JPH05140525A - Heat resistant resin adhesive - Google Patents

Abstract

PURPOSE:To obtain the subject adhesive consisting of a specific soluble polyimidesiloxane, unsaturated compound, epoxy compound and epoxy curing agent, excellent in heat resistance and flexibility and capable of laminating various kinds of metallic foils to a heat resistant supporting material. CONSTITUTION:The objective adhesive is obtained by blending (A) 100 pts. wt. soluble high molecular polyimidesiloxane (preferably 2, 3, 3',4'- biphenyltetracarboxylic acid) obtained by polymerizing (i) an aromatic tetracarboxylic acid component consisting essentially of biphenyltetracarboxylic acids and (ii) a diamine component consisting of 10-80mol% diaminopolysiloxane of the formula [R is divalent hydrocarbon residue; R1 to R4 are lower alkyl or phenyl; (n) is 3-60] with (B) 5-400 pts.wt. unsaturated compound consisting essentially of an acrylate based unsaturated compound [e.g. polyolpoly(meth) acrylate], (c) 20-250 pts.wt. epoxy-containing epoxy compound and (D) an epoxy curing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to (a) a soluble polyimide siloxane, (b) an unsaturated compound having an acrylate unsaturated compound as a main component, (c) an epoxy compound having an epoxy group, and (d) an epoxy. The curing agent relates to a heat resistant resin adhesive containing a resin composition in a specific composition ratio.

The heat-resistant resin 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 film, inorganic sheet) at a relatively low temperature. In the laminate laminated with the above heat-resistant resin adhesive, the adhesive layer exhibits sufficient adhesive force,
Moreover, since it exhibits excellent heat resistance, for example, flexible wiring boards, TABs (Tape Automated)
Bonding) copper-clad substrate
Each board obtained by using the heat-resistant resin adhesive can safely perform various high-temperature processing steps such as subsequent solder processing, improving the quality of the final product and reducing the defect rate. it can.

[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 a soluble polyimide siloxane obtained from 0 mol% of a diamine component, (b) 5 to 400 parts by weight of an unsaturated compound mainly containing an acrylate unsaturated compound, (preferably 10 to 300).
Parts by weight) (c) 20 to 250 parts by weight (preferably 25 to 200 parts by weight) of an epoxy compound having an epoxy group (epoxy resin), and (d) an epoxy curing agent (preferably epoxy resin 10).
0.01 to 110 parts by weight with respect to 0 parts by weight) is contained as a resin component.

In the present invention, the unsaturated compound (b) is 30% by weight or more based on the total amount of the unsaturated compounds,
It is particularly preferable to contain 40 to 100% by weight of the acrylate-based unsaturated compound (b-1), and further, the acrylate-based unsaturated compound (b-1) is added to 100 parts by weight of the (a) polyimidesiloxane. 5 to 300 parts by weight, particularly 5 to 250 parts by weight, and a maleimide unsaturated compound (maleimide resin) (b
-2) is preferably contained in an amount of 0 to 100 parts by weight, particularly 0.1 to 90 parts by weight, based on 100 parts by weight of the (a) polyimidesiloxane.

The polyimidesiloxane used in this 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, in particular 150 kg / mm ² or less, more preferably a 0.5～100Kg / mm ^2, the softening temperature of the film is 5 ° C. or more, and particularly preferably 5-250 about ° 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 biphenyl tetracarboxylic 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 the 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 resin adhesive of the present invention, when the polyimide siloxane is produced by using tetracarboxylic acid other than biphenyl tetracarboxylic acid as a main component, the polyimide siloxane is resistant to the organic polar solvent. It is not suitable because it becomes poorly soluble or the compatibility with the unsaturated compound and / or the epoxy resin deteriorates.

Examples of the tetracarboxylic acid compound that 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.

As the polysiloxane represented by the general formula I used for the production of the above-mentioned polyimide siloxane, R in the general formula I has 2 to 6 carbon atoms, particularly 3 to 5 "a plurality of 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.

Examples of the aromatic diamine used for producing the above-mentioned polyimide siloxane include: 1) biphenyl diamine compounds, diphenyl ether diamine compounds, benzophenone diamine compounds, diphenyl sulfone diamine compounds, diphenylmethane 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, in particular,
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 polyimidesiloxane 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.

In the present invention, the polyimidesiloxane (a) is represented by the aromatic tetracarboxylic acid component containing the above-mentioned biphenyltetracarboxylic acid as a main component (containing 90 mol% or more) and the above-mentioned general formula I. 20-80 mol% of diaminopolysiloxane and 2 benzene rings
It is a soluble polymer (imidization ratio: 95% or more, particularly 100%) obtained from a diamine component consisting of 20 to 80 mol% of aromatic diamine having at least one, and has an elastic modulus of 150 kg when formed into a film. / Mm ² or less, particularly about 0.5 to 100 kg / mm ² , and
The softening temperature of the film is 5 ° C or higher, especially 5 to 250 ° C.
Polyimide siloxanes of the order of magnitude are preferred.

An acrylate unsaturated compound (b-) to be blended with the unsaturated compound (b) used in the present invention.
As 1), an unsaturated compound having an acryloyl group or a methacryloyl group at the terminal or side chain of the molecule may be used, and in particular, it has a molecular weight of about 130 to 2000 and is liquid at room temperature, such as dioxane or tetrahydrofuran. It is preferable that the solubility in an organic polar solvent is as high as 5% by weight or more, and for example, a polyol poly (meth) acrylate ester-bonded with a polyol such as glycerin or pentaerythritol, or a poly (meth) having a triazine skeleton. ) Acrylate and polyester poly (meth) acrylate having a polyester skeleton can be preferably mentioned.

In the present invention, as the acrylate-based unsaturated compound, in particular, a polyol poly (meth) acrylate-based acrylate-unsaturated compound (Aronix-M400 manufactured by Toa Gosei Kagaku Kogyo Co., Ltd., Kayarad manufactured by Nippon Kayaku Co., Ltd.) is used. -TMPTA and the like) can be preferably mentioned.

In the unsaturated compound (b), the maleimide unsaturated compound (b-2) which can be used together with the acrylate unsaturated compound is obtained by condensing a maleic anhydride and a diamine compound. As long as it has an unsaturated group (carbon-carbon double bond) derived from maleic acid at both ends, for example, diaminobenzene, 4,4′-diamino-3,3′-dimethylbiphenyl, 4 , 4'-diaminodiphenyl ether, 4,
4'-diaminodiphenylmethane, 2,2-bis (4-
Aminophenyl) propane, 4,4'-diaminodiphenylsulfone, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) )benzene,
1 mol of an aromatic diamine such as bis [4- (3-aminophenoxy) phenyl] sulfone and about 2 parts of maleic anhydride.
Suitable examples are soluble bismaleimides obtained by reacting with mol.

Further, an imide oligomer having amino groups at both ends obtained by reacting a tetracarboxylic acid component such as biphenyltetracarboxylic acid with an excess of the above-mentioned aromatic diamine component is further added to maleic anhydride. The bismaleimide compound represented by the following general formula (II) obtained by reacting with is also preferred.

[0035]

[Chemical 3] (However, in the formula, A is a divalent residue based on a diamine component, R is a tetravalent residue based on a tetracarboxylic acid component, and m is 1 to 10, particularly about 1 to 5 It is.)

Examples of the above-mentioned maleimide unsaturated compound include bismaleimide resin (bismaleimide compound of 4,4'-diaminophenylmethane and maleic anhydride, bismaleimide resin manufactured by Ajinomoto Co., Inc. (trade name: ATU).
-BMI resin), maleimide resin manufactured by Nippon Polyimide Co., Ltd. (trade name: Kelimide-NE20200), maleimide resin manufactured by Technohemie (trade name: Compit 3)
53) etc. can be mentioned suitably.

The epoxy compound (c) having an epoxy group used in the heat-resistant resin 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 compounds having one or more epoxy groups" such as ether type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins (manufactured by Mitsubishi Gas Chemical Co., Inc., Tetrat X, etc.) 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 hardener (d) used in the heat-resistant resin adhesive of the present invention includes imidars,
Examples include curing catalysts such as tertiary 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. be able to.

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 resin adhesive of the present invention has various advantages as described above and has a thickness of 5 to 150 μm.
A heat-resistant resin film with a certain degree of flexibility and a metal foil such as a copper foil or an aluminum foil are joined via this adhesive layer to obtain a metal foil-bonded material (flexible copper-clad board), which is then etched. In the case of a wiring board, the above-mentioned adhesive layer that has been heat-cured in the bonding operation is extremely flexible, and the wiring board rarely curls violently.

The heat-resistant resin adhesive of the present invention comprises the above-mentioned polyimide siloxane (a), an unsaturated compound (b) containing an acrylate unsaturated compound (b-1) as a main component, and an epoxy compound ( Any heat-resistant resin adhesive containing c) and the epoxy curing agent (d) may be used, but all of the above resin components are contained in a suitable organic polar solvent.
Particularly 3 to 50% by weight, more preferably 5 to 40% by weight
It may be a solution composition of a heat-resistant resin adhesive that is uniformly dissolved at a concentration of.

The solution composition of the above heat-resistant resin adhesive is
The solution viscosity (30 ° C.) is 0.1 to 10,000 poise,
Especially 0.2 to 5000 poise, more preferably 1 to 1
It is preferably about 000 poise. 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 resin 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,
More preferably, it is about 0 to 100 ° C. The heat resistant resin adhesive of the present invention is 100-350.
° C, more preferably 120-300 ° C (especially 140-
It is preferably one that can be thermoset by heating to a curing temperature of 250 ° C.).

The heat-resistant resin 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 in preparing the solution composition of the heat-resistant resin adhesive, the organic polar solvent used in the production of the polyimidesiloxane described above can be used as it is. An organic polar solvent having an oxygen atom in the molecule, such as dioxane or tetrahydrofuran, can be preferably used.

The heat-resistant resin adhesive of the present invention comprises a solution composition of the heat-resistant resin adhesive in which all of the above-mentioned resin components are uniformly dissolved in an organic polar solvent, and a suitable metal foil or aromatic polyimide film. Heat-resistant film surface such as, or
The solvent was removed to 1% by weight or less by coating on the surface of a thermoplastic resin film such as polyester or polyethylene, and drying the coating layer at a temperature of 80 to 200 ° C. for 20 seconds to 100 minutes ( It is possible to form a thin film of a heat-resistant adhesive in an uncured state (a dry film or sheet having a thickness of about 1 to 200 μm), which preferably has a residual solvent ratio of especially 0.5% by weight or less.

The thin film of the uncured heat-resistant resin adhesive produced as described above has suitable flexibility and can be wrapped around a paper tube or the like, or punched by a punching method or the like. Further, for example, a laminated sheet in which a thin layer of an uncured heat-resistant resin adhesive is formed on the heat-resistant or thermoplastic film, a metal foil or a heat-resistant film for a transfer destination, etc. Overlap with about 20 ~
It is also possible to transfer to a transfer destination metal foil or heat resistant film by passing it between a pair of rolls (lamination rolls) heated to 200 ° C.

In order to form a laminated body such as a copper clad substrate by joining a heat resistant film and a metal foil using the heat resistant resin adhesive of the present invention, for example, the thin film formed as described above is used. Of the heat-resistant film and the metal foil via the heat-resistant resin adhesive layer in the shape of 80-200 ° C., particularly 120-180
Laminated (laminated) at a temperature of ℃ under pressure, and further, about 150 ~
At a temperature of 300 ° C., particularly 150 to 280 ° C., for 30 minutes
By heating for 40 hours, particularly for 1 to 30 hours to heat-harden the heat-resistant resin-resin adhesive layer, the above-mentioned laminate can be easily and continuously produced without any trouble.

The heat resistant resin 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 an appropriate metal foil such as a copper foil. It can be preferably used for

[0050]

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.

[0051]

[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. The adhesive strength was 90 ° at a measurement temperature of 25 ° C. and a measurement temperature of 1 using a tensile tester manufactured by Intesco at a peeling rate of 50 mm / min.
The results are obtained by performing an 80 ° peel test at 80 ° C.

[Production of Imidosiloxane Oligomer] Reference Example 1 In a glass flask having a capacity of 500 ml, 1) 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) 0.045 mol , 2) ω, ω'-bis (3-aminopropyl) polydimethylsiloxane (X-22-16 manufactured by Shin-Etsu Silicon Co., Ltd.)
1AS, n: 9) 0.030 mol, and 3) 160 g of N-methyl-2-pyrrolidone (NMP) were charged and stirred at 50 ° C. for 2 hours in a nitrogen stream to generate an amic acid oligomer. 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 Example 2 The same procedure 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. 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, 1) 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) 0.044 mol 2 ) 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 0.066 mol, and 3) 160 g of N-methyl-2-pyrrolidone (NMP) are charged, and it is 50 degreeC in 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:
2) was generated.

Reference Examples 4 to 5 a-BPDA, BAPP and NMP in the amounts shown in Table 1
In the same manner as in Reference Example 4 except that each was used, imide oligomers B-2 (average polymerization degree: 5) and B-3 (average polymerization degree: 10) having an amino group at the end were produced.

[0057]

[Table 1]

[Production of Polyimide Siloxane] Reference Example 6 The imidosiloxane oligomer (A-
1 component) 0.0055 mol of 20 wt% NMP solution, and 0.0055 mol of 20 wt% NMP solution of the imide oligomer (B-2 component) produced in Reference Example 4 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 0.49.

Reference Examples 7 to 9 Polyimide siloxane (block) was prepared in the same manner as in Reference Example 6 except that each of the oligomers prepared in Reference Examples 1 to 5 was 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 10 In a 500 ml glass flask, 1) a
-BPDA: 0.048 mol, 2) diaminopolysiloxane (X-22-161A, manufactured by Shin-Etsu Silicon Co., Ltd.)
S): 0.016 mol, 3) BAPP: 0.032 mol, and 4) NMP: 165 g were charged and then stirred at 50 ° C. for 2 hours in a nitrogen stream to form an amic acid oligomer. 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.

[0061]

[Table 2]

Example 1 [Preparation of Solution Composition of Heat-Resistant Resin Adhesive] In a glass flask having a capacity of 500 ml, the polyimidesiloxane (block polymer, A) produced in Reference Example 6 was used.
-1-B-2) 50 g, acrylate unsaturated compound (Aronix M400, manufactured by Toagosei Kagaku Co., Ltd.)
20 g, epoxy resin (Yukaka Shell Epoxy Co., trade name: Epicoat 807) 17 g, phenol novolak type curing agent (Meiwa Kasei Co., Ltd., H-1) 13 g, and dioxane 185 g were charged, and at room temperature (25 ° C.). , Stirring for about 2 hours to obtain a uniform heat-resistant adhesive solution composition (2
Viscosity at 5 ° C .: 7 poise) was prepared. This solution composition has a uniform solution state (viscosity) even when left at room temperature for 1 week.
Was holding.

[Production of Laminate by Heat-Resistant Resin Adhesive]
125 μ with a doctor blade on the solution composition of the heat-resistant resin adhesive described above on a polyimide film (Ube Industries, Ltd., trade name: UPILEX-S type, thickness 75 μm)
m, and then apply the applied layer at 50 ° C for 30
After heating for 30 minutes at 100 ° C. for 30 minutes to dry, a heat-resistant resin adhesive layer (uncured dried layer, softening point: 60 ° C.) having a thickness of about 20 μm was formed on the polyimide film.

The polyimide film having the heat-resistant resin adhesive layer and the copper foil (35 μm) were laminated together to form 130
The laminated rolls heated to ℃ were pressed together by passing them while applying pressure.
1 hour at 0 ° C, 1 hour at 120 ° C, and 6 at 180 ° C
Heat treatment for a period of time to cure the heat resistant resin adhesive layer,
A laminate was produced. The adhesive strength of the obtained laminate was measured, and the results are shown in Table 3.

Examples 2 to 4 The polyimide siloxanes (blocks) prepared in Reference Examples 6 to 9 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 resin 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 5 A heat-resistant adhesive was prepared in the same manner as in Example 1 except that the polyimide siloxane (random) produced in Reference Example 10 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.

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[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 polyimidesiloxane produced in Reference Example 7 and an epoxy resin (Epicote 80 manufactured by Yuka Shell Co., Ltd.)
7) A solution composition of a heat-resistant resin adhesive was prepared in the same manner as in Example 1 except that only 6 g, phenol novolac (H-1) manufactured by Meiwa Kasei Co., Ltd., and 230 g of dioxane were used. Example 1 except that the solution composition was used
The solution composition was applied onto a polyimide film and dried in the same manner as in 1. to form an adhesive layer (uncured and dried adhesive layer, thickness: 20 μm).

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 40 g of an acrylate unsaturated compound (manufactured by Toagosei Kagaku Kogyo Co., Ltd., trade name: Aronix 215), epoxy resin (produced by Yuka Shell Co., Ltd., trade name: Epicoat 8)
28) A heat-resistant resin adhesive solution composition was prepared in the same manner as in Example 1 except that only 23 g and dioxane 150 g were used. 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, and an adhesive layer (an uncured dried adhesive layer,
Thickness: 20 μm) was formed. A polyimide film having the above-mentioned adhesive layer was formed in the same manner as in Example 1, and the polyimide film and the copper foil were laminated in the same manner as in Example 1, but the adhesive layer flowed during the lamination and was laminated. The body could not be easily formed.

Comparative Example 3 Each of the polyimide siloxanes produced in Reference Example 7 and the acrylate unsaturated compound in the composition ratios shown in Table 3 were used.
A solution composition of the heat-resistant resin adhesive was prepared in the same manner as in Example 1 except that the epoxy resin was used. The same lamination as in Example 1 was performed, but the adhesive layer flowed and the laminate could not be manufactured.

[0073]

The effects of the present invention are as follows:
By coating the solution composition on a support film and drying it at a relatively low temperature, an uncured, heat-resistant resin adhesive layer in a thin layer state can be easily formed, and the heat resistance of the thin layer is high. The resin adhesive layer has sufficient flexibility,
Moreover, the thin heat-resistant resin adhesive layer on the support film does not cause any problems even when subjected to punching processing, and can be transferred onto another heat-resistant support film at an appropriate temperature. The heat-resistant film and the copper foil can be laminated at a relatively low temperature with good workability.

Further, the heat resistant resin adhesive of the present invention is
Even after being heat-cured to form a laminate, it has excellent heat resistance and flexibility, and since the curl of the etching film after etching such as copper foil is also small, especially for flexible wiring boards and TAB It can be suitably used as an adhesive for copper-clad substrates and the like.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Tadao Muramatsu 3-10 Nakamiyakitamachi, Hirakata City, Osaka Prefecture Ube Industries Ltd. Hirakata Laboratory

Claims (1)

[Claims] 1. An aromatic tetracarboxylic acid component comprising (a) a biphenyltetracarboxylic acid as a main component, and a compound represented by the general formula (I): (However, 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 polyimidesiloxane obtained from a diamine component consisting of 10 to 80 mol% of diaminopolysiloxane and 20 to 90 mol% of an aromatic diamine, and (b) containing an acrylate-based unsaturated compound as a main component. 5 to 400 parts by weight of unsaturated compound, (c) epoxy compound having epoxy group 20 to 250
A heat-resistant resin adhesive, characterized in that, by weight, (d) an epoxy curing agent is contained as a resin component.