acid component, 10 to 80 mol% of the diaminopolysiloxane represented by the above general formula I and 20 to 90 mol% of the aromatic diamine represented by the above general formula
Using a diamine component consisting of a phenol-based solvent, an amide-based solvent, a solvent of a compound having a sulfur atom, a glycol-based solvent, an alkylurea-based solvent, or the like, at an elevated temperature (particularly, (Preferably at a temperature of 140 ° C. or higher), a polymerization method in which substantially equimolar amounts of both monomer components are polymerized and imidized.

In addition, as a method for producing the above-mentioned polyimide 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 have a logarithmic viscosity of 0.05. A method in which the above polyamic acid is produced, and the polyamic acid is imidized by any known method to produce a soluble polyimide siloxane.

Further, in the above-mentioned process for producing a polyimide siloxane, an imide siloxane oligomer (X component: average polymerization) obtained by polymerizing an excess amount of the above-mentioned aromatic tetracarboxylic acid component and a diamine component consisting of only diaminosiloxane is used. Degree is about 1 to 10 and has an acid or an acid anhydride group at the terminal.), And an excess amount of the above-mentioned aromatic tetracarboxylic acid component and an excess amount of a diamine component consisting of only an 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) is prepared, and then the X component and the Y component are combined with all the acid components and all the diamine components. A method of producing a block polyimide siloxane by mixing and reacting so that the ratio is approximately equimolar can also be suitably mentioned.

The aromatic tetracarboxylic acids used for the production of the polyimide siloxane are preferably 3,4
3 ', 4,4'-benzophenonetetracarboxylic dianhydride or 3,3', 4,4'-diphenylethertetracarboxylic dianhydride is exemplified.

In the present invention, the polyimide siloxane contains not more than 10 mol% of the above-mentioned aromatic tetracarboxylic acids in 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4 '-Biphenyltetracarboxylic acid, pyromellitic acid, dianhydrides of these acids, or those obtained using aromatic tetracarboxylic acid components replaced with lower alkyl esters of these acids may be used. .

As the polysiloxane represented by the general formula V used for the production of the above-mentioned polyimidesiloxane, R in the general formula I is a compound having 2 to 6 carbon atoms, particularly 3 to 5 carbon atoms. Or a divalent hydrocarbon residue consisting of a phenylene group, wherein R _{1 to} R ₄ are preferably a lower alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group or a propyl group, or a phenyl group. Further, it is preferable that n is particularly about 5 to 20, and more preferably about 5 to 15.

The aromatic diamine represented by the above general formula used for the production of the polyimide siloxane includes:
2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), 2,2-bis [4- (3-
Bis- such as aminophenoxy) phenyl] propane
(Aminophenoxyphenyl) propane-based diamine compound is used.

In the present invention, the polyimide siloxane contains 10 mol% or less of the above-mentioned aromatic diamine as a biphenyl diamine compound, a diphenyl ether diamine compound, a benzophenone diamine compound, a diphenyl sulfone diamine compound, a diphenyl methane diamine compound. Diamine, diphenylalkane diamine compound, 2,2-
Bis (phenyl) hexafluoropropane diamine compound, diphenylenesulfone diamine compound, di (phenoxy) benzene diamine compound, di (phenyl)
Benzene diamine compound, di (phenoxyphenyl)
It is obtained by using an aromatic diamine component substituted with an aromatic diamine having 2 to 5 aromatic rings (such as a benzene ring) such as a hexafluoropropane diamine compound and a di (phenoxyphenyl) sulfone diamine compound. May be used.

[0031]

Examples of the organic polar solvent used in the production of the polyimide siloxane include N, N-dimethylacetamide (DMAC), N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide. , N-methyl-2-pyrrolidone (NM
Amide solvents such as P), solvents containing sulfur atoms such as dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, and hexamethylsulfonamide; phenol solvents such as cresol, phenol and xylenol; acetone, methanol and ethanol , Ethylene glycol, dioxane, a solvent having an oxygen atom in the molecule such as tetrahydrofuran, pyridine,
Other solvents such as tetramethyl urea can be mentioned, and further, if necessary, benzene, toluene, xylene and other aromatic hydrocarbon solvents, solvent naphtha, other types of organic solvents such as benzonitrile It is also possible to use together.

The bismaleimide-triazine resin used in the heat-resistant adhesive of the present invention includes, for example, an imide group and a triazine ring obtained from a bismaleimide component and a triazine monomer or a prepolymer component having a cyanate group. A thermosetting resin composition having
Acrylic esters, divinylbenzene, styrene,
It may be modified with 0 to 30% by weight with triallyl isocyanate or the like, and particularly preferred is "BT resin" manufactured by Mitsubishi Gas Chemical Company, Ltd.

The bismaleimide resin described above may be any resin having an unsaturated (double bond) group based on maleic acid at both ends obtained by condensing maleic anhydride and a diamine compound. "Bismaleimide" manufactured by Mitsui Toatsu Chemicals, Inc .; "ATU-BM" manufactured by Ajinomoto Co., Ltd.
I resin "," Kelimide "manufactured by Nippon Polyimide Co., Ltd.
"Compimide" manufactured by Technohemie Co., Ltd. can be mentioned.

The above-mentioned diamine compounds include diaminobenzene, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diaminodiphenyl ether, 4,4 '
Aromatic diamine compounds such as -diaminodiphenylmethane and 2,2-bis (4-aminophenyl) propane are preferred.

The cyanate compound may be any organic compound having a cyanate group, for example, bisphenol A dicyanate, bis (4-cyanatephenyl)
Ether and 1,1,1-tris (4-cyanatephenyl) ethane may be used. In particular, "XU-71787-02" manufactured by The Dow Chemical Company can be mentioned.

The acrylate compound may be any unsaturated compound having an acryloyl group or a methacryloyl group at the terminal or in the side chain of the molecule. Particularly, the acrylate compound has a molecular weight of about 130 to 2000 and is liquid at room temperature. It is preferable that the solubility in an organic polar solvent such as dioxane, tetrahydrofuran or the like is as high as 5% by weight or more. For example, a polyol poly (meth) acrylate or triazine skeleton ester-bonded to a polyol such as glycerin or erythritol And a polyester (meth) acrylate having a polyester skeleton.

In the present invention, as the acrylate-based unsaturated compound, in particular, a polyol poly (meth) acrylate-based acrylate compound (Aronix-M400 manufactured by Toa Gosei Chemical Industry Co., Ltd., Kayarad-TMPTA manufactured by Nippon Kayaku Co., Ltd. Etc.) can be suitably mentioned.

Examples of epoxy compounds having an epoxy group used in the heat-resistant adhesive of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, glycidyl ether type epoxy resin, Glycidyl ester type epoxy resin, glycidylamine type epoxy resin, epoxy modified polysiloxane and the like "epoxy compound having one or more epoxy groups" can be mentioned,
A plurality of the above-mentioned various epoxy resins may be used in combination. In the present invention, it is particularly preferable that the epoxy resin has a melting point of 90 ° C. or less, particularly about 0 to 80 ° C., or a liquid at a temperature of 30 ° C. or less.

In the heat-resistant adhesive of the present invention, when the film is formed, the elastic polyimide has a modulus of 150 kg / mm ² or less (particularly 0.5 to 100 kg / mm ² ) and a softening temperature. Is 5 ° C. or more (particularly 5 to 250 ° C.), a metal foil such as a copper foil and a heat-resistant film such as an aromatic polyimide film are joined by this heat-resistant adhesive to form a copper-clad substrate. When a wiring board or the like is formed by etching a copper foil or the like of the copper-clad substrate, the wiring board has a radius of curvature of 80 mm or more and is not optimally shown because it does not show a large warp.

In the first invention of this application, an epoxy curing agent, a curing accelerator and the like may be used in combination, but there are cases where the blending of a curing agent and the like is not preferable. As the polyaddition type epoxy curing agent used in the second invention of this application, an aromatic compound having a plurality of hydroxyl groups is preferable, and in particular, a phenol novolak type epoxy curing agent (Phenol Novolak H-1 manufactured by Meiwa Kasei Co., Ltd.) , H-5, etc.)
Can be suitably mentioned.

The heat-resistant adhesive of the present invention comprises a resin component having a specific composition ratio of the above-mentioned polyimide siloxane, thermosetting resin and epoxy compound, or polyimide siloxane, epoxy compound and polyaddition type epoxy curing agent. A resin component having a specific composition ratio as a main component (especially preferably 90% by weight or more, more preferably 9% by weight or more).
Any heat-resistant adhesive containing about 5 to 100% by weight) may be used, but the total amount of the above resin components is preferably 3 to 50% by weight, more preferably 5 to 50% by weight in a suitable organic polar solvent.
A solution composition of a heat-resistant adhesive which is uniformly dissolved at a concentration of 40% by weight may be used.

The solution composition of the heat-resistant adhesive has a solution viscosity (30 ° C.) of 0.1 to 10,000 poise, particularly 0.2 to 5000 poise, and more preferably 0.3 to 5000 poise.
It is preferably about 1,000 poise, and if necessary, an inorganic filler such as silicon dioxide (for example, “Aerosil 200” of Nippon Aerosil Co., Ltd.) may be added to the solution composition.
Etc.) may be added.

The heat-resistant adhesive of the present invention has a softening point (temperature at which softening starts on a hot plate) of a composition comprising only an uncured resin component of 150 ° C. or less, particularly 120 ° C. or less. More preferably, the temperature is 100 ° C. or lower. The heat-resistant adhesive of the present invention is particularly preferably 140 to 300.
It is preferred that the composition can be thermally cured by heating to a curing temperature of 150 ° C., more preferably 150 to 280 ° C. Further, the heat-resistant adhesive of the present invention,
As the resin component, other thermosetting resins such as a phenol resin may be contained in a small proportion.

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 above-mentioned polyimidesiloxane 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 of the present invention is obtained by mixing a solution composition of a heat-resistant adhesive in which all of the resin components described above are uniformly dissolved in an organic polar solvent with a suitable metal foil or aromatic polyimide film. Or the like, or a film of a thermoplastic resin such as polyester or polyethylene, and drying the applied layer at a temperature of 80 to 200 ° C. for 20 seconds to 100 minutes, whereby the solvent becomes 1 A thin film (dry film or sheet having a thickness of about 1 to 200 μm) of an uncured heat-resistant adhesive which has been removed to a weight percent or less (preferably a solvent remaining ratio is particularly 0.5 weight% or less). Can be formed.

The uncured heat-resistant adhesive thin film produced as described above has a suitable flexibility, and is wound around a paper tube or the like, or subjected to a punching process such as a punching method. Further, for example, a laminated sheet having a thin layer of an uncured heat-resistant adhesive formed on the heat-resistant or thermoplastic film, and a metal foil or a heat-resistant film for transfer destination. About 20 ~ 200 ℃
By passing between a pair of rolls (lamination rolls) heated to a temperature, it is also possible to transfer onto a transfer destination metal foil or heat resistant film.

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 of the present invention, for example, a thin film formed as described above is used. The heat-resistant film and the metal foil are laminated (laminated) under pressure at a temperature of 80 to 200 ° C., particularly 100 to 180 ° C., via a heat-resistant adhesive layer having a shape like that. About 150-300
C., especially at 150 to 280.degree. C., for 30 minutes to 40 hours, especially 1 to 30 hours, and heat-curing of the heat-resistant adhesive layer causes no problems with the laminate. It can be easily and continuously manufactured.

The heat-resistant adhesive of the present invention is used for bonding a heat-resistant film such as an aromatic polyimide film, a polyamide film, a polyetheretherketone, a PEEK film or a polyethersulfone film to a suitable metal foil such as a copper foil. It can be suitably used for

[0050]

The present invention will be described below in further detail with reference to examples. In the following examples, logarithmic viscosity (η)
Is a method for preparing a resin solution by uniformly dissolving an aromatic polyimide or imide oligomer in N-methyl-2-pyrrolidone so that the resin component concentration becomes 0.5 g / 100 ml of a solvent, and preparing a solution viscosity of the solution. And the value obtained by measuring the solution viscosity of only the solvent at 30 ° C. and calculating by the following formula.

[0051]

(Equation 1)

The adhesive strength is a result obtained by performing a 90 ° peel test at a peel speed of 50 mm / min using a tensile tester manufactured by Intesco Corporation.

[Production of Polyimidesiloxane] Reference Example 1 In a glass flask having a capacity of 500 ml, 1) 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA) 0.05 mol, 2) ω, ω '
-Bis (3-aminopropyl) polydimethylsiloxane (manufactured by Shin-Etsu Silicon Co., Ltd., X-22-161AS, n:
9) 0.02 mol, 3) 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 0.0
2 mol, and 4) N-methyl-2-pyrrolidone (N
MP) 160 g,

The mixture was stirred at 50 ° C. for 2 hours in a stream of nitrogen to form a polyamic acid.
The temperature was raised to 0 ° C., and the mixture was stirred at that temperature for 3 hours to produce a polyimidesiloxane having an anhydride group at a terminal.

The polyimide siloxane has a logarithmic viscosity of 0.40, and a polyimide siloxane film (thickness: about 50 μm) formed from a solution (reaction liquid) of the polyimide siloxane by a solution casting method.
Had an elastic modulus of 51 kg / mm ² and a softening temperature of 175 ° C.

Reference Example 2 As an aromatic tetracarboxylic acid component, 3,3 ′, 4,4
Using 0.05 mol of 4'-diphenylethertetracarboxylic dianhydride (BTDA), diaminopolysiloxane (X-22-161AS) as a diamine component
A polyimide siloxane was produced in the same manner as in Reference Example 1 except that 0.025 mol and 0.025 mol of BAPP were used.

The above-mentioned polyimide siloxane has a logarithmic viscosity of 0.38, and a polyimide siloxane film (thickness: about 50 μm) formed by a solution casting method from a solution (reaction liquid) of the polyimide siloxane.
Had an elastic modulus of 21 kg / mm ² and a softening temperature of 109 ° C.

Reference Example 3 As the aromatic tetracarboxylic acid component, 3,3 ′, 4,
Using 0.05 mol of 4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), diaminopolysiloxane (X-22-161AS) as a diamine component
A polyimide siloxane was produced in the same manner as in Reference Example 1 except that 0.02 mol and 0.03 mol of bis [4 (3-aminophenoxy) phenyl] sulfone (BAPS) were used.

The polyimide siloxane has a logarithmic viscosity of 0.36, and a polyimide siloxane film (thickness: about 50 μm) formed by a solution casting method from a solution (reaction liquid) of the polyimide siloxane.
Had an elastic modulus of 48 kg / mm ² and a softening temperature of 168 ° C.

Example 1 [Preparation of solution composition of heat-resistant adhesive] In a glass flask having a capacity of 500 ml, 25 g of the polyimidesiloxane prepared in Reference Example 1 described above and bismaleimide-
Triazine resin (BT330, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
9T) 65 g, epoxy resin (trade name: Epikote 152, manufactured by Yuka Shell Epoxy Co., Ltd.), 10 g, dioxane 2
And then stirred at room temperature (25 ° C.) for about 2 hours to obtain a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 0.1).
6 poise) was prepared. This solution composition maintained a uniform solution state (viscosity) even when left at room temperature for one week.

[Production of Laminate with Heat-Resistant Adhesive] A solution composition of the above-mentioned heat-resistant adhesive was applied to a polyimide film (Ube Industries, Ltd., trade name: UPILEX-S type, thickness 75 μm). 125μm with doctor blade
And then dried by heating at 50 ° C. for 30 minutes, 100 ° C. for 30 minutes, 170 ° C. for 20 minutes, and a heat-resistant adhesive layer having a thickness of about 20 μm on a polyimide film. (Uncured dried layer, softening point: 25 ° C)
Was formed.

The polyimide film having the heat-resistant adhesive layer and a copper foil (35 μm) were superposed and the temperature was raised to 160 ° C.
The laminate was pressed by passing the laminate between the heated laminate rolls while applying pressure.
1 hour at 180 ° C., 1 hour at 180 ° C., 1 hour at 200 ° C., 2
Heat treatment was performed at 20 ° C. for 5 hours and further at 250 ° C. for 6 hours in a nitrogen stream to cure the heat-resistant adhesive layer, thereby producing a laminate. The adhesive strength of the obtained laminate was measured, and the results are shown in Table 1.

Example 2 A heat-resistant adhesive solution composition was prepared in the same manner as in Example 1 except that the polyimidesiloxane prepared in Reference Example 2 was used. Further, a laminate was produced in the same manner as in Example 1 except that the above solution composition was used. Table 1 shows the performance of the laminate.

Examples 3 to 9 and Comparative Examples 1 to 4 Polyimide siloxanes prepared in Reference Examples 1 to 3 as shown in Table 1 were used, and the composition of each component was as shown in Table 1. Otherwise, in the same manner as in Example 1, solution compositions of a heat-resistant adhesive were prepared. Further, using each of the solution compositions described above, drying was performed at 50 ° C. for 30 minutes.
Except for 30 minutes at 0 ° C., as in Example 1,
Each of the laminates was manufactured. Table 1 shows the performance of the laminate.

[0065]

[Table 1]

In Table 1, "workability at 30 ° C."
The tackiness (tackability with the protective film), punching property, and workability during heat bonding were comprehensively evaluated. ◎ indicates excellent, 優 indicates good, Δ indicates normal, and × indicates poor.

In the column of “thermosetting resin” in Table 1,
"BT Resin 3309T" is a bismaleimide-triazine resin manufactured by Mitsubishi Gas Chemical Co., Ltd. "Bismaleimide" is a bismaleimide resin manufactured by Mitsui Toatsu Chemicals, Inc. "Cyanate Compound XU-71781"
“-02” is a cyanate compound resin manufactured by Dow Chemical Company, and “Aronix 215” and “Aronix M400” are acrylate compound resins manufactured by Toa Gosei Chemical Co., Ltd.

In Table 1, "Epoxy Compound", "Epicoat 152" and "Epicoat 807" are epoxy resins manufactured by Yuka Shell Epoxy Co., Ltd.
Further, in the column of "curing agent" in Table 1, "phenol novolak H-1" is a polyaddition type epoxy curing agent manufactured by Meiwa Kasei Co., Ltd.

[0069]

The heat-resistant adhesive of the present invention is obtained by applying the solution composition on a support film and drying at a relatively low temperature to form an uncured and thin heat-resistant adhesive layer. It can be easily formed, and the thin heat-resistant adhesive layer has sufficient flexibility, and the thin heat-resistant adhesive layer on the supporting film is perforated. No problem at all, and it is also possible to transfer onto other heat-resistant support film at an appropriate temperature,
And it has good workability that can laminate the heat-resistant film and the copper foil at a relatively low temperature.

The heat-resistant adhesive of the present invention is excellent in heat resistance (excellent adhesiveness at a temperature of 150 ° C. or more) and flexibility even after being 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.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-158681 (JP, A) JP-A-3-14890 (JP, A) JP-A-5-9441 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C09J 1/00-201/10 CA (STN) REGISTRY (STN) Patent file (PATOLIS)

Claims (4)

(57) [Claims] (A) 3,3 ', 4,4'-benzophenonetetracarboxylic acid or 3,3', 4,4'-diphenylethertetracarboxylic acid, a dianhydride of these acids,
Alternatively, 90-100 mol% of esters of these acids and 2,
3,3 ′, 4′-biphenyltetracarboxylic acid, 3,
3 ', 4,4'-biphenyl tetracarboxylic acid, pyromellitic acid, dianhydride thereof acid, or an aromatic tetracarboxylic acid component consisting of an ester 0 to 10 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) ( wherein, R in the formula is a divalent hydrocarbon residue consisting of 2 to 6 more methylene group or a phenylene group having a carbon number, R ₁ , R ₂ , R ₃ and R ₄ represent a lower alkyl group having 1 to 5 carbon atoms or a phenyl group, and n represents an integer of 3 to 60). General formula of H ₂ N-Bz-O-Bz-C ₃ H ₆ -Bz-O-Bz-NH
₂ (where Bz represents a benzene ring) and a diamine component composed of 20 to 90 mol% of an aromatic diamine having a modulus of 150 when formed into a film.
100 parts by weight of a soluble polyimide siloxane having a softening temperature of 5 ° C. or more at kg / mm ² or less; 10 to 500 parts by weight of at least one kind of thermosetting resin obtained, and (C) 5 to 300 parts by weight of an epoxy compound having an epoxy group are contained as resin components, and a solution composition of these resin components and an organic polar solvent is contained. A heat-resistant adhesive characterized in that it has good tackiness and punching property with a protective film of a dried uncured thin film obtained by applying an object to a heat-resistant support material. 2. (a) 100 parts by weight of the soluble polyimidesiloxane according to claim 1, (b) 5 to 300 parts by weight of an epoxy compound having an epoxy group, and (c) epoxy which is an aromatic compound having a plurality of hydroxyl groups. 10 to 100 parts by weight of a curing agent is contained as a resin component, and a solution composition of the resin component and an organic polar solvent is applied to a heat-resistant support material, and the tackiness of the dried uncured thin film with a protective film is improved. A heat resistant adhesive characterized by good punching properties. 3. The heat-resistant adhesive according to claim 2, wherein (c) the epoxy curing agent is a phenol-novolac epoxy curing agent. 4. A solution composition of the resin component according to any one of claims 1 to 3 and an organic polar solvent is applied to a heat-resistant support material, and a dried uncured thin film is provided with a protective film.
A laminated sheet-like heat-resistant adhesive characterized by good tackiness and punching properties.