JPH05140524A - Heat resistant adhesive - Google Patents

Abstract

PURPOSE:To obtain the subject adhesive consisting of a specific soluble polyimidesiloxane, epoxy-modified polysiloxane, other epoxy compound and epoxy curing agent, excellent in heat resistance and flexibility and useful for flexible printed circuit board. CONSTITUTION:The objective adhesive is obtained by blending (A) 100 pts.wt. soluble high molecular polyimidesiloxane obtained by polymerizing and imidating (i) an aromatic tetracarboxylic acid component consisting essentially of biphenyltetracarboxylic acids, (ii) a diamine component consisting of 10-80mol% diaminopolysiloxane component of the formula [R is divalent hydrocarbon residue; R1 to R4 are lower alkyl or phenyl; (n) is 3-60] and 20-90mol% aromatic diamine with (B) 1-60 pts.wt. epoxy-modified polysiloxane, (C) 15-250 pts.wt. epoxy-containing other epoxy compound and (D) an epoxy curing agent (preferably of 0.01-110 pts.wt. based on 100 pts.wt. epoxy resins of the components (B) and (C).

Description

Detailed Description of the Invention

[0001]

The present invention relates to a resin component comprising (a) a soluble polyimide siloxane, (b) an epoxy-modified polysiloxane, (c) another epoxy compound having an epoxy group, and (d) an epoxy curing agent. The present invention relates to a heat-resistant adhesive contained in a specific composition ratio.

The heat-resistant adhesive of the present invention is capable of laminating various metal foils such as copper foil and heat-resistant support materials (for example, heat-resistant films and inorganic sheets) at a relatively low temperature. In the laminate laminated with the heat resistant adhesive, the adhesive layer exhibits sufficient adhesive force and excellent heat resistance, and therefore, for example, a flexible wiring board, a TAB (Tape Automated Bo
When used in the production of copper-clad substrates, etc., each substrate obtained by using the heat-resistant adhesive can safely perform various high-temperature treatment processes such as subsequent soldering treatment. It can improve product quality 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 together using an adhesive such as epoxy resin or urethane resin.

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

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

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

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

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

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

[0010]

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

[0011]

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

[0012]

[Chemical 2]

(Wherein R represents a divalent hydrocarbon residue, R ₁ , R ₂ , R ₃ and R ₄ represent a lower alkyl group or a phenyl group, and n represents 3 to 60, Preferably 5
Indicates an integer of -50. ) 10 to 80 mol% of diaminopolysiloxane and 20 to 9 aromatic diamine
100 parts by weight of soluble polyimide siloxane obtained from 0 mol% of diamine component, (b) 1 to 60 parts by weight (preferably 2 to 50 parts by weight) of epoxy-modified polysiloxane, (c) other epoxy group Epoxy compound (epoxy resin) 15 to 250 parts by weight (preferably 20 to 200)
Parts by weight), and (d) an epoxy curing agent (preferably 0.01 to 110 parts by weight based on 100 parts by weight of the epoxy resin of (b) and (c)) are contained as resin components. The present invention relates to a characteristic heat resistant adhesive.

The polyimidesiloxane used in the present invention is 3,3 ', 4,4'- or 2,3,3',
4'-biphenyltetracarboxylic acid (preferably 2,
Aromatic tetracarboxylic having 3,3 ′, 4′-biphenyltetracarboxylic acid or its acid dianhydride or its acid ester compound as a main component (containing 60 mol% or more, 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% of an aromatic diamine (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 (a) has a logarithmic viscosity (measurement concentration; 0.5 g / 100 ml solvent, solvent; N-methyl-2-pyrrolidone, measurement temperature; 3).
(0 ° C.) is 0.05 to 7, particularly 0.07 to 4, more preferably about 0.1 to 3, and at least 3 in any of organic polar solvents (particularly amide solvents). It is preferable that it can be uniformly dissolved at a concentration of about 5% by weight, particularly about 5 to 40% by weight.

The above-mentioned polyimide siloxane has an imidization ratio of 90% or more, particularly 95% or more as measured by an infrared absorption spectrum analysis method, or has an absorption peak related to the amide-acid bond of the polymer in the infrared absorption spectrum analysis. It is preferable that the imidization ratio is high so that only absorption peaks relating to the imide ring bond are observed.

Further, the above-mentioned polyimide siloxane is
When formed into a film, its elastic modulus is 250 kg /
mm ² or less, particularly 0.5 to 200 kg / mm ² , the thermal decomposition initiation temperature is 250 ° C. or more, particularly 300 ° C. or more, and the secondary transition temperature is −10 ° C. or more, especially 1
It is preferably about 0 to 250 ° C.

The method for producing the polyimidesiloxane is, for example, an aromatic tetracarboxylic acid component containing about 60 mol% or more of 2,3,3 ', 4'-biphenyltetracarboxylic acid, and a diamino represented by the above general formula I. Polysiloxane 20-80 mol% and aromatic diamine 20-8
Using a diamine component consisting of 0 mol%, in an organic polar solvent such as a phenol solvent, an amide solvent, a solvent of a compound having a sulfur atom, a glycol solvent or an alkylurea solvent at high temperature (particularly preferable). Is under a temperature of 140 ° C. or higher), and both monomer components are polymerized and imidized.

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

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 obtain a logarithmic viscosity of 0.05. A method of producing the polyamic acid as described above and imidizing the polyamic acid by any known method to produce a soluble polyimidesiloxane may be used.

Further, in the above-mentioned method 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 only of diaminosiloxane. It has a degree of about 1 to 10 and has an acid or an acid anhydride group at the terminal.), And an aromatic tetracarboxylic acid component and an excess amount of a diamine component consisting of an aromatic diamine. Imide oligomer (Y component: the degree of polymerization is about 1 to 10 and has an amino group at the end) is prepared, and then the X component and the Y component are mixed in a ratio of total acid component and total diamine component. The method of producing a block-type polyimide siloxane can also be suitably mentioned by mixing and reacting so as to be approximately equimolar.

In the heat-resistant adhesive of the present invention, when the polyimide siloxane is manufactured by using tetracarboxylic acids other than biphenyl tetracarboxylic acids as a main component, the polyimide siloxane is difficult to react with an organic polar solvent. It is not suitable because it becomes soluble and the compatibility with epoxy resin deteriorates.

Examples of the tetracarboxylic acid compound which can be used together with a-BPDA as the aromatic tetracarboxylic acid component used in the production of the polyimidesiloxane include, for example, 3,3 ', 4,4'-benzophenone tetra. Carboxylic acid, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, pyromellitic acid, Alternatively, suitable examples thereof include acid dianhydrides and esterified products thereof.

The polysiloxane represented by the general formula I used in the production of the above-mentioned polyimide siloxane includes R 2 in the general formula I having 2 to 6 carbon atoms, particularly 3 to 5 "plural methylene groups". ] Or a divalent hydrocarbon residue consisting of a phenylene group, and 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, a propyl group or a phenyl group. Furthermore, it is preferable that n is particularly 5 to 20, more preferably 5 to 15.

The aromatic diamine used for producing the above-mentioned polyimide siloxane includes, for example, 1) biphenyl diamine compounds, diphenyl ether diamine compounds, benzophenone diamine compounds, diphenyl sulfone diamine compounds, diphenyl methane diamine compounds, 2 , A diphenylalkane-based diamino compound such as 2-bis (phenyl) propane,
2,2-bis (phenyl) hexafluoropropane-based diamine compound, diphenylene sulfone-based diamine compound,

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

As the above-mentioned aromatic diamine,
Diphenyl ether type 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-bis (4-aminophenoxy) benzene. ) Benzene diamine compound,
Bis (phenoxyphenyl) propane-based diamine compounds such as 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 2,2-bis [4- (3-aminophenoxy) phenyl] propane, bis [ 4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3
Aromatic diamines mainly containing (90 mol% or more) "aromatic diamine compound having 2 to 4 aromatic rings" such as di (phenoxyphenyl) sulfone-based diamine compounds such as -aminophenoxy) phenyl] sulfone are suitable. Can be listed in.

Examples of the organic polar solvent used in the production of the polyimide siloxane include N, N-dimethylacetamide, N, N-diethylacetamide, N, N.
An amide solvent such as dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone,
Dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, solvent containing a sulfur atom such as hexamethyl sulfolamide, cresol, phenol, phenolic solvents such as xylenol, acetone, methanol, ethanol, ethylene glycol,
Examples thereof include solvents having an oxygen atom in the molecule such as dioxane and tetrahydrofuran, and other solvents such as pyridine and tetramethylurea. Further, if necessary, aromatic hydrocarbon-based solvents such as benzene, toluene and xylene can be used. It is also possible to use other kinds of organic solvents such as a solvent, solvent naphtha and benzonitrile together.

The epoxy-modified polysiloxane compound (b) used in the present invention has a hydroxyl group at the terminal,
A reactive polysiloxane oil having a carboxyl group or an amino group and an epoxy compound such as a bisphenol type epoxy resin, a phenol novolac type epoxy resin, a glycidyl ether type epoxy resin or a glycidyl ester type epoxy resin are heated at a temperature of about 80 to 140 ° C. Any epoxy-modified polysiloxane having at least one epoxy group at the terminal or inside of the polysiloxane, which is obtained by the reaction in step (1), may be used.

Epoxy-modified polysiloxane compound (b)
As those having a melting point of 90 ° C. or lower, or those which are liquid at 30 ° C. or lower, for example, polyglycidoxypropylmethylsiloxane (P
S920, PS922, etc.), Toray Dow Corning
Epoxy / glycol-modified silicone oil (SF-8421, SF-8421EG, manufactured by Silicone Co., Ltd.)
BY-16-845), epoxy terminal reactive silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. (KF105, X-2).
2-163).

When the heat-resistant adhesive of the present invention is prepared using an epoxy-modified polysiloxane compound, if compatibility with a solvent, another epoxy resin, or polyimide siloxane is not so good, a polyether is used. Compatibilizer such as modified polysiloxane [eg, polyether modified polysiloxane manufactured by Shin-Etsu Chemical Co., Ltd. (KF615
A, etc.)] may be used in combination.

The other epoxy compound (c) having an epoxy group used in the heat resistant adhesive of the present invention is, for example, bisphenol A type or bisphenol F type.
Type Epoxy Resin (Yukaka Shell Co., Ltd., Epicoat 8
07, 828, etc.), phenol novolac type epoxy resin, alkyl polyhydric phenol type epoxy resin (Nippon Kayaku Co., Ltd., RE701 etc.), polyfunctional epoxy resin (Sumitomo Chemical Co., Ltd., ELM-100 etc.), glycidyl "Epoxy compound having one or more epoxy groups" such as ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin (manufactured by Mitsubishi Gas Chemical Co., Inc., Tetrad X, etc.) and the like can be mentioned. A plurality of various epoxy resins can be used in combination. In the present invention, the epoxy resin has a melting point of 90 ° C. or lower, particularly about 0 to 80 ° C., or 30 ° C.
Those which are liquid at the following temperatures are particularly preferable.

The epoxy curing agent (d) used in the heat-resistant adhesive of the present invention includes imidars,
Examples include curing catalysts such as secondary amines and triphenylphosphines, dicyandiamides, hydrazines, aromatic diamines, polyaddition type curing agents such as phenol novolac type curing agents having a hydroxyl group, and organic peroxides. it can.

The above-mentioned epoxy curing agent can be used in an appropriate proportion, but can be used in an amount of 0. 0 with respect to 100 parts by weight of an epoxy resin composed of the epoxy-modified polysiloxane compound (b) and another epoxy compound (c). 01-110
It is preferable to use parts by weight, especially about 0.03 to 100 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 110 parts by weight, particularly 10 to 100 parts by weight, based on 100 parts by weight of the epoxy resin.

The heat-resistant adhesive of the present invention comprises the polyimide siloxane (a), the epoxy-modified polysiloxane compound (b), the other epoxy compound (c), and the epoxy curing agent (d). Any heat-resistant adhesive may be used as long as it contains a resin component having a composition ratio of (4) as a main component (particularly 90% by weight or more, and more preferably about 95 to 100% by weight). In an organic polar solvent, particularly 3 to 50% by weight, more preferably 5
It may be a solution composition of a heat resistant adhesive that is uniformly dissolved at a concentration of -40% by weight.

The solution composition of the above heat-resistant adhesive has a solution viscosity (30 ° C.) of about 0.1 to 10000 poise,
Especially 0.2 to 5000 poise, more preferably 0.3
It is preferably about 1000 poises. Further, the solution composition may contain a fine inorganic filler such as silicon dioxide (for example, "Aerosil 200" manufactured by Nippon Aerosil Co., Ltd.).

The heat-resistant adhesive of the present invention has a softening point (temperature at which softening starts on a hot plate) of a composition containing only an uncured resin component of 150 ° C. or lower, particularly 120 ° C. or lower, and more preferably. Is preferably about 0 to 100 ° C.
The heat-resistant adhesive of the present invention has a temperature of 100 to 350 ° C, more preferably 120 to 300 ° C (especially 140 to 250 ° C).
It is preferably one that can be thermoset by heating to a curing temperature of (° C.).

The heat-resistant adhesive of the present invention may contain, as a resin component, another thermosetting resin such as a phenol resin 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 polyimide siloxane can be used as it is, for example, dioxane. An organic polar solvent having an oxygen atom in the molecule, such as tetrahydrofuran, can be preferably used.

The heat-resistant adhesive of the present invention comprises 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, and a suitable metal foil, aromatic polyimide film or the like is prepared. It is coated on a heat-resistant film surface or a thermoplastic resin film surface such as polyester or polyethylene, and the coating layer is applied at a temperature of 80 to 200 ° C. for 20 minutes.
1% by weight of solvent by drying for 100 seconds
Forming a thin film (a dry film or sheet having a thickness of about 1 to 200 μm) of an uncured heat-resistant adhesive that has been removed to the following level (preferably the residual amount of solvent is 0.5% by weight or less) can do.

The thin film of the uncured heat-resistant adhesive produced as described above has suitable flexibility, and is wound around a paper tube or the like, or punched by a punching method or the like. It is also possible to further include, for example, a laminated sheet in which a thin layer of an uncured heat-resistant adhesive is formed on the heat-resistant or thermoplastic film, and a metal foil or a heat-resistant film for a transfer destination. Overlap, about 20-200 ℃
By passing between a pair of rolls (laminating rolls) heated to a temperature, it is possible to transfer onto a metal foil or a heat resistant film for a transfer destination.

To form a laminate such as a copper clad substrate by joining a heat resistant film and a metal foil using the heat resistant adhesive of the present invention, for example, the thin film formed as described above is used. The heat-resistant film and the metal foil were laminated (bonded) under pressure at a temperature of 80 to 200 ° C., particularly 120 to 180 ° C. via the heat resistant adhesive layer of, and further laminated. About 140-250
By heating at 30 ° C., particularly 150 to 230 ° C., for 30 minutes to 40 hours, particularly 1 to 30 hours to heat-cure the heat-resistant adhesive layer, the laminate described above can be used without any trouble. It can be easily and continuously manufactured.

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 polyether ether ketone, a PEEK film or a polyether sulfone film, and a suitable metal foil such as a copper foil. Can be preferably used for

[0044]

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

[0045]

[Formula 1]

The softening temperature of the polyimidesiloxane film is a value determined from Tan δ (high temperature side) of the viscoelastic peak in the viscoelastic test. Further, the adhesive strength is measured by using a tensile tester manufactured by Intesco with a peeling speed of 50 mm / min, a 90 ° (T type) at a measuring temperature of 25 ° C., and a 180 ° peeling test at a measuring temperature of 180 ° C. This is the result.

The radius of curvature showing the curl property of the wiring board after forming a copper-clad substrate using a heat resistant adhesive and removing the copper foil by etching treatment is the calculation formula shown in JIS standard C5012. [Radius of curvature (mm) = L ² / 8h (L:
Sample length, h: height of sled)]].

[Production of Imidosiloxane Oligomer] Reference Example 1 1) 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) 0.054 mol in a glass flask having a capacity of 500 ml. , 2) ω, ω'-bis (3-aminopropyl) polydimethylsiloxane (X-22-16 manufactured by Shin-Etsu Silicon Co., Ltd.)
1AS, n: 9) 0.027 mol, and 3) N-methyl-2-pyrrolidone (NMP) 160 g were charged and stirred in a nitrogen stream at 50 ° C. for 2 hours to generate an amic acid oligomer, and then. The reaction solution was heated to about 200 ° C. and stirred at that temperature for 3 hours to generate an imidosiloxane oligomer having an anhydride group at the end (A-1 component, average degree of polymerization: 1).

Reference Examples 2 to 3 In the same manner as in Reference Example 1 except that the amounts of a-BPDA, diaminopolysiloxane (X-22-161AS) and NMP shown in Table 1 were used, respectively, an anhydrous group was added to the terminal. The imidosiloxane oligomers (A-2, average degree of polymerization: 2, and A-3, average degree of polymerization: 6) were prepared.

[Production of Imide Oligomer] Reference Example 4 In a glass flask having a capacity of 500 ml, 1) 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) 0.035 mol 2 ) 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 0.070 mol, and 3) N-methyl-2-pyrrolidone (NMP) 155 g were charged, and it was at 50 ° C in a nitrogen stream. The mixture was stirred for 2 hours to form an amic acid oligomer, and then the reaction solution was added to about 20
The temperature was raised to 0 ° C. and the mixture was stirred at that temperature for 3 hours, and an imide oligomer having an anhydrous group at the terminal (B-1 component, average degree of polymerization:
1) was generated.

Reference Examples 5 to 7 a-BPDA, BAPP and NMP in the amounts shown in Table 1.
In the same manner as in Reference Example 4, except that the imide oligomers B-2 (average degree of polymerization; 2), B-3 (average degree of polymerization; 5) and B-4 (average degree of polymerization) were used. Degree: 10) was produced.

[0052]

[Table 1]

[Production of Polyimide Siloxane] Reference Example 8 The imidosiloxane oligomer (A-
3 component) 0.0025 mol of 20 wt% NMP solution, and 0.0025 mol of 20 wt% NMP solution of the imide oligomer (B-4 component) produced in Reference Example 6 were placed in a glass flask having a capacity of 500 ml. Charge and stir in a nitrogen stream at 50 ° C for 1 hour to form a polyamic acid block polymer, and then the reaction solution is heated to 200 ° C.
The temperature was raised to 1, and the mixture was stirred at that temperature for 3 hours to generate polyimide siloxane (block polymer). The polyimidesiloxane had an imidization ratio of 95% or more and an inherent viscosity of 0.45.

Reference Examples 9 to 11 Polyimide siloxanes (blocks) were prepared in the same manner as in Reference Example 8 except that the oligomers prepared in Reference Examples 1 to 7 were used in the amounts and reaction conditions shown in Table 2. Polymers) were prepared respectively. Table 2 shows the logarithmic viscosity, the elastic modulus when formed into a film and the softening temperature of each polyimide siloxane produced.

Reference Example 12 In a glass flask having a capacity of 500 ml, 1) a
-BPDA: 0.048 mol, 2) diaminopolysiloxane (X-22-161A, manufactured by Shin-Etsu Silicon Co., Ltd.)
After charging S): 0.016 mol, 3) BAPP: 0.032 mol, and 4) NMP: 165 g, the mixture was stirred in a nitrogen stream 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 generate polyimide siloxane (random polymer, logarithmic viscosity: 0.56, siloxane unit content: 33.3 mol%). Table 2 shows the physical properties of these polyimidesiloxanes.

[0056]

[Table 2]

Example 1 [Preparation of Solution Composition of Heat-Resistant Adhesive] In a glass flask having a capacity of 500 ml, the polyimide siloxane (block polymer, A-3) produced in Reference Example 8 was used.
-B-4) 50 g, epoxy-modified siloxane (manufactured by Chisso Corporation, PS920) 10 g, epoxy resin (manufactured by Yuka Shell Epoxy Co., trade name: Epicoat 807) 30
g, 20 g of phenol novolac type curing agent (H-1 manufactured by Meiwa Kasei Co., Ltd.), and 185 g of dioxane were charged, and stirred at room temperature (25 ° C.) for about 2 hours to obtain a uniform heat-resistant adhesive solution composition. (Viscosity at 25 ° C .: 7 poise) was prepared. This solution composition maintained a uniform solution state (viscosity) even when left at room temperature for 1 week.

[Production of Laminated Body Using Heat-Resistant Adhesive] A doctor composition was coated with the solution composition of the heat-resistant adhesive described above on a polyimide film (manufactured by Ube Industries, Ltd., trade name: UPILEX-S type, thickness 75 μm). Coating with a blade to a thickness of 125 μm, and then applying the coating layer at 50 ° C. for 30 minutes, 1
It was heated and dried at 00 ° C. for 30 minutes to form a heat-resistant adhesive layer (uncured dried layer, softening point: 60 ° C.) having a thickness of about 20 μm on the polyimide film.

The polyimide film having the heat-resistant adhesive layer and the copper foil (35 μm) were superposed on each other and pressure-fed between the laminate rolls heated to 130 ° C. so that the laminate was pressure-bonded. 100 ° C
For 1 hour, at 120 ° C. for 1 hour, and at 160 ° C. for 10 hours to cure the heat resistant adhesive layer to produce a laminate. The adhesive strength of the obtained laminate was measured, and the results are shown in Table 3.

Examples 2 to 7 The polyimide siloxanes (blocks) prepared in Reference Examples 9 to 11 as shown in Table 3 were used, and the composition of each component was as shown in Table 3 except that In the same manner as in Example 1, a heat-resistant adhesive solution composition was prepared. A laminate was produced in the same manner as in Example 1 except that each of the solution compositions described above was used. The performance of the laminate is shown in Table 3.

Example 8 A heat-resistant adhesive was prepared in the same manner as in Example 1 except that the polyimide siloxane (random) produced in Reference Example 12 was used and the composition of each component was as shown in Table 3. Each solution composition of the agent was prepared. A laminate was produced in the same manner as in Example 1 except that each of the solution compositions described above was used. The performance of the laminate is shown in Table 3.

[0062]

[Table 3]

In Table 3, "workability at 30 ° C" is
Tack property (tack property with protective film), punching property, and workability at the time of heat bonding are comprehensively evaluated, and ⊚ indicates excellent, ∘ indicates good, Δ indicates normal, and × indicates poor.

Comparative Example 1 80 g of the polyimide siloxane produced in Reference Example 8, 1 g of epoxy-modified polysiloxane (FS-8421EG manufactured by Toray Dow Corning Epoxy Co., Ltd.), and bisphenol A type epoxy resin (produced by Yuka Shell Co., Ltd.) , Epicoat 828) 12 g, phenol novolak (manufactured by Meiwa Kasei Co., Ltd., H-1) 17 g, and dioxane 230 g were used to prepare a heat-resistant adhesive solution composition in the same manner as in Example 1. The solution composition was applied onto a polyimide film and dried in the same manner as in Example 1 except that the solution set * was used to form an adhesive layer (uncured and dried adhesive layer, thickness: 20 μm). ) Was formed.

The adhesive layer formed on the above-mentioned polyimide film is poor in tackiness and easily peeled off from the polyimide film, and it is practically impossible to laminate it with a copper foil to produce a laminate. It was The results are shown in Table 3.

Comparative Example 2 Polyimide siloxane 50 produced in Reference Example 9 above
Heat resistance in the same manner as in Example 1 except that only g, 20 g of epoxy resin (manufactured by Yuka Shell Co., Epicoat 807), and polyfunctional epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., ELM-100 and dioxane 150 g) were used. A solution composition of an adhesive was prepared, and the solution composition was applied onto a polyimide film and dried in the same manner as in Example 1 except that the solution composition was used. An adhesive layer having a thickness of 20 μm) was formed, and a laminate was produced in the same manner as in Example 1 except that the polyimide film having the above-mentioned adhesive layer was used. Is shown in Table 3, and the curl of the etching film was very large with a radius of curvature of 30 mm.

Comparative Example 3 A heat-resistant adhesive solution composition was prepared in the same manner as in Example 1 except that the composition of each component was as shown in Table 3, and the solution composition was used. A laminated body was manufactured in the same manner as in Example 1 except for the above. The results of the performance test of the laminate are shown in Table 3, and the curl of the etching film was very large.

In the column of "Type of epoxy-modified polysiloxane" in Table 3, "PS920" indicates epoxy-modified polysiloxane manufactured by Chisso Corporation, and "SF-84".
21EG ”represents an epoxy-modified polysiloxane manufactured by Toray Dow Corning Co., Ltd. In addition, in the column of "Types of other epoxy compounds" in Table 3, "Epicoat 8
"07" and "Epicoat 828" indicate bisphenol A type or bisphenol F type epoxy resin manufactured by Yuka Shell Co., Ltd., "RE701" indicates alkyl polyhydric phenol type epoxy resin manufactured by Nippon Kayaku Co., Ltd., and "E"
“LM-100” indicates a polyfunctional epoxy resin manufactured by Sumitomo Chemical Co., Ltd., and “Tetrad X” indicates a glycidylamine type epoxy resin manufactured by Mitsubishi Gas Chemical Co., Inc.

[0069]

The heat-resistant adhesive of the present invention can easily form an uncured and thin heat-resistant adhesive layer by coating the solution composition on a supporting film and drying at a relatively low temperature. The heat-resistant adhesive layer as a thin layer has sufficient flexibility, and the heat-resistant adhesive layer as a thin layer on the supporting film is not perforated. There is no problem even if it is received, it is also possible to transfer onto another heat resistant support film at an appropriate temperature, and the lamination of the heat resistant film and the copper foil should be carried out at a relatively low temperature. It has good workability.

Further, the heat-resistant adhesive of the present invention is excellent in heat resistance and flexibility even after being heat-cured to form a laminate, and etching after etching copper foil or the like. Since the curl of the film is small, it can be suitably used as an adhesive for flexible wiring boards, copper-clad boards for TAB, and the like.

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

Claims (1)

[Claims] 1. An aromatic tetracarboxylic acid component comprising (a) a biphenyltetracarboxylic acid as a main component, and a compound represented by the general formula (I): (However, R in the formula represents a divalent hydrocarbon residue,
₁ , R ₂ , R ₃ and R ₄ represent a lower alkyl group or a phenyl group, and n represents an integer of 3-60. ) 100 parts by weight of a soluble polyimide siloxane obtained from a diamine component consisting of 10 to 80 mol% of diaminopolysiloxane and 20 to 90 mol% of an aromatic diamine, and (b) 1 to 60 parts by weight of an epoxy-modified polysiloxane. , (C) Another epoxy compound having an epoxy group 15-2
50 parts by weight and (d) an epoxy curing agent are contained as a resin component.