JPH05117617A - Heat-resistant adhesive composition - Google Patents

Abstract

PURPOSE:To improve adhesive strength, flexibility, and heat resistance by mixing a soluble aromatic polyimide with an imidosiloxane oligomer terminated with unsaturated bond, a specific compound, and an epoxy hardener. CONSTITUTION:100 pts.wt. soluble aromatic polyimide obtained from aromatic tetracarboxylic acids consisting mainly 2,3,3',4'--biphenyltetracarboxylic acid and diamines consisting mainly of an aromatic diamine represented by the formula (wherein X is -O or -CH2- and Y is -SO- or -CH(CH3)2-) is mixed with 2-50 pts.wt. terminal-modified imidosiloxane oligomer, 5-150 pts.wt. epoxy compound having an aliphatic ester bond, and an epoxy hardener. The oligomer is one obtained by reacting an aromatic tetracarboxylic acid with diamines consisting mainly of diaminopolysiloxane and either an unsaturated monoamine or a dicarboxylic acid, and has a softening point of 300 deg.C or lower.

Description

Detailed Description of the Invention

[0001]

This invention relates to a soluble aromatic polyimide having no unsaturated group at the terminal (A) as a flexible polymer component, and an unsaturated group at the terminal ((B1) as a curing component. End-modified imide siloxane oligomer and (C1) epoxy compound having aliphatic acid ester bond and epoxy group ”, or“ (B2) end-modified imide oligomer having unsaturated group at the end and (C
2) Epoxy-modified polysiloxane compound ”, and further includes (D) an epoxy curing agent as a resin component in a specific composition ratio, relating to a heat-resistant adhesive composition for a bonding sheet.

The heat-resistant adhesive composition of the present invention is used for bonding various metal foils such as copper foil and a heat-resistant supporting material (eg heat-resistant film, inorganic sheet, etc.) via the adhesive composition. Can be carried out at a relatively low temperature, and the laminate laminated with the adhesive composition has a cured adhesive layer exhibiting sufficient adhesive force and excellent heat resistance, and is not rigid but flexible. , Flexible wiring board, TAB (Ta
When used in the manufacture of copper-clad boards for pe automated bonding, each board can perform various high-temperature processing steps such as subsequent soldering processing with peace of mind, and the final product does not curl violently and its quality is improved. It is possible to raise the defect rate and reduce the defective rate of the product.

[0003]

2. Description of the Related Art Conventionally, a flexible wiring board is often manufactured by bonding a polyimide film and a metal foil using an adhesive such as epoxy resin or urethane resin. However, when a flexible wiring board manufactured using a known adhesive is exposed to high temperatures in the subsequent soldering process, it causes "blisters" and "peeling" in the adhesive layer.
There is a problem in that the heat resistance of the adhesive is improved.

As the heat-resistant adhesive, an imide resin adhesive has been proposed, for example, N, N '-(4,4'-
A precondensate composed of diphenylmethane) bismaleimide and 4,4′-diaminodiphenylmethane is 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-mentioned drawbacks, an adhesive film (dry film or bonding sheet) is formed from a resin composition obtained by mixing an aromatic polyimide obtained from benzophenonetetracarboxylic acid and an aromatic diamine with polybismaleimide. Then, a method has been proposed in which the adhesive film is sandwiched between a heat resistant 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 / cm. ^It is necessary to carry out under a high pressure of about ^{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. Was a problem.

On the other hand, as a composition for coating 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 composed of the cured resin and a wiring board or the like. Although various proposals have been made to improve the adhesiveness of the known coating composition, the known coating composition is "adhesive for adhering copper foil and aromatic polyimide film" in the production of the copper clad substrate as described above. As the bonding or curing temperature is high, 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 flexible. However, there was a problem that it could not be used as an adhesive.

[0008]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to solve the above-mentioned problems with known adhesives, and to easily form an adhesive film (bonding sheet), and to bond the same. The sheet itself has flexibility (flexibility), has tackiness, and is preferably laminated with a heat-resistant film and various metal foils through a process of laminating a copper foil and curing an adhesive layer, It is an object of the present invention to provide a "heat-resistant adhesive composition that serves as a bonding sheet exhibiting high adhesiveness at high temperature", which can obtain a laminate having excellent performance without curling.

[0009]

The present invention comprises (A)
An aromatic tetracarboxylic acid component containing 2,3,3 ′, 4′-biphenyltetracarboxylic acid as a main component (preferably containing 80 mol% or more);

[Chemical 3]

(In the formula, X is --O-- or --CH
₂ -, Y is, -SO ₂ -, or -CH _(CH 3)
₂ - aromatic polyimide 100 parts by weight of the soluble obtained from a diamine component mainly comprising an aromatic diamine represented by the illustrated),

(B1) Aromatic tetracarboxylic acid component,
Mainly composed of diaminopolysiloxane (preferably 9)
2 to 50 parts by weight of a terminal-modified imide siloxane oligomer having a softening point of 300 ° C. or lower, which is obtained by reacting a diamine component (containing 0 to 100 mol%) and a monoamine or dicarboxylic acid having an unsaturated group (preferably Is 5
To 20 parts by weight), and (C1) 5 to 150 parts by weight (preferably 10 to 100 parts by weight) of an epoxy compound having an aliphatic acid ester bond and having an epoxy group,
Alternatively,

(B2) aromatic tetracarboxylic acid component,
End-modified imide oligomers 2 to 50 having a softening point of 300 ° C. or lower, which are obtained by reacting an aromatic diamine component and an unsaturated group-containing monoamine or dicarboxylic acid
Parts by weight (preferably 5 to 20 parts by weight), and (C2)
Epoxy-modified polysiloxane compound 5 to 150 parts by weight (preferably 10 to 100 parts by weight),

(D) Epoxy curing agent (preferably epoxy compound or epoxy-modified polysiloxane compound 10)
0.01 to 90 parts by weight based on 0 parts by weight) is contained as a resin component, and the present invention relates to a heat-resistant adhesive composition.

The soluble aromatic polyimide (A) used as one component of the resin component in the present invention is, for example,
The main component is 3,3 ′, 4′-biphenyltetracarboxylic acid (for example, 2,3,3 ′, 4′-biphenyltetracarboxylic acid or an acid dianhydride thereof or an acid esterified product thereof) (80 Aromatic tetracarboxylic acid component containing at least mol%, especially 90 to 100 mol%, and a specific aromatic diamine represented by the general formula I as main components (at least 80 mol%, particularly from 90 to 100 mol%). ) Polymerization and imidization at a temperature of 140 ° C. or higher in an organic polar solvent using approximately equimolar amounts of the diamine component as a monomer component, a high molecular weight polymer having no unsaturated group at the end It is preferably an aromatic polyimide.

The method for producing the aromatic polyimide (A) is
A process for producing a polyamic acid by polymerizing approximately equimolar amounts of an aromatic tetracarboxylic acid component and a diamine component in an organic polar solvent at a low temperature of 0 to 80 ° C., and imidizing the polyamic acid by any known method is used. It can also be adopted.

The aromatic polyimide (A) has a logarithmic viscosity (measured concentration; 0.5 g / 100) corresponding to the molecular weight of the polymer.
Milliliter solvent, solvent; N-methyl-2-pyrrolidone, measurement temperature; 30 ° C.) is 0.3 to 6, particularly 0.5 to
It is a polymer of about 5 and at least 3 wt% in an organic polar solvent (particularly an amide solvent), especially 5 to
Those that can be uniformly dissolved at a concentration of about 40% by weight are preferable.

In other words, the aromatic polyimide (A) has the general formula II

[Chemical 4] (However, in the general formula II, Ar is a divalent residue obtained by removing two amino groups of a diamine compound such as an aromatic diamine.) The repeating unit represented by 80 mol% or more, particularly 90 to
It is preferably a high molecular weight aromatic polyimide which contains 100 mol% and is soluble in an organic polar solvent and does not have unsaturated groups at both ends.

The aromatic polyimide (A) has an imidization ratio of 90% or more, particularly 95% or more as measured by an infrared absorption spectrum analysis method, or an absorption peak relating to the amide-acid bond of the polymer in the infrared absorption spectrum analysis. Is not found and only the absorption peak related to the imide ring bond is seen, and the imidization ratio is preferably 100%.

In the present invention, when the aromatic polyimide is produced by using tetracarboxylic acids other than 2,3,3 ', 4'-biphenyltetracarboxylic acid as a main component, the aromatic polyimide is organic. It is not suitable because it may be sparingly soluble in a polar solvent or may have low compatibility with the above-mentioned terminal-modified imide oligomer or imide siloxane oligomer, or an epoxy compound.

Examples of the tetracarboxylic acid that can be used in combination with a-BPDA in the tetracarboxylic acid component used in the production of the aromatic polyimide (A) are:
3 ', 4,4'-biphenyltetracarboxylic acid, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid,
3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane,
2,2-bis (3,4-dicarboxyphenyl) propane, or dianhydrides or esterified products of those acids can be mentioned.

The aromatic diamine represented by the general formula I used as the diamine component in the production of the aromatic polyimide (A) is 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), 2 , 2-bis [4- (4
-Aminophenylmethyl) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone,
Examples thereof include bis [4- (4-aminophenylmethyl) phenyl] sulfone (BAPS).

As the diamine compound which can be used in combination with the aromatic diamine represented by the general formula I in the production of the aromatic polyimide (A), biphenyl type diamine, diphenyl ether type diamine, benzophenone type diamine, diphenyl sulfone type diamine, diphenylmethane type diamine, Diphenylpropane diamine, 2,2-bis (phenyl) hexafluoropropane diamine, diphenylene sulfone diamine, di (phenoxy) benzene diamine, di (phenyl) benzene diamine, di (phenoxyphenyl) hexafluoropropane diamine “Aromatic diamine compound having two or more aromatic rings (benzene ring etc.)” such as diamine can be mentioned.

In the present invention, the terminal-modified imide siloxane oligomer (B
1) is, for example, an aromatic tetracarboxylic acid component, a diamine component, and a monoamine or dicarboxylic acid having an unsaturated group, the total amount of an acid anhydride group (or a pair of adjacent carboxyl groups) and an amino group in each component. Of the aromatic tetracarboxylic acid component and the diamine component in an organic polar solvent.
The reaction is carried out at a temperature of 0 ° C. or lower to form an amic acid oligomer having an amide-acid bond, and then the amic acid oligomer is reacted with a monoamine or dicarboxylic acid having an unsaturated group, and further at 140 to 250 ° C. Any material can be used as long as it can be obtained by a manufacturing method in which it is heated to a high temperature.

End-modified imide siloxane oligomer (B
1) has a softening point of 300 ° C or lower, especially 40 to 250 ° C.
And a logarithmic viscosity of 0.5 or less, particularly 0.01 to 0.
A terminal-modified imide siloxane oligomer having an unsaturated group at the terminal and an imide bond in the molecule is preferable.

End-modified imide siloxane oligomer (B
1) is represented by the general formula III or IV

[Chemical 5] (In the formula, Ar ₁ is a tetravalent aromatic residue obtained by removing four carboxyl groups of aromatic tetracarboxylic acid, and Ar ₂
Is a divalent residue excluding two amino groups of a diamine compound, R ₁ is a monovalent organic residue obtained by removing one amino group of a monoamine compound having an unsaturated group, and R ₂ is a divalent organic residue obtained by removing two carboxyl groups of a dicarboxylic acid having an unsaturated group, and further,
m and n are integers of about 1 to 50, particularly about 1 to 30), and are preferably end-modified imide siloxane oligomers.

As the aromatic tetracarboxylic acid component used in the method for producing the terminal-modified imide siloxane oligomer, any of the aromatic tetracarboxylic acids already exemplified in the method for producing an aromatic polyimide can be used.

The aromatic tetracarboxylic acid component used in the method for producing the terminal-modified imide siloxane oligomer includes 2,3,3 ', 4'-biphenyltetracarboxylic acid and 3,3', 4,4'-biphenyl. Aromatic tetracarboxylic acid containing as a main component (80 mol% or more, particularly 90 mol% or more) biphenyltetracarboxylic acid such as tetracarboxylic acid, acid dianhydride thereof, or ester value of acid thereof Acid components are preferred, and benzophenone tetracarboxylic acids, biphenyl ether tetracarboxylic acids, bis (3,4-dicarboxyphenyl) benzenes, 2,2-bis (3,4-dicarboxyphenyl) propane, etc. Can also be used as the aromatic tetracarboxylic acid component.

Examples of the diaminopolysiloxane used in the method for producing the terminal-modified imide siloxane oligomer include those represented by the general formula V

[Chemical 6] (However, in the formula, R represents a divalent hydrocarbon residue, and R ₃ ,
R ₄ , R ₅ and R ₆ represent a lower alkyl group having 1 to 4 carbon atoms or a phenyl group, and p is 3 to 60, preferably 5 to 5
Indicates an integer of 0. The diamino polysiloxane shown by these can be mentioned.

The diaminopolysiloxane represented by the general formula V is a divalent hydrocarbon residue in which R in the general formula V is a "plurality of methylene groups" having 2 to 6 carbon atoms or a phenylene group. It is preferable that _{3 to} R ₆ are an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group, or a phenyl group, and p is about 5 to 20.

Examples of the monoamine compound having an unsaturated group used in the method for producing the terminal-modified imide siloxane oligomer include propargyl amine, 3-aminobutyne, 4-aminobutyne, 4-aminopentine, 5-aminopentine, 6-aminohexyne, and 4-amino-. “Aliphatic monoamine compound having an unsaturated group” such as 3-methylbutyne and allylamine, or m- or p-aminostyrene, m-amino-α-methylstyrene, 1-isopropenyl-3- (2-aminoisopropyl) ) Benzene, 3-
"Aromatic monoamine compounds having unsaturated groups" such as aminophenylacetylene and 4-aminophenylacetylene can be mentioned.

Examples of the dicarboxylic acid compound having an unsaturated group used in the method for producing the terminal-modified imide siloxane oligomer include maleic acid, citraconic acid, nadic acid, itaconic acid, tetrahydrophthalic acid, or acid anhydrides thereof. Preferable examples include "unsaturated dicarboxylic acids having two carboxyl groups adjacent to each other" such as acid esterified products.

The terminal-modified imide oligomer (B2) used as one component of the resin component in the present invention includes, for example, an aromatic tetracarboxylic acid component, an aromatic diamine, and a monoamine or dicarboxylic acid compound having an unsaturated group. , And adjusting so that the total amount of acid anhydride groups (or a pair of adjacent carboxyl groups) in each component and the total amount of amino groups are equal to each other, first, the aromatic tetracarboxylic acid component and aromatic Diamine component in organic polar solvent 10
The reaction is performed at a temperature of 0 ° C. or lower to form an amic acid oligomer having an amide-acid bond, and then the amic acid oligomer is reacted with a monoamine or dicarboxylic acid having an unsaturated group, and the temperature is raised to 140 to 250 ° C. Any material can be used as long as it can be obtained by a heating method.

In other words, the terminal-modified imide oligomer (B2) has the general formula VI or VII.

[Chemical 7] (In the formula, Ar ₃ is a divalent aromatic residue excluding two amino groups of the aromatic diamine compound, and A 3
r ₁ , R ₁ and R ₂ , and m and n have the same definitions as those in the above general formulas III and IV. It is preferable that it is the terminal modification imide oligomer shown by these.

As the aromatic tetracarboxylic acid, aromatic diamine, monoamine or dicarboxylic acid compound having an unsaturated group used in the production of the terminal-modified imide oligomer, those described above can be used.

End-modified imide siloxane oligomer (B
1) or the terminal-modified imide oligomer (B2) has an imidization ratio of 95% or more 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 imidation ratio is substantially 100%, which is not found and only the absorption peak relating to the imide ring bond is observed.

End-modified imide siloxane oligomer (B
Examples of the organic polar solvent used in 1) or the production of the terminal-modified imide oligomer (B2) include N, N-
Amide solvents such as dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexa Solvents containing sulfur atom such as methyl sulfolamide, phenolic solvents such as cresol, phenol, xylenol, acetone, methanol, ethanol, ethylene glycol, dioxane, tetrahydrofuran, pyridine, other solvents such as tetramethyl urea You can

The epoxy compound having an aliphatic acid ester bond and an epoxy group (C
As 1), a polyglycidyl ester compound obtained by reacting an aliphatic acid with glycidyl alcohol, for example, a flexible epoxy resin such as polyglycidyl ester of an aliphatic acid such as linoleic acid or linolenic acid, or carbon Ester compounds of synthetic aliphatic acid (dibasic acid) of about several tens to 30 and glycidyl alcohol, for example, polyglycidyl ester such as Epicoat 871 manufactured by Yuka Shell Co., Ltd. and IPU-22G manufactured by Okamura Oil Co., Ltd. be able to.

As the epoxy-modified polysiloxane compound (C2) used in the present invention, a reactive polysiloxane oil having a hydroxyl group, a carboxyl group or an amino group at the terminal, a bisphenol type epoxy resin,
At least one epoxy group at the terminal or inside of polysiloxane obtained by reacting with an epoxy compound such as phenol novolac type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin at a temperature of about 80 to 140 ° C. Any epoxy modified polysiloxane may be used.

Epoxy-modified polysiloxane compound (C
As 2), those having a melting point of 90 ° C. or lower, or 30
Those which are liquid at a temperature of ℃ or less are preferable, for example, polyglycidoxypropylmethylsiloxane (PS920, PS922, etc.) manufactured by Chisso Corporation, epoxy-glycol modified silicone oil (SF manufactured by Toray Dow Corning Silicone Co., Ltd. (SF -8421, BY-16-84
No. 5, etc.), epoxy terminal reactive silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. (KF105, X-22-163, etc.), and the like.

In the present invention, the epoxy compound (C
Along with 1) or (C2), "epoxy compound having one or more epoxy groups" such as bisphenol type epoxy resin, phenol novolac type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, etc. It can also be used in combination at a ratio of 20% by weight or less.

The epoxy curing agent (D) used in the heat-resistant adhesive composition of the present invention includes imidazoles, tertiary amines, phenols, triphenylphosphines, dicyandiamides, hydrazines, Examples thereof include anion type curing agents such as aromatic diamines, polyaddition type curing agents such as phenol novolac type curing agents having a hydroxyl group, and organic peroxides. The above-mentioned epoxy curing agent is about 0.01 to 100 parts by weight of the epoxy resin.
It is preferable to use about 90 to 90 parts by weight, particularly about 0.03 to 80 parts by weight.

The heat-resistant adhesive composition of the present invention comprises an aromatic polyimide (A), an end-modified imide siloxane oligomer (B1) and an epoxy compound (C1) having an aliphatic acid ester bond, or an end-modified imide oligomer (B1).
2) and an epoxy-modified polysiloxane compound (C2),
Further, any heat-resistant resin composition may be used as long as it contains a resin component having a specific composition ratio of the epoxy curing agent (D) as a main component (90% by weight or more), but all the above resin components are suitable organic polar solvents. It may be a solution composition of a heat-resistant adhesive which is uniformly dissolved in a concentration of 3 to 50% by weight.

The solution composition of the above heat-resistant adhesive preferably has a solution viscosity (30 ° C.) of about 0.1 to 10,000 poises, particularly about 0.2 to 5,000 poises.
Further, the uncured heat-resistant adhesive composition has a softening point (temperature at which softening starts on a hot plate) of 150 ° C. or lower, particularly 120 ° C.
Or less, and 130 to 400 ° C., especially 140 to 35
It is preferable to cure by heating to a curing temperature of 0 ° C.

The organic polar solvent used in preparing the heat-resistant adhesive composition of the present invention is an organic polar solvent for polymerization used in the production of the aromatic polyimide, the terminal-modified imide siloxane oligomer, and the terminal-modified imide oligomer. The polar solvent can be used as it is, but it is particularly preferable to use an organic polar solvent having an oxygen atom in the molecule, such as dioxane or tetrahydrofuran.

The above heat-resistant adhesive solution composition is applied to a suitable metal foil, aromatic polyimide film surface, or polyester film surface, and the applied layer is 60 to 140.
By drying at a temperature of C for 20 to 100 minutes, the solvent is substantially removed (the residual ratio of the solvent is 1% by weight or less). The sheet of the uncured heat-resistant adhesive composition (thickness: approx. A dry film or a bonding sheet) having a thickness of 1 to 200 μm can be formed.

The above-mentioned bonding sheet has suitable flexibility and can be wound around a paper tube or the like, or can be punched by a punching method or the like, and can be uncured on the peelable film. A sheet on which a heat-resistant adhesive layer is formed and a heat-resistant film etc. for the transfer destination are stacked,
It is also possible to transfer the adhesive sheet layer onto the heat resistant film by passing it between a pair of laminating rolls heated to a temperature of about 20 to 140 ° C.

In order to form a laminate such as a copper clad substrate by bonding a heat resistant film and a metal foil using the heat resistant adhesive composition of the present invention, for example, a heat resistant adhesive composition A heat-resistant film and a metal foil are laminated at a temperature of 100 to 180 ° C. via a film or sheet, and the laminated body is further laminated at a temperature of 100 to 350 ° C.
By heating for 30 hours to heat and cure the adhesive layer, the above-mentioned laminate can be easily and continuously produced.

The heat resistant adhesive composition of the present invention comprises a heat resistant film such as an aromatic polyimide film, a polyamide film, a polyether ether ketone, a PEEK film and a polyether sulfone film, and a suitable metal foil such as a copper foil. It can be preferably used for joining.

The heat-resistant adhesive composition of the present invention has various advantages as described above, and has a thickness of 5 to 150 μm.
A metal foil laminating material (such as a flexible copper-clad board) obtained by bonding a flexible heat-resistant resin film of about m and a metal foil such as copper foil or aluminum foil via a heat-resistant adhesive composition layer When the wiring board is formed by etching, the adhesive layer that is heat-cured at the time of bonding is extremely flexible, and the wiring board does not curl extremely violently.

[0050]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the following examples, the logarithmic viscosity (η
_inh ) is an aromatic polyimide, an end-modified imide siloxane oligomer, or an end-modified imide oligomer, which is N-methyl-containing so as to have a concentration of 0.5 g / 100 ml solvent.
It is a value calculated by the following calculation formula by uniformly dissolving in 2-pyrrolidone, measuring the solution viscosity of the solution and the viscosity of the solvent at 30 ° C.

[0051]

[Formula 1]

The tackiness of the bonding sheet is
It is measured by sandwiching a bonding sheet between aromatic polyester films (PET), laminating by pressure bonding between rolls at 40 ° C., ◯ indicates that they are sufficiently adhered, and x indicates that they are spontaneously peeled. .. Then, the adhesive strength of the bonding sheet is a result measured by performing a T-type peeling test at a peeling speed of 50 mm / min using a tensile tester manufactured by Intesco.

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

Reference Example 1 [Production of Aromatic Polyimide A] In a glass flask having a capacity of 500 ml, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) 29.4 was added.
2 g (0.1 mol) and 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 41.
1 g (0.1 mol) and 282 g of N-methyl-2-pyrrolidone (NMP) were charged, and the monomer component was stirred in NMP at a polymerization temperature of 200 ° C. for 2 hours to polymerize and imidize, A solution containing 18% by weight of soluble aromatic polyimide A and uniformly dissolved was prepared. The aromatic polyimide A had an imidization ratio of substantially 100% and an inherent viscosity (30 ° C.) of about 1.5.

Reference Example 2 [Production of terminal-modified imide siloxane oligomer B1-1] In a glass flask having a capacity of 500 ml,
11.77 g (0.4 mol) of 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA), diaminopolysiloxane represented by the general formula V (R: -CH
_{2 CH 2 CH 2 -, R} 3 ~R 6: -CH 3, p: 9) 5
2.8 g (0.06 mol), dimethylacetamide (D
258 g of MAc) was charged and stirred in a nitrogen stream at 50 ° C. for 1 hour to form an amic acid oligomer, and then the reaction solution was heated to about 165 ° C. and stirred at that temperature for 3 hours. An imide oligomer having an amino group at the terminal was produced.

After cooling the reaction solution to 50 ° C., maleic anhydride (6.87 g) (0.07 mol) and 35 g of toluene were added, and the reaction solution was heated to about 160 ° C. to generate toluene. While being removed with water, the mixture is stirred at that temperature for 3 hours for imidization to form a terminal-modified imide siloxane oligomer having a maleic acid-based unsaturated group (B1-1 component, average degree of polymerization p: 2). It was

Reference Example 3 [Production of terminal-modified imide siloxane oligomer B1-2] In a glass flask having a capacity of 1000 ml,
2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) 14.71 g (0.05 mol),
Diaminopolysiloxane represented by the general formula V (R: -C
_{H 2 CH 2 CH 2 -,} R 3 ~R 6: -CH 3, p: 9)
88 g (0.1 mol), maleic anhydride (11.77)
g) (0.12 mol) and DMAc 411 gg, but in the same manner as in Reference Example 2, a terminal-modified imide siloxane oligomer having a maleic acid-based unsaturated group at the end (B1-2 component, average polymerization degree). p: 1) was generated.

Reference Example 4 [Production of terminal-modified imide oligomer B2-1] Capacity 50
In a 0 ml glass flask, add 2, 3, 3 ',
4'-biphenyltetracarboxylic dianhydride (a-BP
DA) 14.71 g (0.05 mol), 1,3-bis (4-aminophenoxy) benzene 29.23 g (0.
1 mol) and 11.77 g (0.12 mol) of maleic anhydride and 176 g of DMAc were added, but Reference Example 2
In the same manner as above, a terminal-modified imide oligomer (B2-1 component, average degree of polymerization p: 1) having a maleic acid-based unsaturated group at the terminal was produced.

Reference Example 5 [Production of terminal-modified imide oligomer B2-2] Capacity 50
In a 0 ml glass flask, add 2, 3, 3 ',
4'-biphenyltetracarboxylic dianhydride (a-BP
DA) 14.71 g (0.05 mol), 1,3-bis (4-aminophenoxy) benzene 17.54 g (0.5.
06 mol), 6.87 g of maleic anhydride (0.07 mol) and 150 g of DMAc were charged, and Reference Example 2
In the same manner as above, a terminal-modified imide oligomer (B2-2 component, average degree of polymerization p: 5) having a maleic acid-based unsaturated group at the terminal was produced.

Example 1 [Preparation of Solution Composition of Heat-Resistant Adhesive] 60 parts by weight of the aromatic polyimide (A) produced in Reference Example 1 described above was added to a glass flask having a volume of 1 liter, in Reference Example 2. End-modified imidosiloxane oligomer (B1-1) 10 produced
Parts by weight, glycidyl ester epoxy resin of synthetic aliphatic acid (C1) (Okamura Oil Co., Ltd., trade name: IPU-2)
2G) 30 parts by weight, polyaddition type curing agent: phenol novolac type curing agent 11 parts by weight, anion type curing agent: 2-phenylimidazole (2PZ) 0.01 parts by weight, tetrahydrofuran (THF) 200 parts by weight are charged at room temperature. (2
At 5 ° C.), the mixture was stirred for about 2 hours to prepare a heat-resistant adhesive solution composition (viscosity at 25 ° C .: 10 poise). This solution composition maintained a uniform solution state even when left at room temperature for 1 week.

[Production of Laminate by Heat-Resistant Adhesive Composition] The above-mentioned solution composition of heat-resistant adhesive was applied on a polyimide film (manufactured by Ube Industries, Ltd., trade name: UPILEX S type, thickness 75 μm). 175μ with doctor blade
m, and then apply the applied layer at 60 ° C for 10
For 10 minutes at 100 ° C, and then for 10 minutes at 120 ° C to dry and dry it on a polyimide film to a thickness of about 25μ.
m heat-resistant adhesive composition sheet layer (uncured and dried adhesive composition bonding sheet layer, softening point: 95
C) was formed.

Polyimide film having a bonding sheet layer of this heat resistant adhesive composition and copper foil (35 μm)
And are overlapped with each other, and pressure is applied between the laminating rolls heated to 130 ° C. while applying pressure, so that pressure bonding is performed.
This pressure-bonded laminated body is heated at 180 ° C. for 2 hours and then at 100 ° C.
Hour, 120 ° C for 1 hour, 140 ° C for 1 hour, then 1
The bonding sheet layer was cured by heat treatment at 60 ° C. for 10 hours in a nitrogen stream to produce a laminate. The adhesive strength of the obtained laminate was measured, and the results are shown in Table 1.

Examples 2 to 4 and Comparative Example 1 Instead of the terminal-modified imide siloxane oligomer (B1), the terminal-modified imide oligomer (B2) prepared in Reference Examples 3 to 5 as shown in Table 1 was used. In the same manner as in Example 1, except that the other thermosetting resins, epoxy compounds and curing agents shown in Table 1 were used, and the composition of each component was as shown in Table 1, A solution composition of each adhesive was prepared. Further, as in Example 1 except that each of the above-mentioned solution compositions was used,
Each laminate was manufactured. The performance of the laminate is shown in Table 1.

[0064]

[Table 1]

In Table 1, "Epicoat 807" in the column of epoxy compound is a bisphenol type epoxy resin manufactured by Yuka Shell Co., Ltd., and "KF105".
Is an epoxy-terminated reactive silicone oil (epoxy-modified polysiloxane compound) manufactured by Shin-Etsu Chemical Co., Ltd., and “PS920” is polyglycidoxypropyl siloxane (epoxy-modified polysiloxane compound) manufactured by Chisso Corporation. Then, in Table 1, "2-PZ" in the column of anionic curing agent represents 2-phenylimidazole manufactured by Shikoku Kasei Co., Ltd., and "2.
E4MZ "is 2-methyl-4- manufactured by Shikoku Kasei Co., Ltd.
Indicates methyl imidazole.

[0066]

The heat-resistant adhesive composition of the present invention contains a resin component composed of an aromatic polyimide, an end-modified imide oligomer, an epoxy resin and an epoxy curing agent, and contains siloxane as a thermosetting resin. It is characteristic that an end-modified imide silicon oligomer having a bond or an epoxy-modified polysiloxane is used.

The heat-resistant adhesive composition of the present invention is prepared by coating the solution composition on a supporting film and drying it at a low temperature to give an uncured and thin bonding layer (adhesive layer).
Can be easily formed, and moreover, while the thin bonding layer has sufficient flexibility, there is no problem even if the bonding sheet layer on the supporting film is subjected to perforation processing, It is also possible to transfer onto another heat-resistant film at an appropriate temperature, and it is possible to laminate a heat-resistant film and a copper foil at a relatively low temperature, which has good workability. ..

Furthermore, since the heat-resistant adhesive composition of the present invention is excellent in heat resistance (adhesiveness at a temperature of 150 ° C. or higher) and flexibility even after being heat-cured,
In particular, it can be preferably used as an adhesive for a laminated material such as a flexible wiring board or a copper-clad board for TAB that requires flexibility.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Tetsuji Hirano 3-10 Nakamiyakitamachi, Hirakata-shi, Osaka Ube Industries Ltd. Hirakata Laboratory

Claims (2)

[Claims] 1. An aromatic tetracarboxylic acid component containing (A) 2,3,3 ′, 4′-biphenyltetracarboxylic acid as a main component, and a compound represented by the general formula I: [In the formula, X is, -O-, or -CH ₂ -,
Y is, -SO ₂ -, or -CH _{(CH 3) 2} - shows a]
100 parts by weight of a soluble aromatic polyimide obtained from a diamine component containing an aromatic diamine as a main component, (B1) an aromatic tetracarboxylic acid component, a diamine component containing a diaminopolysiloxane as a main component, and 2 to 50 parts by weight of an end-modified imide siloxane oligomer having a softening point of 300 ° C. or less, obtained by reacting a monoamine or dicarboxylic acid having an unsaturated group, (C1) having an aliphatic acid ester bond, and an epoxy group 5 to 150 parts by weight of an epoxy compound having (4), and (D) an epoxy curing agent are contained as a resin component, a heat-resistant adhesive composition. 2. An aromatic tetracarboxylic acid component containing (A) 2,3,3 ', 4'-biphenyltetracarboxylic acid as a main component, and a compound represented by the general formula I: [In the formula, X is, -O-, or -CH ₂ -,
Y is, -SO ₂ -, or -CH _{(CH 3) 2} - shows a]
100 parts by weight of a soluble aromatic polyimide obtained from a diamine component containing an aromatic diamine as a main component, (B2) an aromatic tetracarboxylic acid component, an aromatic diamine component, and a monoamine having an unsaturated group. Or 2 to 50 parts by weight of an end-modified imide oligomer having a softening point of 300 ° C. or lower, obtained by reacting a dicarboxylic acid, (C2) epoxy-modified polysiloxane compound 5 to 15
0 parts by weight, and (D) Epoxy curing agent is contained as a resin component, a heat-resistant adhesive composition.