JP2943953B2 - Heat resistant adhesive - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermosetting resin comprising (a) a soluble polyimide siloxane, (b) a bismaleimide-triazine resin, a maleimide resin and / or a cyanate compound resin, and (c) an epoxy group. The present invention relates to a heat-resistant adhesive containing an epoxy compound having a specific composition ratio as a resin component.

The heat-resistant adhesive of the present invention can bond various metal foils such as a copper foil and a heat-resistant support material (eg, a heat-resistant film, an inorganic sheet, etc.) at a relatively low temperature, Since the adhesive layer of the laminate bonded with the heat-resistant adhesive exhibits a sufficient adhesive strength and excellent heat resistance, for example, a flexible wiring board, TAB (Tape Automated Bo) is used.
When used for the production of copper-clad substrates for bonding, each substrate obtained using the heat-resistant adhesive can be subjected to various high-temperature processing steps such as soldering, etc. It can improve the quality of products and reduce 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, 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 used to form 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. 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]

The present invention relates to (a) biphenyltetracarboxylic acid , its dianhydride or its acid;
Aromatic hydrocarbon containing 60 mol% or more of ester
An aromatic tetracarboxylic acid component which is a rubonic acid derivative component;

[0010]

Embedded image

(Wherein R in the formula is a group having 2 to 6 carbon atoms)
Represents a divalent hydrocarbon residue comprising a plurality of methylene groups or a phenylene _{group,, R 1, R 2,} R 3 and R ₄ are carbon
Represents an alkyl group or a phenyl group of the number 1 to 5 , and n is 3
Indicates an integer of -60. 10) to 80 mol% of a diaminopolysiloxane represented by the following formula and a diamine of an aromatic hydrocarbon.
A diamine component comprising 20 to 90 mol% of a certain aromatic diamine (a combination of a diaminopolysiloxane and an aromatic diamine)
(A total of 100 mol%) and 100 parts by weight of a polyimide siloxane soluble in an organic polar solvent obtained from (b) a bismaleimide-triazine-based resin, a bismaleimide resin and a cyanate compound-based resin. The present invention relates to a heat-resistant adhesive comprising 10 to 500 parts by weight of one kind of thermosetting resin and (c) 5 to 50 parts by weight of an epoxy compound having an epoxy group as a resin component. In addition, the present invention provides the above-mentioned adhesive on a resin film.
The laminated film with adhesive, and the adhesive,
The present invention relates to a laminate laminated between a thermal support material and a metal.

(B) 10 to 500 parts by weight (preferably 12 to 300 parts by weight) of at least one thermosetting resin selected from the group consisting of a bismaleimide-triazine resin, a bismaleimide resin, and a cyanate compound resin Part), and

(C) An epoxy compound having an epoxy group (epoxy resin): 5 to 50 parts by weight are contained as a resin component.

The polyimide siloxane used in the present invention is 3,3 ', 4,4'- or 2,3,3',
4'-biphenyltetracarboxylic acids (preferably 2,
Aromatic tetracarboxylic acid containing 3,3 ', 4'-biphenyltetracarboxylic acid or its acid dianhydride or its acid ester) as a main component (containing at least 60 mol%, particularly 80 to 100 mol%) An acid component, 10 to 80 mol% (particularly 15 to 70 mol%, more preferably 20 to 60 mol%) of the diaminopolysiloxane represented by the general formula I, and 20 to 90 mol% (particularly 30 -85 mol%, more preferably 40-80 mol%)
A high molecular weight polyimide siloxane obtained by polymerizing and imidizing a diamine component consisting of

The above-mentioned polyimide siloxane 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%, especially at least 95%, as measured by infrared absorption spectroscopy, or has a substantial absorption peak relating to amide-acid bonds of the polymer 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, particularly about 0.1 to 200 kg / mm ² , more preferably 0.5 to 150 kg / mm ² ,
The thermal decomposition onset temperature is 250 ° C. or higher, particularly 300 ° C. or higher, and the secondary transition temperature is −10 ° C. or higher, particularly 5 to 2 ° C.
The temperature is preferably about 50 ° C.

The method for producing the polyimide siloxane includes, for example, an aromatic tetracarboxylic acid component containing about 60 mol% or more of 2,3,3 ′, 4′-biphenyltetracarboxylic acid and a diamino acid represented by the above general formula I. 20 to 80 mol% of polysiloxane and 20 to 8 of aromatic diamine
Using a 0 mol% 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 alkylurea solvent, at an elevated temperature (particularly preferred) At a temperature of 140 ° C. or higher), and polymerize and imidize both monomer components.

The above biphenyltetracarboxylic acids are
2,3,3 ', 4'-Biphenyltetracarboxylic dianhydride (a-BPDA) is useful for the solubility of polyimidesiloxane obtained by polymerization with a diamine component in an organic polar solvent and the compatibility with an epoxy compound. Is optimal.

The polyimide siloxane may 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. and having 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 polyimidesiloxane, 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.

In the heat-resistant adhesive according to the present invention, if the polyimidesiloxane is produced mainly from tetracarboxylic acids other than biphenyltetracarboxylic acids, the polyimidesiloxane is difficult to use in an organic polar solvent. It is not suitable because it becomes soluble or the compatibility with the epoxy resin deteriorates.

Examples of the tetracarboxylic acid compound which can be used together with a-BPDA or the like as the aromatic tetracarboxylic acid component used in the production of the polyimide siloxane include 3,3 ', 4,4'-benzophenonetetracarboxylic acid. Carboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, pyromellitic acid, Alternatively, their acid dianhydrides, esterified products and the like can be preferably mentioned.

The polysiloxane represented by the above general formula I used for the production of the above-mentioned polyimide siloxane includes a compound represented by the general formula I wherein R has 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.

Examples of the aromatic diamine used in the production of the polyimide siloxane include (a) a biphenyl diamine compound, a diphenyl ether diamine compound, a benzophenone diamine compound, a diphenyl sulfone diamine compound, a diphenylmethane diamine compound, Diphenylalkane diamino compounds such as 2,2-bis (phenyl) propane, 2,2-bis (phenyl) hexafluoropropane diamine compounds,
Diphenylene sulfone diamine compound,

(B) di (phenoxy) benzene diamine compound, di (phenyl) benzene diamine compound, (c) di (phenoxyphenyl) hexafluoropropane diamine compound, di (phenoxyphenyl) propane diamine compound And aromatic diamines mainly containing "aromatic diamine compounds having two or more aromatic rings (such as benzene rings), particularly 2 to 5" such as di (phenoxyphenyl) sulfone diamine compounds, They can be used alone or as a mixture.

As the aromatic diamine, in particular,
Diphenyl ether diamine compounds such as 1,4-diaminodiphenyl ether and 1,3-diaminodiphenyl ether; di (phenoxy) such as 1,3-di (4-aminophenoxy) benzene and 1,4-di (4-aminophenoxy) benzene ) Benzene diamine compounds, 2,
Bis (phenoxyphenyl) propane-based diamine compounds such as 2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) and 2,2-bis [4- (3-aminophenoxy) phenyl] propane; [4-
"Aromatic diamine compounds having 2 to 4 aromatic rings, such as di (phenoxyphenyl) sulfone diamine compounds such as (4-aminophenoxy) phenyl] sulfone and bis [4- (3-aminophenoxy) phenyl] sulfone ] (90 mol% or more).

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 comprises, 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 known thermosetting resin composition, which may be modified with acrylates, divinylbenzene, styrene, triallyl isocyanate, or the like in an amount of 0 to 30% by weight.
T resin ”and the like can be suitably mentioned.

The bismaleimide resin 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 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.

Examples of the epoxy compound 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, and glycidyl. An "epoxy compound having one or more epoxy groups" such as an ester-type epoxy resin and a glycidylamine-type epoxy resin can be mentioned, and a plurality of the above-mentioned various epoxy resins can be used in combination. In the present invention, it is particularly preferable that the epoxy resin has a melting point of 90 ° C. or lower, particularly about 0 to 80 ° C., or a liquid state at a temperature of 30 ° C. or lower.

In the heat-resistant adhesive of the present invention, the soluble polyimide siloxane having an elastic modulus of 15
0 kg / mm ² or less (especially 0.5-100 kg / m
m ² ) and the softening temperature is 5 ° C. or more (especially 5-250
C)), 10-500 parts by weight of at least one thermosetting resin selected from the group consisting of bismaleimide-triazine-based resin, bismaleimide resin and cyanate compound-based resin.
2-150 parts by weight) and 5-50 parts by weight (particularly 5-40 parts by weight) of an epoxy compound having an epoxy group.
The heat-resistant adhesive contained as a resin component is, for example, a metal foil such as a copper foil and a heat-resistant film such as an aromatic polyimide film are joined with the heat-resistant adhesive to form a copper-clad board, 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 large warpage.

In the heat-resistant adhesive of the present invention, a curing agent for the epoxy compound (resin), a curing accelerator, and the like may be used in combination. However, in some cases, the combination of the curing agent and the like is not preferable. The heat-resistant adhesive of the present invention comprises the above-mentioned polyimide siloxane, thermosetting resin, epoxy compound and a resin component having a specific composition ratio as a main component (particularly preferably 90%).
% By weight, more preferably about 95 to 100% by weight), but all of the above resin components are contained in a suitable organic polar solvent, particularly 3 to 5%.
At a concentration of 0% by weight, more preferably 5-40% by weight,
It may be a solution composition of a heat-resistant adhesive that is uniformly dissolved.

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 1 to 100 poise.
It is preferably about 0 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.

The heat-resistant adhesive of the present invention has a softening point (temperature at which softening starts on a hot plate) of a composition consisting of only an uncured resin component of 150 ° C. or less, particularly 120 ° C. or less. Preferably it is 100 ° C. or lower. The heat-resistant adhesive of the present invention is particularly preferably 150 to 400.
° C, more preferably 180-350 ° C (especially 200-
It is preferable that the composition can be thermally cured by heating to a curing temperature of 300 ° C.). Further, the heat-resistant adhesive of the present invention may contain a small proportion of other thermosetting resin such as phenol resin as a resin component.

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 polyimidesiloxane can be used as it is. Organic polar solvents having an oxygen atom in the molecule, such as tetrahydrofuran, can be suitably used.

The heat-resistant adhesive of the present invention is obtained by mixing a solution composition of the 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, aromatic polyimide film or the like. Apply on a heat-resistant film surface or a film surface of a thermoplastic resin such as polyester or polyethylene, and apply the applied layer at a temperature of 80 to 200 ° C for 20 minutes.
By drying for seconds to 100 minutes, the solvent becomes 1% by weight.
Forming 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 the following extent (preferably, the solvent remaining ratio is particularly 0.5% by weight or less). can do.

The uncured heat-resistant adhesive thin film produced as described above has 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 140 to 180 ° C., via the heat-resistant adhesive layer of About 180-350
C., especially at a temperature of 200 to 300.degree. C., for 30 minutes to 40 hours, especially 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 of the present invention is bonded to 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.

[0043]

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.

[0044]

(Equation 1)

The adhesive strength was measured by performing a T-peel test at a peeling speed of 50 mm / min using a tensile tester manufactured by Intesco Corporation. Furthermore, the "curvature radius" of a wiring board formed by etching a copper-clad substrate obtained by bonding a copper foil and a polyimide film using an adhesive is calculated according to JIS C-6418.

[0046]

(Equation 2)

(Where L represents the length of the sample,
h indicates its height).

[Production of Imidosiloxane Oligomer] Reference Example 1 In a glass flask having a capacity of 500 ml, (a)
0.045 mol of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA), (b) ω,
ω'-bis (3-aminopropyl) polydimethylsiloxane (X-22-161AS, manufactured by Shin-Etsu Silicon Co., Ltd.)
n: 9) 0.030 mol, and (c) 160 g of N-methyl-2-pyrrolidone (NMP) were charged,

In a nitrogen stream, the mixture was stirred at 50 ° C. for 2 hours to form an amic acid oligomer. Then, the reaction solution was heated to about 200 ° C., and stirred at that temperature for 3 hours to form an anhydride group at the terminal. (A-1)
The components, average degree of polymerization: 1) were produced.

REFERENCE EXAMPLE 2 The same procedure as in Reference Example 1 was repeated except that the amounts of a-BPDA, diaminopolysiloxane (X-22-161AS) and NMP shown in Table 1 were used. A siloxane oligomer (A-2, average degree of polymerization: 5) was produced.

[Production of imide oligomer] Reference Example 3 In a glass flask having a capacity of 500 ml, (a) 0.044 mol of 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) (B) 0.066 mol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) and (c) 160 g of N-methyl-2-pyrrolidone (NMP)
,

In a nitrogen stream, the mixture was stirred at 50 ° C. for 2 hours to form an amic acid oligomer, and then the reaction solution was heated to about 200 ° C. and stirred at that temperature for 3 hours to form an anhydride group at the terminal. Having an imide oligomer (B-1 component, average degree of polymerization: 1).

REFERENCE EXAMPLES 4-5 a-BPDA, BAPP and NMP in the amounts shown in Table 1
Imide oligomers B-2 (average degree of polymerization; 5) and B-3 (average degree of polymerization; 10) each having an amino group at the terminal, except that each was used.

[0054]

[Table 1]

[Production of Polyimide Siloxane] Reference Example 6 The imidosiloxane oligomer (A-
(1 component) 14.14 g (0.0055 mol) of a 20 wt% NMP solution and 24.33 g (0.0055 mol) of imido oligomer (component B-2) produced in Reference Example 4
As to generate and then heating the reaction mixture to 200 ° C. - charged 20 wt% NMP solution in a glass flask of 500ml capacity of, in a nitrogen stream, and stirred for 1 hour at 50 ° C., block polymer The mixture was stirred at the temperature for 3 hours to produce a polyimidesiloxane (block polymer). The polyimide siloxane had an imidation ratio of 100%, a logarithmic viscosity of 0.49, and a siloxane unit content of 22.22.

Reference Examples 7 to 11 In the same manner as in Reference Example 6, except that the oligomers produced in the above Reference Examples 1 to 5 were used under the amounts and reaction conditions shown in Table 3, the imidation ratio was reduced. Substantially 100% of polyimidesiloxane (block polymer) was produced. Regarding the logarithmic viscosity of each polyimide siloxane produced as described above, the content of the siloxane unit, and the polyimide siloxane film (thickness: about 50 μm) formed by a casting method from a reaction solution of the polyimide siloxane, Table 2 shows the elastic modulus and softening temperature.

Reference Example 12 In a glass flask having a capacity of 500 ml, (a) a-BPDA: 0.054 mol (b) diaminopolysiloxane (Shin-Etsu Silicon Co., Ltd.)
X-22-161AS): 0.012 mol (c) BAPP: 0.042 mol, and (d) NMP: 175 g.

The mixture was stirred at 50 ° C. for 2 hours in a stream of nitrogen to form an amic acid oligomer.
The temperature was raised to 00 ° C., and the mixture was stirred at that temperature for 3 hours to prepare polyimide siloxane (random polymer, logarithmic viscosity: 0.5
9, siloxane unit content: 22.2 mol%, imidation ratio: 100%).

Reference Example 13 In a glass flask having a capacity of 500 ml, (a) a-BPDA: 0.048 mol (b) diaminopolysiloxane (Shin-Etsu Silicon Co., Ltd.)
X-22-161AS): 0.016 mol (c) BAPP: 0.032 mol, and (d) NMP: 165 g

The mixture was stirred at 50 ° C. for 2 hours in a stream of nitrogen to form an amic acid oligomer.
The temperature was raised to 00 ° C., and the mixture was stirred at that temperature for 3 hours to prepare polyimide siloxane (random polymer, logarithmic viscosity: 0.56,
Siloxane unit content: 33.3 mol%, imidation ratio: 100%).

Reference Example 14 In a glass flask having a capacity of 500 ml, (a)
a-BPDA: 0.054 mol (b) diaminopolysiloxane (Shin-Etsu Silicon Co., Ltd.)
X-22-161AS): 0.018 mol (c) BAPP: 0.036 mol, and (d) NMP: 175 g,

In a nitrogen stream, the mixture was stirred at 50 ° C. for 2 hours to form an amic acid oligomer.
The temperature was raised to 00 ° C., and the mixture was stirred at that temperature for 3 hours to prepare polyimide siloxane (random polymer, logarithmic viscosity: 0.54,
And the content of siloxane units: 33.33 mol%). A polyimide siloxane film (thickness: about 50 μm) formed by a casting method from the polyimide siloxane reaction solution produced as described above,
Table 2 shows the elastic modulus and softening temperature.

[0063]

[Table 2]

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 (block) produced in Reference Example 6 described above, and a bismaleimide-triazine resin ( 65 g of Mitsubishi Gas Chemical Co., Ltd., BT3309T), epoxy resin (manufactured by Yuka Shell Epoxy), trade name: Epicoat 1
52) 10 g and 200 g of dioxane were charged at room temperature (2
(5 ° C.) for about 2 hours to prepare a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 0.5 poise). This solution composition maintained a uniform solution state (viscosity) even when left at room temperature for one week.

[Production of Laminated Body Using Heat-Resistant Adhesive] A solution composition of the above-mentioned heat-resistant adhesive was placed on a polyimide film (Ube Industries, Ltd., trade name: UPILEX-S type, thickness: 75 μm) by a doctor. Apply with a blade to a thickness of 125 μm, then apply the applied layer at 50 ° C. for 30 minutes
The resultant was dried by heating at 00 ° C. for 30 minutes and at 170 ° C. for 20 minutes to form a heat-resistant adhesive layer (uncured dried layer, softening point: 25 ° C.) having a thickness of about 20 μm on the polyimide film.

The polyimide film having the heat-resistant adhesive layer and a copper foil (35 μm) were superposed and the laminate was heated at 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 3.

Examples 2-17 Examples 3, 5, 11, and 17 are shown for reference. Second
Using the polyimide siloxane (block) produced in each of Reference Examples 6-9 as shown in the table, the composition of each component was changed to the third.
Except as shown in the table, a heat-resistant adhesive solution composition was prepared in the same manner as in Example 1. further,
Laminates were produced in the same manner as in Example 1 except that each of the above solution compositions was used. Table 3 shows the performance of the laminate.

Examples 18 to 19 The same procedures as in Example 1 were carried out except that the polyimidesiloxanes (random) produced in Reference Examples 12 and 13 were used, and the compositions of the respective components were as shown in Table 3. A solution composition of the heat-resistant adhesive was prepared. Further, a laminate was produced in the same manner as in Example 1 except that each of the above solution compositions was used. Table 3 shows the performance of the laminate.

Comparative Example 1 Using 20 g of the polyimidesiloxane obtained in Reference Example 6, 60 g of an epoxy resin (Epicoat 152), 0.1 g of a curing agent: 2-phenylimidazole, and a bismaleimide-triazine resin (Mitsubishi Gas Chemical Co., Ltd.) ) BT-3
309T), and a solution composition of a low-viscosity heat-resistant adhesive was prepared in the same manner as in Example 1 except that 20 g of dioxane and 200 g of dioxane were used.

Except for using the above-mentioned solution composition of a heat-resistant adhesive, the solution composition was applied on a polyimide film in the same manner as in Example 1 and dried to form a heat-resistant adhesive layer (uncured). Dried adhesive layer, thickness: 25 μm). As a result of bending the polyimide film on which the adhesive layer was formed, many cracks occurred in the adhesive layer. Lamination of the polyimide film having the heat-resistant adhesive layer formed thereon and copper foil was substantially impossible.

Comparative Example 2 95 g of the polyimidesiloxane obtained in Reference Example 7 was mixed with 5 g of an epoxy resin (Epicoat 152), 0.1 g of a curing agent: 2-phenylimidazole, and 200 g of dioxane.
g in the same manner as in Example 1 except that
A solution composition of a heat-resistant adhesive was prepared, applied on a polyimide film, and dried to form an adhesive layer (25 μm). Lamination of the polyimide film on which the heat-resistant adhesive layer was formed with a copper foil was substantially impossible.

[0072]

[Table 3]

Example 20 [Preparation of solution composition of heat-resistant adhesive] In a glass flask having a capacity of 500 ml, 55 g of the polyimidesiloxane (polymer block A-1-B-1) produced in Reference Example 8 described above was placed. , Bismaleimide-triazine resin (BT3309, manufactured by Mitsubishi Gas Chemical Company, Ltd.)
T) 35 g, epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.)
Product name: Epicoat 152) 10 g, dioxane 200
g and stirred at room temperature (25 ° C.) for about 2 hours to prepare a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 25 poise). This solution composition maintained a uniform solution state (viscosity) even when left at room temperature for one week.

[Production of Laminate Using Heat Resistant Adhesive] A laminate was produced in the same manner as in Example 1 except that the above solution composition was used. Table 4 shows the performance of the laminate.

Examples 21 to 35 Using the polyimidesiloxanes (blocks) produced in Reference Examples 7, 9 to 11 and 14 as shown in Table 2,
A solution composition of a heat-resistant adhesive was prepared in the same manner as in Example 1 except that the composition of each component was as shown in Table 4. Further, each of the laminates was manufactured in the same manner as in Example 20, except that each of the above solution compositions was used. Table 4 shows the performance of the laminate.

Example 36 A heat-resistant adhesive was prepared in the same manner as in Example 20 except that the polyimidesiloxane (random) produced in Reference Example 14 was used and the composition of each component was as shown in Table 4. Was prepared. Further, a laminate was produced in the same manner as in Example 20, except that the above solution composition was used. Table 4 shows the performance of the laminate.

[0077]

[Table 4]

[0078]

The heat-resistant adhesive of the present invention can easily form an uncured thin-layer heat-resistant adhesive layer by applying the solution composition on a support film and drying at a relatively low temperature. In addition, the thin heat-resistant adhesive layer has sufficient flexibility, and the thin heat-resistant adhesive layer on the support film can be formed by punching. It is possible to transfer the heat-resistant film to another heat-resistant support film at an appropriate temperature, and to laminate the heat-resistant film and the copper foil at a relatively low temperature. It has good workability.

Further, 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.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 183/10 C09J 183/10 // C08G 73/08 C08G 73/08 (72) Inventor Tetsuji Hirano 3 Nakamiyakitamachi, Hirakata City, Osaka Prefecture No. 10 Ube Industries, Ltd. Examiner in the Hirakata Research Laboratory Kimitaka Murakami (56) References JP-A-5-25452 (JP, A)

Claims (3)

(57) [Claims] (1) (a) biphenyltetracarboxylic acid and its acid
Contains 60 mol% or more of dianhydride or its acid ester
An aromatic tetracarboxylic acid component, which is a carboxylic acid derivative component of an aromatic hydrocarbon, and a compound represented by the general formula (I): (However, R in the formula represents a plurality of methyls having 2 to 6 carbon atoms.
Shows the emission group or a divalent hydrocarbon residue consisting of phenylene _{group,, R 1, R 2,} R 3 and R ₄ represents a 1-5 amino <br/> alkyl group or a phenyl group having a carbon number, n Represents an integer of 3-60. The diaminopolysiloxane 10-8 represented by
A diamine component comprising 0 mol% and 20 to 90 mol% of an aromatic diamine which is a diamine of an aromatic hydrocarbon ( diamine component )
100 mol total of nopolysiloxane and aromatic diamine
%) Of a polyimide siloxane soluble in an organic polar solvent obtained from (b) a bismaleimide-triazine resin, a bismaleimide resin and a cyanate compound resin. A heat-resistant adhesive comprising 10 to 500 parts by weight of a thermosetting resin and (c) 5 to 50 parts by weight of an epoxy compound having an epoxy group as a resin component. 2. A resin film comprising the adhesive according to claim 1.
Film with adhesive laminated on top . 3. An adhesive according to claim 1, wherein said adhesive is a heat-resistant support material.
Laminated body between metal and metal.