JPH05117616A - Heat-resistant adhesive - Google Patents

Abstract

PURPOSE:To improve adhesive strength by mixing a specific aromatic poly(amide-imide) with a terminal-modified imide (siloxane) oligomer or other polymer, a polyfunctional epoxy compound, and a hardener. CONSTITUTION:100 pts.wt. soluble aromatic poly(amide-imide) is mixed with 10-200 pts.wt. either of a terminal-modified imide (siloxane) oligomer or a bismaleimide-triazine resin, 5-80 pts.wt. polyfunctional epoxy compound, and an epoxy hardener. The poly(amide-imide) in one obtained from aromatic tricarboxylic acids consisting mainly of trimellitic acid and diamines consisting mainly of diaminopolysiloxane, and is composed of repeating units 80% or more of which are represented by the formula. The oligomer is one obtained by reacting aromatic tetracarboxylic acids consisting mainly of either 2,3,3',4'- biphenyltetracarboxylic acid or a derivative thereof with either diamines consisting mainly of diaminopolysiloxane or an aromatic diamine and with 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]

FIELD OF THE INVENTION The present invention relates to (A) a soluble aromatic polyamideimide having no unsaturated group at the terminal as a flexible polymer component, and a curing component as a curing component.
(B1) Terminal-modified imide siloxane oligomer having an unsaturated group at the terminal, (B2) Terminal-modified imide oligomer having an unsaturated group at the terminal or (B3) Bismaleimide-triazine resin, (C) Polyfunctional having an epoxy group The present invention relates to a heat-resistant adhesive that can be used as a bonding sheet and that contains a conductive epoxy compound and (D) an epoxy curing agent as a resin component in a specific composition ratio.

The heat-resistant adhesive of the present invention is used for bonding various metal foils such as copper foil and a heat-resistant support material (for example, heat-resistant film, inorganic sheet) through the heat-resistant adhesive. Since it can be performed at a relatively low temperature, and the cured adhesive layer exhibits sufficient adhesive strength, excellent heat resistance, and is not rigid, it is flexible, so that it can be used for flexible wiring boards and TAB (Tape Automated Bonded).
ng) copper-clad substrate, etc., can be used with confidence in the various high-temperature treatment processes such as each substrate obtained using the heat-resistant adhesive or the subsequent solder treatment. The product does not curl violently, its quality can be improved and the defective rate of the product can be reduced.

[0003]

2. Description of the Related Art Conventionally, a flexible wiring board is often manufactured by bonding an aromatic polyimide film and a copper foil together using an adhesive such as epoxy resin or urethane resin. However, flexible wiring boards manufactured using known adhesives have the problem that if they are exposed to high temperatures in the subsequent soldering process, they will cause "blisters" and "peeling" in the adhesive layers. It was desired to improve the heat resistance of the agent.

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. A method has been proposed in which the adhesive film is sandwiched between a heat resistant film and a copper foil and thermocompression bonded. (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 heat-resistant film and the copper foil is maintained at a high temperature of about 260 to 280 ° C. and further 30 to 60 kg / cm. _It is necessary to carry out under a high pressure of about _{2, and} under such bonding conditions, it is extremely difficult to continuously laminate the heat resistant film and the copper foil using a pressure roll made of an organic resin, It was a problem in terms of practicality.

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) and tackiness, and after the process of laminating the copper foil and curing the adhesive layer, the heat-resistant film and various metal foils are suitably bonded together. It is an object of the present invention to provide a "heat-resistant adhesive that can be used as a bonding sheet exhibiting high adhesiveness at high temperature" that can obtain a laminate having excellent performance.

[0009]

The present invention comprises (A) trimellitic acid as a main component (preferably 60 mol%).
Above, especially 80 to 100 mol% is contained. ) Aromatic tricarboxylic acid component and diaminopolysiloxane as main components (preferably 30 mol% or more, particularly 40 to 80 mol%)
A general formula I obtained from

[Chemical 2]

[Wherein A is a divalent residue of the diamino compound excluding two amino groups (preferably 30 mol% or more,
In particular, 40 to 80 mol% is a divalent residue obtained by removing two amino groups of diaminopolysiloxane, and the rest is a divalent residue based on another diamino compound), and Ar is an aromatic group. Trivalent aromatic residue excluding three carboxyl groups of tricarboxylic acid (Ar is mainly 60%
The above is a trivalent benzene ring residue obtained by removing three carboxyl groups from trimellitic acid, and the rest is a trivalent aromatic residue based on other aromatic tricarboxylic acids. ) And Y represents hydrogen or a methyl group. ] The repeating unit represented by 80% or more (preferably 90-100)
%) Containing 100 parts by weight of soluble aromatic polyamideimide,

(B1) An aromatic tetracarboxylic acid component containing 2,3,3 ', 4'-biphenyltetracarboxylic acids as a main component, a diamine component containing diaminopolysiloxane as a main component, and a monoamine having an unsaturated group, or Terminal-modified imide siloxane oligomers 10 to 20 having a softening point of 300 ° C. or lower, obtained by reacting dicarboxylic acid
0 parts by weight (preferably 20 to 150 parts by weight),

(B2) Aromatic tetracarboxylic acid component containing 2,3,3 ', 4'-biphenyltetracarboxylic acid as a main component, aromatic diamine component, and monoamine or dicarboxylic acid having an unsaturated group are reacted. 10 to 200 parts by weight (preferably 20 to 150 parts by weight) of the terminal-modified imide oligomer having a softening point of 300 ° C. or lower, or

(B3) Bismaleimide-triazine resin 10 to 200 parts by weight (preferably 20 to 150 parts by weight) (C) Epoxy group-containing polyfunctional epoxy compound 5
80 parts by weight (preferably 10 to 50 parts by weight), and (D) epoxy curing agent (preferably epoxy compound 10)
0.01 to 90 parts by weight with respect to 0 parts by weight) is contained as a resin component.

The soluble aromatic polyamideimide (A) used as one of the resin components in the present invention contains, for example, trimellitic acid as a main component (preferably about 60 mol% or more, particularly 80 to 100). Aromatic tricarboxylic acid component (containing mol%) and diaminopolysiloxane as main components (preferably 80 mol% or more, particularly 90 to 90%).
Diamine component (containing 100 mol%), approximately equimolar,
It is a soluble aromatic polyamideimide obtained by polymerization in an organic polar solvent.

The above-mentioned aromatic polyamide-imide has an inherent viscosity (measurement concentration: 0.5 g / 100 ml solvent, solvent: N-methyl-2-pyrrolidone, measurement temperature: 30 ° C.).
Is preferably 0.2 to 3.0.

The trimellitic acids used in the production of the aromatic polyamideimide (A) and the aromatic tricarboxylic acids used together with the trimellitic acids are represented by the general formula II

[Chemical 3]

Alternatively, the general formula III

[Chemical 4] (However, in the general formulas II and III, Ar is a trivalent aromatic residue and R is hydrogen or a lower alkyl group.) The aromatic tricarboxylic acid or its monoester compound (general formula II) Alternatively, it may be an aromatic tricarboxylic acid anhydride (general formula III).

As the above Ar, for example,

[Chemical 5] And trivalent aromatic residues such as

As the aromatic tricarboxylic acids represented by the general formulas II and III, for example, 3,4,3'-trimellitic acid or an acid anhydride thereof or a monomethyl esterified product of the acid is a representative one. And 1,2,8-benzenetricarboxylic acid or an acid anhydride thereof, 1,2,4-, 1,4,5-,
Or 2,3,6-naphthalene tricarboxylic acid or an acid anhydride thereof, 3,4,4′-benzophenone tricarboxylic acid or an acid anhydride thereof, 3,4,4′-biphenyl tricarboxylic acid or an acid anhydride thereof, or , Monomethyl esterified products of those acids, and the like.

In the production of the aromatic polyamide-imide (A), in addition to the aromatic tricarboxylic acids, aromatic dicarboxylic acids are used as long as the characteristics of obtaining a high-molecular-weight aromatic polyamide-imide having excellent solubility are not impaired. Acids or aromatic tetracarboxylic acids are used together in a small ratio (per mol of aromatic tricarboxylic acid, aromatic dicarboxylic acid or aromatic tetracarboxylic acids 0.5 mol or less, particularly 0.2 mol or less). Good.

Examples of the aromatic dicarboxylic acid include terephthalic acid, 2-methylterephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid,
4,4'-diphenylmethanedicarboxylic acid, 4,4'-
Examples thereof include diphenyl sulfone dicarboxylic acid and 4,4′-benzophenone dicarboxylic acid.

Examples of the aromatic tetcarboxylic acids include biphenyltetracarboxylic acid or its acid dianhydride, diphenylethertetracarboxylic acid or its acid dianhydride, naphthalenetetracarboxylic acid or its acid dianhydride. You can

Examples of the diaminopolysiloxane used in the above-mentioned method for producing an aromatic polyamide-imide include those represented by the general formula IV

[Chemical 6] (However, in the formula, R ₀ represents a divalent hydrocarbon residue,
R ₁ , R ₂ , R ₃ and R ₄ represent a lower alkyl group having 1 to ₄ carbon atoms or a phenyl group, and p is 3 to 60, particularly 5 to 5.
Indicates an integer of 0. Suitable examples thereof include diaminopolysiloxanes represented by

In the diaminopolysiloxane represented by the general formula IV, R in the general formula IV has 2 to 6 carbon atoms, particularly 3 to R.
A divalent hydrocarbon residue consisting of five "plurality of methylene groups" or a phenylene group, wherein R _{1 to} R ₄ are methyl groups,
It is preferably a lower alkyl group having 1 to 5 carbon atoms such as an ethyl group or a propyl group, or a phenyl group, and further, p is preferably about 5 to 20, particularly preferably about 5 to 15.

Examples of the diamine component used in combination with the diaminopolysiloxane in the production of the above-mentioned aromatic polyamide-imide include hyphenyl diamine, diphenyl ether diamine, benzophenone diamine,
Diphenylsulfone-based diamine, diphenylmethane-based diamine, diphenylpropane-based diamine, 2,2-bis (phenyl) hexafluoropropane-based diamine, diphenylenesulfone-based diamine, di (phenoxy) benzene-based diamine, di (phenyl) benzene-based diamine,
2,2-bis (phenoxyphenyl) propane-based diamine, bis (phenoxyphenyl) sulfone-based diamine,
Two or more "aromatic rings (benzene rings, etc.)" such as di (phenoxyphenyl) hexafluoropropane-based diamine,
Particularly, "aromatic diamine compound having 2 to 5" can be preferably mentioned.

In the present invention, the terminal-modified imide siloxane oligomer (B
1) is, for example, an aromatic tetracarboxylic acid component, a diamine component containing diaminopolysiloxane as a main component, and
The monoamine or dicarboxylic acid having an unsaturated group is used as an acid anhydride group (or a pair of adjacent carboxyl groups) in each component.
Of the aromatic tetracarboxylic acid component and a diamine component having a diaminopolysiloxane component as a main component in an organic polar solvent. , To produce an amic acid oligomer having an amide-acid bond, and then reacting the amic acid oligomer with a monoamine or dicarboxylic acid having an unsaturated group,
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 of 140 to 250 ° C.

Terminal-modified imide siloxane oligomer (B
1) has a softening point of 300 ° C. or lower, particularly 40 to 250.
C. and the above logarithmic viscosity (measured concentration: 0.5 g / 1
00 ml solvent, solvent: N-methyl-2-pyrrolidone, measurement temperature: 30 ° C.) is 0.5 or less, especially 0.0
It is a low molecular weight oligomer having a molecular weight of about 1 to 0.4, and an end-modified imide siloxane oligomer having an unsaturated group at the end and having an imide bond in the molecule is preferable.

End-modified imide siloxane oligomer (B
1) is the general formula V or VI

[Chemical 7] (In the formula, Ar ₁ is a tetravalent aromatic residue obtained by removing four carboxyl groups of the aromatic tetracarboxylic acid compound,
Ar ₂ is a divalent residue obtained by removing two amino groups of the diaminopolysiloxane compound, and R ₅ is a monovalent organic residue obtained by removing one amino group of the monoamine compound having an unsaturated group. And R ₆ is a divalent organic residue obtained by removing two carboxyl groups of a dicarboxylic acid having an unsaturated group, and m and n are about 1 to 50, particularly about 1 to 30. Is an integer. It is preferable that it is the terminal modification imide siloxane oligomer shown by these.

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 1
The reaction is performed at a temperature of 00 ° 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 a high temperature of 140 to 250 ° C. Any material can be used as long as it can be obtained by the manufacturing method in which the heating is performed.

The terminal-modified imide oligomer (B2) has the general formula VII or VIII.

[Chemical 8] (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 ₅ and R ₆ , and m and n are the same as defined in the general formulas V and VI. It is preferable that it is the terminal modification imide oligomer shown by these.

The terminal-modified imide oligomer (B2) has a softening point of 300 ° C. or lower, especially 40 to 250 ° C., and an inherent viscosity of 0.5 or lower, especially 0.01 to 0.4. An oligomer having a low molecular weight, which has an unsaturated group at the terminal and has an imide bond in the molecule, is preferably an end-modified imide oligomer.

End-modified imide siloxane oligomer (B
1) and the aromatic tetracarboxylic acid component used in the method for producing the terminal-modified imide oligomer (B2),
2,3 ', 4'-biphenyltetracarboxylic acid or its acid dianhydride, or its acid ester compound, etc.
An aromatic tetracarboxylic acid component containing 3,3 ′, 4′-biphenyltetracarboxylic acid as a main component (80 mol% or more, particularly 90 mol% or more) is preferable.

The aromatic tetracarboxylic acid component used together with 2,3,3 ', 4'-biphenyltetracarboxylic acid as the aromatic tetracarboxylic acid component is 3,3', 4,4 '. -Biphenyltetracarboxylic acid or its acid dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid or its acid dianhydride, 3,
3 ', 4,4'-biphenyl ether tetracarboxylic acid or its acid dianhydride, bis (3,4-dicarboxyphenyl) benzene or its acid dianhydride, 2,2-bis (3,4-dicarboxy) Examples thereof include phenyl) propane and its acid dianhydride.

As the aromatic diamine used in the method for producing the terminal-modified imide oligomer (B2), the above-mentioned "aromatic diamine compound having two or more aromatic rings (benzene ring etc.), particularly 2 to 5" is used. It is preferable to use preferably, especially 1,4'-diaminodiphenyl ether, 1,
4-bis (4-aminophenoxy) benzene, 2,2-
Suitable examples include bis [4- (4-aminophenoxy) phenyl] propane and the like.

End-modified imide siloxane oligomer (B
1) or the monoamine compound having an unsaturated group used in the method for producing the terminal-modified imide oligomer (B2),
Propargylamine, 3-aminobutyne, 4-aminobutyne, 4-aminopentine, 5-aminopentine, 6-
“Aliphatic monoamine compound having an unsaturated group” such as aminohexyne, 4-amino-3-methylbutyne, allylamine, or m- or p-aminostyrene, m-amino-α-methylstyrene, 1-isopropenyl-3 −
"Aromatic monoamine compound having unsaturated group" with (2-aminoisopropyl) benzene, 3-aminophenylacetylene, 4-aminophenylacetylene and the like can be mentioned.

End-modified imide siloxane oligomer (B
1) or the dicarboxylic acid compound having an unsaturated group used in the method for producing the terminal-modified imide oligomer (B2) includes maleic acid, citraconic acid, nadic acid, itaconic acid, tetrahydrophthalic acid, or their acid anhydrides. ,
Suitable examples thereof include "unsaturated dicarboxylic acids having two carboxyl groups adjacent to each other" such as an esterified product of the acid.

The organic polar solvent used in the production of the aromatic polyamideimide (A), the terminal-modified imide siloxane oligomer (B1) or the terminal-modified imide oligomer (B2) is, for example, N, N-dimethylacetamide, N, N. -Adiamide acetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone and other amide solvents, sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethyl sulfolamide Such as a solvent containing a sulfur atom, cresol, phenol, a phenolic solvent such as xylenol, a solvent having an oxygen atom in the molecule such as acetone, methanol, ethanol, ethylene glycol, dioxane, and tetrahydrofuran. Pyridine, can be given other solvents such as tetramethylurea.

The above-mentioned terminal-modified imide siloxane oligomer (B1) or terminal-modified imide oligomer (B2)
Has an imidation ratio of 90% or more, particularly 95% or more, as measured by infrared absorption spectrum analysis, or an absorption peak relating to the amide-acid bond of the polymer is not substantially found in infrared absorption spectrum analysis, and the imide ring Substantially imidization rate of 10 where only absorption peak related to binding is seen
It is preferably 0%.

The bismaleimide-triazine resin (B3) used as one of the resin components in the present invention.
Is, for example, a known thermosetting resin composition having an imide group and a triazine ring, which is obtained from a bismaleimide component and a triazine monomer having a cyanate group or a prepolymer component, and is an acrylic acid ester or divinyl ester. It may be modified with 0 to 30% with benzene, styrene, triallyl isocyanate, etc., and in particular, "BT resin, trade name: BT3309T" manufactured by Mitsubishi Gas Chemical Co., Inc.
Etc. "can be mentioned suitably.

The polyfunctional epoxy compound (C) used in the heat-resistant adhesive of the present invention is a reaction product of an aromatic diamine and an epoxy compound such as epichlorohydrin [eg, a reaction product of metaxylenediamine and epichlorohydrin ( Multifunctional epoxy resin having four glycidyl groups, "Tetrad-" manufactured by Mitsubishi Gas Chemical Co., Inc.
X "etc.]], a reaction product of a diaminophenol compound and an epoxy compound such as epichlorohydrin (a polyfunctional epoxy resin having three glycidyl groups," ELM-100 "manufactured by Sumitomo Chemical Co., Ltd., etc.) Polyfunctional epoxy compound having at least one epoxy group ”, and a plurality of the various epoxy resins described above may be used in combination. In the present invention, the polyfunctional epoxy compound is
Those which are liquid at room temperature and have a solution viscosity of 10,000 centipoises or less, particularly 100 to 6000 centipoises, are preferable.

The epoxy hardener (D) used in the heat-resistant adhesive of the present invention includes imidazoles, tertiary amines, triphenylphosphines, dicyandiamides, hydrazines and aromatic diamines. Examples thereof include anionic polymerization type curing agents, polyaddition type curing agents such as polyphenols, organic peroxides and the like.

The above-mentioned epoxy curing agent can be used in any proportion, but the multifunctional epoxy resin 10
0.01 to 90 parts by weight, especially 0.0
It is preferable to use about 3 to 80 parts by weight.

The heat-resistant adhesive of the present invention comprises an aromatic polyamideimide (A), an end-modified imide siloxane oligomer (B1) or an end-modified imide oligomer (B2), a polyfunctional epoxy compound (C), and an epoxy curing agent. The resin component having a specific composition ratio of (D) may be a resin composition containing (90% by weight or more, particularly 95 to 100% by weight) as a main component, but all the resin components described above are It may be a solution composition of a heat-resistant adhesive which is uniformly dissolved in a suitable organic polar solvent, particularly at a concentration of 3 to 50% by weight, more preferably 5 to 40% by weight.

The solution composition of the above heat-resistant adhesive has a solution viscosity (30 ° C.) of 0.1 to 10000 poise, particularly preferably 0.2 to 5000 poise, more preferably 1 to 1000 poise. Preferably. Further, the solution composition has a softening point (a temperature at which softening starts on a hot plate) of a composition containing only an uncured resin component is 150.
℃ or less, especially 120 ℃ or less, more preferably 100 ℃
The following is preferable, 130 to 400 ° C., especially 1
It is preferably one that can be cured by heating to a curing temperature of 40 to 350 ° C.

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

The solution of the heat-resistant adhesive is applied to the heat-resistant film surface of a suitable metal foil, aromatic polyimide film, aromatic polyester or the like, and the coating layer is 60 to 14
The solvent was substantially removed by drying at a temperature of 0 ° C. for 0.5 to 100 minutes (preferably the residual solvent ratio was 1).
Sheets of uncured heat-resistant adhesive (up to wt%) (dry film or bonding sheet having a thickness of about 1 to 200 μm) can be formed.

The above-mentioned bonding sheet has suitable flexibility, and can be wrapped around a paper tube or punched by punching.
A laminated sheet in which a sheet layer of an uncured heat-resistant adhesive is formed on a peelable film and a heat-resistant film for a transfer destination are superposed on each other and heated to a temperature of about 20 to 140 ° C. It is also possible to transfer the sheet layer of the heat-resistant adhesive onto the heat-resistant film for transfer destination by passing it between the laminate rolls.

In order 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, a heat resistant adhesive film or sheet is used. The heat resistant film and the metal foil from 100 to
By laminating at a temperature of 180 ° C. and then heating the laminated one at a temperature of 80 to 350 ° C. for 1 to 30 hours to heat-cure the adhesive layer,
The above-mentioned laminated body can be easily and continuously manufactured.

The heat-resistant adhesive of the present invention is joined 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

[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 polyamideimide, an end-modified imide siloxane oligomer or an end-modified imide oligomer, which is _{added to the} solvent at a concentration of 0.5 g / 100 ml of a solvent.
It is a value calculated by the following calculation formula by uniformly dissolving it in methyl-2-pyrrolidone to prepare a solution, 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 sandwiched between aromatic polyester films (PET) and measured by laminating between rolls at 40 ° C., and indicates that they are sufficiently adhered, and x indicates that they are spontaneously peeled. Then, the adhesive strength of the bonding sheet, using a tensile tester manufactured by Intesco,
It is the result measured by performing a T-type peel test at a peel speed of 50 mm / min.

Reference Example 1 [Production of Aromatic Polyamideimide A] In a 2 liter autoclave equipped with a thermometer, a distillation outlet connected to a vacuum system, and a stirrer, 88.4 g (0.
2 moles), diamino polysiloxane represented by the general formula _{IV (R: -CH 2 CH 2} CH 2 -, R 1 ~R 4: -CH
₃ , p: 9) 105.6 g (0.12 mol), 2,2-
32.84 g (0.08 mol) of bis [4- (4-aminophenoxy) phenol] propane and sulfolane 68
0g was charged.

The monomer component in the reaction solution was heated in sulfolane to a temperature of 270 ° C., and stirred at this temperature for 2 hours to carry out polymerization and polymerization while continuously distilling a part of produced water and sulfolane from the distillation outlet. Imidization was performed to prepare a solution containing 25% by weight of soluble aromatic polyamideimide A and uniformly dissolved.

The aromatic polyamideimide A is a repeating unit represented by the general formula I (A in the general formula I is a residue based on the diaminopolysiloxane represented by the general formula IV, and is therefore represented by the general formula I. Y in which is a hydrogen atom) was a polymer, the imidization ratio was substantially 100%, and the inherent viscosity (30 ° C.) was about 0.7.

Reference Example 2 [Production of terminal-modified imide siloxane oligomer B1] In a glass flask having a capacity of 500 ml, 2, 3,
3 ', 4'-biphenyltetracarboxylic dianhydride (a
-BPDA) 11.77 g (0.04 mol), general formula I
A diaminopolysiloxane represented by V (R ₀ : -CH _{2
CH 2 CH 2 -, R 1} ~R 4: -CH 3, p: 9) 5
2.8 g (0.06 mol), dimethylacetamide (D
258 g of MAc) was charged, and the mixture was stirred in a nitrogen stream at 50 ° C. for 1 hour to form an amic acid oligomer.
The reaction solution was heated to about 165 ° C. and stirred at that temperature for 3 hours to form an imide oligomer having an amino group at the terminal.

After cooling the reaction solution to 50 ° C., 6.87 g (0.07 mol) of maleic anhydride and 35 of toluene.
g, the temperature of the reaction solution was raised to about 160 ° C., toluene was removed together with water to generate toluene, and the mixture was stirred at that temperature for 3 hours for imidization to give a terminal having a maleic acid-based unsaturated group. Modified imide siloxane oligomer (B1
Component, average degree of polymerization p: 2) was generated.

Reference Example 3 [Production of terminal-modified imide oligomer B2] 2, 3, 3 ', 4'in a glass flask having a capacity of 500 ml.
-Biphenyltetracarboxylic dianhydride (a-BPD
A) 14.71 g (0.05 mol), 1.3-bis (4
-Aminophenoxy) benzene 29.23 g (0.1 mol), maleic anhydride 11.77 g (0.12 mol) and DMAc 176 g were used in the same manner as in Reference Example 2 except that maleic acid-based terminals were used. Terminal-modified imide oligomer having a saturated group (B2 component, average degree of polymerization p:
1) was generated.

Example 1 [Preparation of Solution Composition of Heat-Resistant Adhesive] In a glass flask having a volume of 1 liter, 60 parts by weight of the aromatic polyamideimide (A) produced in Reference Example 1 was used, and in Reference Example 2 End-modified imide siloxane oligomer (B1) 30 produced
Parts by weight, polyfunctional epoxy resin (Shell Petrochemical Co., Ltd.)
Made, trade name: Epicoat 152) 10 parts by weight, phenol novolac resin 22 parts by weight, curing agent: 2-phenylimidazole (manufactured by Shikoku Kasei Co., Ltd., trade name: 2PZ)
0.01 g and 200 parts by weight of tetrahydrofuran (THF) were charged and stirred at room temperature (25 ° C.) for about 2 hours to prepare a uniform heat-resistant adhesive solution composition (viscosity at 25 ° C .: 5 poise). This solution composition maintained a uniform solution state even when left at room temperature for 1 week.

[Manufacture of Laminated Body Using Heat-Resistant Adhesive] The above-mentioned solution composition of heat-resistant adhesive was applied onto a polyimide film (manufactured by Ube Industries, Ltd., trade name: UPILEX S type, thickness 75 μm) with a doctor blade. At a thickness of 125 μm, and then the coating layer is applied at 60 ° C. for 10 minutes for 1 minute.
A sheet layer of a heat-resistant adhesive composition having a thickness of about 25 μm on a polyimide film, which was dried by heating at 00 ° C. for 10 minutes and further at 120 ° C. for 10 minutes (bonding sheet of uncured dried adhesive composition). Layer, softening point: 40 ° C.).

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.
The pressure-bonded laminate was heated at 80 ° C. for 2 hours, 100 ° C. for 2 hours, 120 ° C. for 1 hour, 140 ° C. for 1 hour, and 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 2-3 and Comparative Example 1 Terminal-modified imide siloxane oligomer (B1) prepared in Reference Example 2, terminal-modified imide oligomer (B2) prepared in Reference Example 3, or bismaleimide-triazine Resin (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name: BT33)
09T), the epoxy compound and the curing agent shown in Table 1 are used, and the composition of each component is
A heat-resistant adhesive solution composition was prepared in the same manner as in Example 1 except that the components shown in the table were used. further,
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 1.

[0063]

[Table 1]

In Table 1, in the epoxy compound column, "Epicoat 152" is Shell Petrochemical, "Tetrad-X" and "EL-100" are Mitsubishi Gas Chemical's multifunctional epoxy resins, and curing agent column. "2-PZ" is 2-
Phenylimidazole is shown, and "H-1" is a Meiwa Kasei phenol novolac type curing agent.

[0065]

The function and effect of the present invention are as follows:
(A) Aromatic polyamide imide, (B1) Terminal-modified imide siloxane oligomer, (B2) Terminal-modified imide oligomer or (B3) Bismaleimide-triazine resin, (C) Polyfunctional epoxy resin, and (D) Epoxy curing It contains a resin component composed of an agent.

The heat-resistant adhesive of the present invention can easily form a thin uncured bonding sheet layer (adhesive layer) by coating the solution composition on a supporting film and drying at a relatively low temperature. It can be formed, and the thin bonding sheet layer has sufficient flexibility, and there is no problem even if the thin 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 bond a laminate (joining) of the heat resistant film and copper foil at a relatively low temperature, and workability is improved. Is a good one.

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Taiji Narahara 3-10 Nakamiyakitamachi, Hirakata-shi, Osaka Ube Industries Ltd. Hirakata Laboratory

Claims (1)

[Claims] 1. A general formula I obtained from (A) an aromatic tricarboxylic acid component containing trimellitic acid as a main component and a diamine component containing diaminopolysiloxane as a main component. (However, A represents a divalent residue excluding two amino groups of a diamino compound, Ar represents a trivalent aromatic residue excluding three carboxyl groups of an aromatic tricarboxylic acid, and , Y represents hydrogen or a methyl group.) 100 parts by weight of a soluble aromatic polyamideimide having 80% or more of the repeating unit represented by the formula (B1) 2,3,3 ′, 4′-biphenyltetracarboxylic acid Aromatic tetracarboxylic acid component as the main component,
10 to 200 parts by weight of a terminal-modified imide siloxane oligomer having a softening point of 300 ° C. or lower, obtained by reacting a diamine component containing diaminopolysiloxane as a main component and a monoamine or dicarboxylic acid having an unsaturated group (B2) 2 , 3,3 ', 4'-biphenyltetracarboxylic acid-based aromatic tetracarboxylic acid component,
End-modified imide oligomers 10 to 2 having a softening point of 300 ° C. or less obtained by reacting an aromatic diamine component and a monoamine or dicarboxylic acid having an unsaturated group
00 parts by weight, or (B3) bismaleimide-triazine resin 10 to 2
00 parts by weight (C) Epoxy group-containing polyfunctional epoxy compound 5
80 parts by weight, and (D) epoxy curing agent is contained as a resin component, a heat resistant adhesive.